Liquid laundry compositions

Abstract

A liquid laundry composition comprising: (i) 1 to 60 wt% of one or more surfactants selected from non-soap anionic surfactants, nonionic surfactants and mixtures thereof; and (ii) 0.05 to 10 wt% of an amphoteric modified oligopropyleneimine ethoxylate having the following formula (I), wherein E is a residue corresponding to the formula (RO): n -R' (I) an ethoxy side chain, wherein the R unit is ethylene; n has an average value of 5 to 50, preferably 10 to 40; the R' units are each independently selected from hydrogen and SO3 ‑ , wherein at least 30%, preferably at least 50%, of the R' units are SO3 ‑ ; Each Q unit is independently selected from C1-C4 alkyl, H and a free electron pair, wherein at least 50%, preferably at least 80%, more preferably at least 90% of the Q units are C1-C4 alkyl; and x is 1 to 3. #imgabs0#

Description

Technical Field

[0001] The present invention relates to liquid laundry compositions comprising specific amphoteric modified oligopropyleneimine ethoxylates and the use of said compositions for removing soils, especially particulate soils, from fabrics. Background Art

[0002] Laundry detergents remain an area of ​​active research and development. Today, consumers are becoming more aware of environmental impact and greenhouse gas emissions, so more and more are turning to lower wash temperatures and shorter cycles. At the same time, they are seeking laundry products with environmental credentials that can provide improved cleaning performance under those milder wash conditions.

[0003] Since laundry detergents usually contain surfactants, one way to meet the above needs is to introduce high weight efficiency ingredients that can work in conjunction with those surfactants. These ingredients can partially replace surfactants and contribute to the cleaning performance of residual surfactants. Therefore, more clothes can be cleaned with the same amount of active chemicals or less chemicals are needed to remove the same amount of dirt and stains. Suitable ingredients that have been widely studied are polymers with cleaning functions, such as anti-redeposition polymers that can help surfactant systems remove dirt from fabrics.

[0004] WO03 / 015906A1 relates to novel oligomeric hydrophobic dispersants and laundry detergent compositions comprising oligomeric dispersants. It describes in one embodiment suitable dispersants for use in the dispersant system of the invention, including polyalkyleneimines.

[0005] EP 1 865 050 B1 describes a composition suitable for treating soiled fabrics comprising a hypohalite bleach and a soil suspending agent selected from the group consisting of ethoxylated diamines, ethoxylated polyamines, ethoxylated amine polymers and mixtures thereof.

[0006] EP2961821B1 describes the use of alkoxylated polypropyleneimines selected from linear polypropyleneimines with a molecular weight Mn in the range of 300 to 4000 g / mol for laundry care. It also describes a detergent composition comprising at least one of said polymers, at least one anionic surfactant and at least one builder selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates and polycarboxylates. A process for preparing said laundry detergent composition is also described.

[0007] Despite all of the above prior art, there is a continuing need to improve the effectiveness of anti-redeposition polymers in removing soils, especially particulate soils. In addition, it has been found that the inclusion of such anti-redeposition polymers can reduce the viscosity of the resulting liquids, resulting in reduced consumer acceptance, thus requiring the inclusion of additional viscosity-boosting technology.

[0008] It is therefore an object of the present invention to provide a liquid laundry composition comprising an anti-redeposition polymer which provides improved soil removal. Another object of the present invention is to provide a liquid laundry composition having improved soil removal without compromising the viscosity characteristics of the composition. Yet another object is to provide such a composition with reduced overall chemical levels.

[0009] Surprisingly, it has been found that specific anti-redeposition polymers, namely amphiphilically modified oligopropyleneimine ethoxylates, can provide the desired improvement in soil removal when applied from a laundry liquor. Furthermore, the benefits can be achieved without compromising product viscosity. Summary of the invention

[0010] In a first aspect of the present invention, there is provided a liquid laundry composition comprising: (i) 1 to 60 wt% of one or more surfactants selected from non-soap anionic surfactants, nonionic surfactants and mixtures thereof; and (ii) 0.05 to 10 wt% of an amphoteric modified oligopropyleneimine ethoxylate having the following formula (I):

[0011]

[0012] Where E is the formula corresponding to -(RO) n -R'(I) an ethoxy side chain, wherein the R unit is ethylene; n has an average value of 5 to 50, preferably 10 to 40; the R' units are each independently selected from hydrogen and SO3 - , wherein at least 30%, preferably at least 50%, of the R' units are SO3 - ; Q units are each independently selected from C1-C4 alkyl, H and a free electron pair, wherein at least 50%, preferably at least 80%, more preferably at least 90% of the Q units are C1-C4 alkyl; and x is 1 to 3.

[0013] In a second aspect of the present invention, there is provided the use of a composition according to the first aspect of the present invention for removing dirt from fabrics. There is also provided a method for removing dirt from fabrics, comprising the following steps in sequence: (a) diluting a dose of a composition according to the first aspect of the present invention to obtain a wash liquor, wherein the dose is 10 to 100 g; and (b) washing fabrics with the wash liquor thus formed. Preferably, the dirt is particulate dirt.

[0014] In a third aspect of the present invention, there is provided a product comprising a composition according to the first aspect of the present invention, wherein the composition is contained in a multi-dose package, preferably a multi-dose package with dosing means, or in a unit dose package made of a polymer film, the polymer film being adapted to be insoluble before addition to water.

[0015] These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. DETAILED DESCRIPTION

[0016] Any feature of one aspect of the present invention can be used in any other aspect of the present invention. Any feature described as "preferred" should be understood as particularly preferably combined with one or more further preferred features. Herein, any feature of a particular embodiment can be used in any other embodiment of the present invention. The word "comprising" is intended to mean "including", but not necessarily "consisting of" or "consisting of". In other words, the steps or options listed do not need to be exhaustive. The examples given in the following description are intended to illustrate the present invention rather than to limit the present invention. Unless otherwise stated, all percentages are weight percentages based on the total weight of the composition. Except in the operating and comparative examples, or where otherwise clearly stated, all numbers indicating the amount of material or reaction conditions, the physical properties of the material and / or the use in this specification should be understood to be modified by the word "about". Unless otherwise stated, a numerical range expressed in the form of "x to y" should be understood to include x and y. When multiple preferred ranges are described in the format of "x to y" for a particular feature, it should be understood that all ranges combining different endpoints are also covered.

[0017] The oligopropylene imine ethoxylate of the present invention is amphoteric and conforms to the following formula (I):

[0018]

[0019] Where E is the formula corresponding to -(RO) n -R'(I) an ethoxy side chain, wherein the R unit is ethylene; n has an average value of 5 to 50; the R' units are each independently selected from hydrogen and SO3 - , where at least 30% of the R' units are SO3 - ; The Q units are each independently selected from C1-C4 alkyl, H and a free electron pair, wherein at least 50% of the Q units are C1-C4 alkyl; and x is 1 to 3.

[0020] The counter ion of the quaternized nitrogen atom in formula (I) may be SO3 -Ions or alkyl sulfate ions (C1-C4 monoalkyl sulfate). It will be appreciated by those skilled in the art that additional anions and cations may be present with the oligomers conforming to formula (I) after the optional neutralization and / or optional water dilution steps during the manufacturing process.

[0021] Preferably, at least 80% of all Q units are C1-C4 alkyl. More preferably, at least 90% of all Q units are C1-C4 alkyl. Most preferably, 93% to 97% of all Q units are C1-C4 alkyl.

[0022] Preferably, at least 50% of the R' units are SO3 - .

[0023] Preferably, Q = C1-C4 alkyl and R' = SO3 - The ratio is 1:1 to 1:0.8.

[0024] Preferably, x is 2 or 3.

[0025] Preferably, at least 90% of all Q units are methyl and / or x is 2 or 3.

[0026] Preferably, n has an average value of 10-40, more preferably 15-30.

[0027] Preferably, x is 2, and / or n has an average value of from 15 to 30, and / or at least 90% of all Q units are methyl groups.

[0028] In some preferred embodiments, x=1, 2 or 3, at least 80% of the Q units are C1-C4 alkyl, and Q=C1-C4 alkyl and R'=SO3 - The ratio is 1:1 to 1:0.8.

[0029] In a further preferred embodiment, at least 90% of all Q units are methyl, x is 2 or 3, and Q = methyl and R' = SO3 - The ratio is 1:1 to 1:0.8.

[0030] In a still further preferred embodiment, x is 2, at least 90% of all Q units are C1-C4 alkyl, preferably C1, n has an average value of 15 to 30, and Q = C1-C4 alkyl R' = SO3 - 1:1 to 1:0.8.

[0031] Mixtures of any of the above materials may also be used.

[0032] Preferably, the liquid laundry composition according to the present invention comprises an amphoteric modified oligomeric polypropylene imine ethoxylate according to formula (I) (wherein x=2) and one or more isomeric compounds of the following formula (II)

[0033]

[0034] Where E is the formula corresponding to -(RO) n -R'(I) an ethoxy side chain, wherein the R unit is ethylene; n has an average value of 5 to 50; the R' units are each independently selected from hydrogen and SO3 - , wherein at least 30%, preferably at least 50%, of the R' units are SO3 - ; and Q units are each independently selected from C1-C4 alkyl, H and a free electron pair, wherein at least 50%, preferably at least 80%, more preferably at least 90% of the Q units are C1-C4 alkyl.

[0035] Preferably, in the composition according to the invention, the molar ratio of the amphiphilically modified oligopropyleneimine ethoxylate of formula (I) to the isomeric compound of formula (II) is at least 10:1.

[0036] Preferably, the composition according to the invention further comprises alkali metal and / or amine sulfates. Typical examples are amine sulfates, such as alkanolamine sulfates.

[0037] The amphiphilically modified oligopropyleneimine ethoxylates according to formula (I) can be prepared by the following processes in sequence: (a) providing an amine selected from ammonia, 1,3-propylenediamine, bis-(3,3'-aminopropyl)amine, bis-(3,3'-aminopropyl)-1,3-propylenediamine and mixtures thereof, (b) optionally cyanoethylating the amine with acrylonitrile in a ratio of 100:1 to 1:2.5, preferably 10:1 to 1:2.5, more preferably 3:1 to 1:2.1, followed by hydrogenation to obtain oligopropyleneimine having 2, 3 and 4 repeating units, (c) optionally purification of the oligopropyleneimine from step (b), (d) ethoxylation of the amine and / or oligopropyleneimine from step a, b or c, and (e) at least partial quaternization and transsulfation with di-C1-C4-alkyl sulfate.

[0038] Preferably, the purification step (c) is carried out to obtain oligopropyleneimines with 2, 3 and 4 repeating units and mixtures thereof in a purity of at least 80 wt%, preferably at least 90 wt%. Preferably, the ethoxylation step (d) is carried out in two sub-steps, namely (d.1) the conversion of up to 1 mol of EO per NH functional group, followed by (d.2) the conversion of more EO under basic catalysis. Preferably, the quaternization in step (e) is carried out with dimethylsulfate. Preferably, the transsulfation in step (e) is carried out with sulfuric acid as catalyst. Preferably, the transsulfation in step (e) is carried out quantitatively (>=80%) and slightly cationic or net neutral oligomers are obtained.

[0039] The process may further comprise a subsequent step of neutralizing the sulfuric acid with a base selected from alkali metal hydroxides and amines. Preferably, a base selected from amines, more preferably alkanolamines or aqueous solutions thereof may be used.

[0040] Process steps (a) to (c) can be performed via route A or route B.

[0041] Route A: As described in CN107311891, 1 equivalent of acrylonitrile can be added dropwise to an excess of 1,3-propylenediamine, bis-(3,3'-aminopropyl)amine or bis-(3,3'-aminopropyl)-1,3-propylenediamine or a mixture thereof (up to 100 equivalents) (optionally dissolved in a solvent) in a reaction vessel at a temperature of 5°C to 80°C. After the addition is complete, the reaction can be stirred at a specified temperature until the starting material is completely consumed and then cooled to room temperature. After optional purification, the crude mixture can be subjected to hydrogenation in a pressure reactor catalyzed by a [Cu], [Co], [Ni], [Pd], [Pt] or [Ru] catalyst, as described in DD238043 and / or JP08333308 and / or WO2018046393, under elevated hydrogen pressure and optional ammonia pressure, with or without a solvent. During the hydrogenation, the temperature may be between 70° C. and 200° C., preferably between 70° C. and 150° C., and the hydrogen pressure between 1 and 250 bar, preferably between 50 and 250 bar. The catalyst may be removed, for example, by filtration, and the volatiles may be removed under reduced pressure. The obtained mixture of the desired oligomeric amino compounds may then be separated in the next step by distillation under reduced pressure (<1 bar) to produce the purified target compound, bis-(3,3′-aminopropyl)amine, bis-(3,3′-aminopropyl)-1,3-propylenediamine or tris-(3,3′,3″-aminopropyl)-1,3-propylenediamine.

[0042] Route B: As described in CN102941160 and / or WO9214709, acrylonitrile (up to 2.5 equivalents) can be added dropwise to 1 equivalent of ammonia, 1,3-propylenediamine, bis-(3,3'-aminopropyl)amine or bis-(3,3'-aminopropyl)-1,3-propylenediamine, or a mixture thereof (optionally dissolved in a solvent) in a reaction vessel at a temperature of 5°C to 80°C. After completion of the addition reaction, the reaction can be stirred at a specified temperature until the starting material is completely consumed and then cooled to room temperature. After optional purification, the crude mixture can be subjected to hydrogenation in a pressure reactor catalyzed by a [Cu], [Co], [Ni], [Pd], [Pt] or [Ru] catalyst under elevated hydrogen pressure and optional ammonia pressure, with or without a solvent, as described in DD238043 and / or JP08333308 and / or WO2018046393. During the hydrogenation, the temperature may be between 70° C. and 200° C., preferably between 70° C. and 150° C., and the hydrogen pressure between 1 and 250 bar, preferably between 50 and 250 bar. The catalyst may be removed, for example, by filtration, and the volatiles may be removed under reduced pressure. The obtained mixture of the desired oligomeric amino compounds may then be separated in the next step by distillation under reduced pressure (<1 bar) to produce the purified target compound, bis-(3,3′-aminopropyl)amine, bis-(3,3′-aminopropyl)-1,3-propylenediamine or tris-(3,3′,3″-aminopropyl)-1,3-propylenediamine.

[0043] The crude mixture according to route (A) or (B) contains mainly (>50 mol%) linear oligoamines, preferably more than 70 mol%, more preferably more than 80 mol% linear oligoamines. Preferably, the crude mixture according to route (A) or (B) is purified by distillation to remove any impurities from monomers, other oligomers or branched structures and branched isomers, respectively, to obtain a linear target compound, bis-(3,3'-aminopropyl)amine, bis-(3,3'-aminopropyl)-1,3-propylenediamine or tris-(3,3',3"-aminopropyl)-1,3-propylenediamine or a mixture thereof, with a purity of at least 80 wt%, more preferably at least 90 wt% and even more preferably >95 wt%. In one embodiment, the oligoamines may additionally contain isomeric compounds, which after ethoxylation and zwitterionic modification correspond to formula (II) as described above.

[0044] Step (d) of the process can be carried out as follows. In the first step (i) of the process step (d), ethylene oxide is added in an amount of 0.2 to 1.0 ethylene oxide units per NH group of the oligopropylene imine (PPI), preferably 0.5 to 0.99, more preferably 0.6 to 0.95 ethylene oxide units per NH group of the oligopropylene imine (PPI), even more preferably 0.70 to 0.95 ethylene oxide units per NH group of the oligopropylene imine (PPI) (low hydroxyethylation). In a preferred embodiment, the minimum amount of ethylene oxide units / NH groups added in step (i) is at least the same as or higher than the amount of basic catalyst C added subsequently in step (ii) to prevent the formation of polyethylene glycol via direct reaction of catalyst C with ethylene oxide during step (ii). Preferably, the sum of the amount of ethylene oxide EO added in steps (i) and (ii) is within the range of 5-50 ethylene oxide units / NH groups of low polypropylene imine (PPI), more preferably 10-40 ethylene oxide units / NH groups of low polypropylene imine (PPI), and further preferably 15-30 ethylene oxide units / NH groups of low polypropylene imine (PPI). Preferably, the first step (i) of process step (d) is carried out in the absence of a basic catalyst. Preferably, water can be added in step (i). In one embodiment, the second step (ii) of step (d) is carried out in the presence of a basic catalyst. Suitable alkalis are, for example, LiOH, NaOH, KOH, CsOH and mixtures thereof, sodium alkoxides or potassium alkoxides such as potassium methoxide (KOCH3), potassium tert-butoxide, sodium methoxide (NaOCH3), sodium n-hexanolate and sodium ethoxide. Other examples of catalysts are alkali metal hydrides and alkaline earth metal hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Preferred are alkali metal hydroxides, further preferred are potassium hydroxide and sodium hydroxide, and alkali metal alkoxides, further preferred are potassium methoxide (KOCH3) and sodium methoxide (NaOCH3). Potassium hydroxide and potassium methoxide (KOCH3) are particularly preferred. The typical amount of base (e.g. KOH) used relative to the oligopropylene imine ethoxylate (EPPI) is 0.02-10 wt%, in particular 0.05-1 wt%. In a preferred embodiment, the alkaline catalyst C is used only in the second step (ii) and is selected from alkaline catalysts containing alkaline earth metals. A particularly preferred alkaline catalyst is KOH; KOH can be used as an aqueous solution. In one embodiment, the alkaline catalyst C is added in an amount of 0.05 to 0.3 wt%, preferably 0.15 to 0.25 wt%, relative to the ethoxylated oligopropylene imine (EPPI).

[0045] In one embodiment, the temperature during the first step (i) of step (d) is in the range of 90°C to 160°C, preferably 100°C to 150°C, more preferably 110°C to 140°C. In one embodiment, the temperature during the second step (ii) of step (d) is in the range of 100°C to 180°C, preferably 120°C to 160°C, more preferably 120°C to 145°C. During the alkoxylation step, higher temperatures than specified above are also possible, but not preferred, as they generally lead to (more) colored products. Preferably, the first step (i) of step (d) can be carried out at a total pressure of up to 15 bar, preferably up to 10 bar, for example 1 to 6 bar. Preferably, the second step (ii) of step (d) can be carried out at a total pressure of up to 15 bar, preferably up to 10 bar, for example 2 to 10 bar. Preferred containers for carrying out the reaction are autoclaves and tubular reactors. The reaction during the second step (ii) of step (d) can be interrupted at different intermediate stages (ie degrees of alkoxylation) and can be continued with or without addition of further catalyst.

[0046] The product obtained after step (ii) of step (d), ie ethoxylated oligopropyleneimine (EPPI), may be treated with a bleaching agent. The bleaching agent is preferably selected from borates, hypochlorites, borohydrates and hydrogen peroxide.

[0047] The quaternization and transsulfation step (e) can be a combined process based on the quaternization of the amino groups in the EPPI backbone and the sulfation of the terminal hydroxyl moieties of the polyethylene oxide side chains. In a more general perspective, the quaternization and transsulfation step (e) comprises a sub-step (e1) of forming a sulfated species (=quaternization) and a sub-step (e2) of providing a controlled sulfation of one or more hydroxyl moieties (=transsulfation). The first required sub-step (e1) of the process can be carried out under alkaline or near neutral pH conditions. The second sub-step (e2) of the process can be carried out under acidic conditions.

[0048] Sub-step (e1) (quaternization):Preferably 0.5-1.0 equivalents, more preferably 0.8-0.99 equivalents, most preferably 0.9-0.99 equivalents of a sulfating agent react with a tertiary amino group of the ethoxylated oligopropylene imine to form a quaternary ammonium ion in the backbone of the oligoamine and an equivalent amount of a sulfated substance. If desired, the process can be carried out in the presence of a solvent, preferably a non-reactive solvent such as toluene, glycol dimethyl ether or diglycol dimethyl ether can be used. According to the present invention, the preferred sulfating agent is a dialkyl sulfate, preferably a di-C1-C4-alkyl sulfate, more preferably a di-C1-C2-alkyl sulfate, and most preferably dimethyl sulfate. Sub-step (e1) is carried out under alkaline or near pH neutral conditions at a temperature of 0°C to 180°C, preferably 40°C to 100°C, and even more preferably 50°C to 90°C. The reaction during exotherm can be controlled by any suitable means, for example by cooling the reaction vessel or by providing a reflux condenser.

[0049] Sub-step (e2) (transsulfation) : 1 equivalent of sulfated substance is required for each hydroxyl moiety to be sulfated. The number of sulfated substances is the same as the number of quaternary ammonium ions in the oligoamine backbone. Depending on the degree of conversion during the transsulfation step, the product obtained after substep (e2) is an amphiphilically modified polymer having (i) a net zero charge (= neutral polymer), i.e. the same number of quaternary ammonium ions and sulfated hydroxyl groups in the oligoamine backbone in case of complete (100%) conversion of the sulfated substance during the transsulfation step; or (ii) a net positive charge (= slightly cationic polymer), i.e. a slightly higher number of quaternary ammonium ions in the oligoamine backbone compared to sulfated hydroxyl groups in case of only partial (<100%) conversion during the transsulfation step. In order to control the degree of conversion during the transsulfation step, the formulator can remove the alcohol formed as a by-product, preferably a C1-C4-alcohol, most preferably methanol (depending on the type of di-C1-C4-alkyl sulfate used in step (e1). In fact, the relative amount of alcohol by-product removed can be used as a tool to control the degree of conversion of the transsulfation step. Any method convenient to the formulator can be used, such as distillation, absorption into molecular sieves, crystallization or precipitation, preferably distillation. In many cases, it is preferred to remove the by-product alcohol during the reaction, preferably by distillation.

[0050] In case of incomplete conversion (<100%) of the sulfated species during the transsulfation step, the final product after substep (e2) is generally obtained as an internal zwitterion with a potential additional cationic charge. In case of incomplete conversion during the transsulfation step, the counterion of the quaternized nitrogen atom is SO3 resulting in the formation of an internal zwitterion. - ions and potentially additional alkyl sulfate ions (C 1-4 Monoalkyl sulfate), preferably methyl sulfate ion.

[0051] Substep (e2) can be carried out under acidic conditions. Suitable acids are especially sulfuric acid, hydrochloric acid, methanesulfonic acid or Lewis acid (e.g. boron trifluoride). Sulfuric acid is preferably used. Acid can be added in any amount sufficient to form the desired product, however, the process is carried out at a pH of less than about 6, preferably less than about 4, more preferably less than about 3 and most preferably at a pH of about 2. In fact, an acid level of about 0.01-1 molar ratio is preferred relative to ethoxylated oligopropylene imine. The catalyst can be introduced in any manner convenient to the formulator, however, good mixing should be utilized. Alternatively, an acid can be generated in situ by adding an excess of a sulfating agent and reacting the excess of the sulfating agent with a limited proton source, especially water. Substep (e2) of the process of the present invention can be carried out at a temperature of 0°C to 200°C, preferably 40°C to 150°C, and even more preferably 70°C to 120°C. The reaction during exothermicity can be controlled by any suitable means, for example by cooling the reaction vessel or by providing a reflux condenser. Besides the conversion of the hydroxyl groups into sulfate groups from the transsulfation process (ie via the di-C1-C4-alkyl sulfates employed), the use of sulfuric acid can lead to an additional sulfation to a lesser extent of the hydroxyl groups of the ethoxylated oligopropyleneimine as a side reaction.

[0052] The final product after sub-step (e2) can be further purified to remove volatile by-products and / or acidic catalysts, preferably sulfuric acid, or can be separated as a mixture. Volatile by-products (e.g., 1,4-dioxane) can be removed, for example, by vacuum distillation or stripping. In the case where the acidic catalyst is not removed from the final product after sub-step (e2), the mixture can be separated as is or the acidic catalyst can be neutralized. Preferably, the acidic catalyst is not removed, but neutralized. Any suitable base can be used to neutralize the acidic substance, especially ammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide or amine. Lithium hydroxide, sodium hydroxide, potassium hydroxide or amine are preferably used, and even more preferably sodium hydroxide, alkanolamine or its aqueous solution. Preferably, alkanolamine is used for the neutralization of the acidic catalyst. If the acid used is sulfuric acid, the sulfate of the alkanolamine is formed, and if an aqueous solution of an alkali is used, the amphiphilic modified oligopropylene imine ethoxylate of formula (I) of the present invention is finally obtained in a mixture of sulfate and water that further comprises the alkanolamine.

[0053] The weight average molecular weight (determined by GPC, see experimental part) of the finally obtained amphiphilic modified oligopropyleneimine ethoxylate of formula (I) can be 1000-20000 g / mol, preferably 1500-15000 g / mol, more preferably 2000-10000 g / mol, most preferably 2500-8000 g / mol.

[0054] The final product after substep (e2) (if applicable, after removal or neutralization of the acidic catalyst) can be mixed with water in a weight ratio of 100:1-1:100. Preferably, the final product after substep (e2) is mixed with 1 to 80 wt% of water, more preferably 1 to 60 wt% of water, even more preferably 5 to 50 wt% of water, most preferably 10 to 40 wt% of water to reduce viscosity and improve handling. In this article, all weight percentages of water are relative to the total weight of the mixture.

[0055] The optional post-treatment step may also include adjusting the pH of the final product, in particular if the product is obtained as an aqueous solution. Any suitable base or acid can be used to adjust the pH. Preferably, sodium hydroxide, potassium hydroxide or an amine is used as a base; sulfuric acid, hydrochloric acid or methanesulfonic acid is used as an acid. In one embodiment of the present invention, an alkanolamine is used to adjust the pH. A neutral to weakly alkaline pH of the aqueous solution of the polymer of the present invention is preferred to protect the sulfate groups from being hydrolyzed and cleaved into free hydroxyl groups. Therefore, the pH of the final product is preferably adjusted to pH 6 to 14 in water, more preferably to pH 6 to 11, and even more preferably to pH 7 to 10. In addition, an antimicrobial agent may be added to improve the preservation of the aqueous solution of the final product. Preferably, 2-phenoxyethanol (CAS No. 122-99-6, available from BASF, for example) is used. PE) or 4,4'-dichloro-2-hydroxydiphenyl ether (CAS: 3380-30-1) and combinations thereof. 4,4'-dichloro-2-hydroxydiphenyl ether can be used as a solution, for example, a 30 wt% solution of 4,4'-dichloro-2-hydroxydiphenyl ether in 1,2-propylene glycol, such as available from BASF HP100. The antimicrobial agent may be added at a concentration of 0.0001-10%. Preferably, the antimicrobial agent is 2-phenoxyethanol at a concentration of 0.01-5%, more preferably 0.1-2%, and / or 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration of 0.001-1%, more preferably 0.002-0.6%. Herein, all concentrations are relative to the total weight of the oligomer conforming to formula (I).

[0056] In the liquid laundry composition of the present invention, the content of the amphoteric modified oligopropyleneimine ethoxylate according to formula (I) ranges from 0.05 to 10 wt%, preferably from 0.10 to 5 wt%, more preferably from 0.15 to 3 wt%.

[0057] In the context of the present invention, the term "laundry composition" means a formulated composition intended for and capable of wetting and cleaning household laundry such as clothes, linens and other household textiles. The term "linen" is commonly used to describe certain types of laundry, including bed sheets, pillowcases, towels, tablecloths, napkins and uniforms. Textiles may include woven, nonwoven and knitted fabrics; and may include natural or synthetic fibers, such as silk fibers, flax fibers, cotton fibers, polyester fibers, polyamide fibers, such as nylon, acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends.

[0058] Examples of liquid laundry compositions include heavy duty liquid laundry compositions for use in the wash cycle of an automatic washing machine, and liquid delicates and liquid color care compositions such as those suitable for washing delicate garments (e.g., garments made of silk or wool) by hand or in the wash cycle of an automatic washing machine.

[0059] In the context of the present invention, the term "liquid" means that the continuous phase or main part of the composition is liquid, and the composition is flowable at 15 ° C and above. Therefore, the term "liquid" can cover emulsions, suspensions and compositions with a flowable but harder consistency, referred to as gels or pastes. The viscosity of the composition can be suitably measured at 23 ° C in the range of 200 to 10,000 mPa.s by a rotational rheometer Rheolab QC (Anton Paar Ostfildern, Germany) with a rotor CC27 at a shear rate of 0 to 1200 / s. Pourable liquid detergent compositions typically have a viscosity of 200 to 2,500 mPa.s, preferably 200 to 1500 mPa.s. Liquid detergent compositions as pourable gels typically have a viscosity of 1,500 mPa.s to 6,000 mPa.s, preferably 1,500 mPa.s to 2,000 mPa.s.

[0060] The composition of the present invention may generally contain 3 to 95 wt %, preferably 10 to 90 wt %, more preferably 15 to 85 wt % of water. The composition may also incorporate non-aqueous carriers such as hydrotropes, cosolvents and phase stabilizers. Such materials are generally low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n-propanol or isopropanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); weight average molecular weight (M) w ) range of about 200 to 600; C1-C3 alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as sodium and potassium xylene, toluene, ethylbenzene, and cumene (cumene) sulfonates). Mixtures of any of the above materials may also be used.

[0061] When included, the non-aqueous carrier may be present in an amount of 0.1 to 20 wt%, preferably 1 to 15 wt%, more preferably 3 to 12 wt%.

[0062] The composition of the present invention preferably has a pH in the range of 5 to 9, more preferably 6 to 8, when measured when the composition is diluted to 1% using demineralised water.

[0063] The composition of the present invention comprises from 1 to 60 wt% of one or more surfactants selected from non-soap anionic surfactants, nonionic surfactants or mixtures thereof.

[0064] The non-soap anionic surfactants of the present invention are typically salts of organic sulfuric and sulfonic acids having an alkyl group containing 8 to 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of the higher acyl group. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkylaryl sulfonates, α-olefin sulfonates, and mixtures thereof. The alkyl group preferably contains 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulfates may contain 1 to 10 ethylene oxide or propylene oxide units per molecule, preferably 1 to 3 ethylene oxide units per molecule. The counterions of the anionic surfactants are typically alkali metals such as sodium or potassium; or ammonia counterions such as monoethanolamine (MEA), diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions may also be used.

[0065] A class of preferred non-soap anionic surfactants of the present invention includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) having an alkyl chain length of 10 to 18 carbon atoms. Commercially available LAS is a mixture of closely related isomers and homologous alkyl chain homologues, each containing an aromatic ring sulfonated in the "para-position" and connected to a linear alkyl chain at any position except the terminal carbon. The linear alkyl chain usually has a chain length of 11 to 15 carbon atoms, and the main material has a chain length of C12. Each alkyl chain homologue is composed of a mixture of all possible sulfophenyl isomers except the 1-phenyl isomer. LAS is usually formulated into a composition in the form of an acid (i.e., HLAS) and then at least partially neutralized in situ.

[0066] Also suitable are alkyl ether sulfates having a linear or branched alkyl group of 10 to 18, more preferably 12 to 14 carbon atoms, and containing an average of 1 to 3 EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES), in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3 EO units per molecule.

[0067] Some alkyl sulfate surfactants (PAS), such as non-ethoxylated primary and secondary alkyl sulfates having an alkyl chain length of 10 to 18, may be used.

[0068] Mixtures of the above materials may also be used.

[0069] A preferred mixture of non-soap anionic surfactants of the present invention comprises (ai) linear alkylbenzene sulfonate (preferably C 11 To C 15 linear alkylbenzene sulfonates) and (aii) alkyl ether sulfates (preferably C 10 To C 18 alkyl sulfate).

[0070] The weight ratio of (ai) / (aii) is preferably in the range of 20:1 to 1:20, more preferably 10:1 to 1:10, still more preferably 4:1 to 1:4.

[0071] In the composition of the present invention, the total content of non-soap anionic surfactant may suitably range from 5 to 30 wt%, preferably from 8 to 25 wt%, more preferably from 10 to 20 wt%.

[0072] The nonionic surfactant of the present invention is generally a polyoxyalkylene compound, i.e., the reaction product of an alkylene oxide (e.g., ethylene oxide or propylene oxide or a mixture thereof) and a starting molecule having a hydrophobic group and an active hydrogen atom reactive to the alkylene oxide. Such starting molecules include alcohols, acids, amides, or alkylphenols. When the starting molecule is an alcohol, the reaction product is referred to as an alcohol alkoxylate. The polyoxyalkylene compound can have a variety of block and hetero (random) structures. For example, they can contain a single alkylene oxide block, or they can be a diblock alkoxylate or a triblock alkoxylate. Within the block structure, the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a mixed mixture of alkylene oxides. Examples of such materials include aliphatic alcohol ethoxylates such as C8-C 18 Primary or secondary straight or branched chain alcohol ethoxylates having an average of 2 to 40 moles of ethylene oxide per mole of alcohol.

[0073] A preferred class of nonionic surfactants of the present invention includes aliphatic C8 to C 18 , more preferably C 12 To C 15 Straight chain primary alcohol ethoxylates having an average of 3 to 20, more preferably 5 to 10, moles of ethylene oxide per mole of alcohol.

[0074] Mixtures of any of the above materials may also be used.

[0075] In the composition of the present invention, the total content of nonionic surfactants may suitably range from 0.2 to 25 wt%, preferably from 1 to 15 wt%, more preferably from 2 to 10 wt%.

[0076] Preferably, the total amount of non-soap anionic surfactant and nonionic surfactant in the composition of the present invention ranges from 5 to 40 wt%, more preferably from 10 to 30 wt%, most preferably from 15 to 20 wt%.

[0077] Preferably, the weight ratio of non-soap anionic surfactant to nonionic surfactant in the composition is in the range of 20:1 to 1:20, more preferably 10:1 to 1:10, most preferably 5:1 to 1:5.

[0078] Particularly preferred compositions of the present invention comprise: (i) 2 to 25 wt% of one or more linear alkylbenzene sulfonates (preferably C 11 To C 15 linear alkylbenzene sulfonate), (ii) 2 to 20 wt% of one or more alkyl ether sulfates (preferably C 10 To C 18 alkyl sulfate) and / or 2 to 25 wt% of one or more nonionic surfactants, which are fatty alcohol ethoxylates (preferably C 12 To C 15 Straight chain primary alcohol ethoxylate having an average of 5 to 10 moles of ethylene oxide per mole of alcohol). In such preferred compositions, the weight ratio of the anionic surfactant to the nonionic surfactant may suitably range from 20:1 to 1:20, preferably from 10:1 to 1:10, more preferably from 5:1 to 1:5.

[0079] The compositions of the present invention may contain optional components to further enhance cleaning performance and / or consumer viscosity acceptance.

[0080] In addition to the non-soap anionic and / or nonionic surfactants described above, the compositions of the present invention may contain one or more co-surfactants which are amphoteric (zwitterionic) and / or cationic surfactants.

[0081] Specific cationic surfactants include C8 to C 18 Alkyl dimethyl ammonium halides and derivatives thereof wherein one or two hydroxyethyl groups replace one or two methyl groups, and mixtures thereof. When included, the cationic surfactant may be present in an amount ranging from 0.1 to 5 wt%.

[0082] Specific amphoteric (zwitterionic) surfactants include alkylamine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sultaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycocinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates having an alkyl group containing from 8 to 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl groups. When included, the amphoteric (zwitterionic) surfactant may be present in an amount ranging from 0.1 to 5%. Mixtures of any of the above materials may also be used.

[0083] The composition of the present invention may include one or more builders. Builders improve or maintain the cleaning efficiency of surfactants primarily by reducing water hardness. This can be achieved by sequestration or chelation (keeping hardness inorganics in solution), by precipitation (forming insoluble substances) or by ion exchange (exchanging charged particles). In the context of the present invention, there is no distinction between builders and such components referred to elsewhere as "co-builders" or "chelating agents". In addition to the above benefits, chelating agents can help improve the stability of the composition and prevent, for example, transition metal-catalyzed decomposition of certain ingredients.

[0084] The builder used for the present invention can be organic or inorganic type, or its mixture. Suitable inorganic builders include hydroxides, carbonates, sesquicarbonates, bicarbonates, silicates, phosphates, zeolites and mixtures thereof. Specific examples of these materials include sodium hydroxide and potassium hydroxide, sodium carbonate and potassium carbonate, sodium bicarbonate and potassium bicarbonate, sodium sesquicarbonate, sodium silicate and mixtures thereof. Suitable organic builders include polycarboxylates in acid and / or salt form. When used in salt form, preferably alkali metals (e.g. sodium and potassium) or alkanolammonium salts. Specific examples of such materials include sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium tartrate monosuccinic acid, sodium and potassium tartrate disuccinic acid, sodium and potassium ethylenediaminetetraacetic acid, sodium and potassium N-(2-hydroxyethyl)-ethylenediaminetriacetic acid, sodium and potassium nitrilotriacetic acid and sodium and potassium N-(2-hydroxyethyl)-nitrilodiacetic acid. Polymeric polycarboxylic acids, such as polymers of unsaturated monocarboxylic acids (e.g., acrylic acid, methacrylic acid, vinyl acetic acid, and crotonic acid) and / or unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid and their anhydrides) may also be used. Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic acid and maleic acid. The polymer may be in the form of an acid, salt, or partially neutralized form and may suitably have a molecular weight (Mw) ranging from about 1,000 to 100,000, preferably from about 2,000 to about 85,000, and more preferably from about 2,500 to about 75,000.

[0085] Other suitable builders which may be referred to as "chelating agents" include phosphonates in acid and / or salt form. When used in salt form, alkali metal (e.g. sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include aminotri(methylenephosphonic acid) (ATMP), 1-hydroxyethylidene diphosphonic acid (HEDP) and diethylenetriamine penta(methylenephosphonic acid) (DTPMP) and their corresponding sodium or potassium salts. HEDP is preferred.

[0086] Mixtures of any of the above materials may also be used.

[0087] Preferred builders of the present invention can be selected from citrate, phosphate, silicate, carbonate, phosphonate, aminocarboxylate, polymeric polycarboxylate or mixtures thereof. When included, the builder can be present in an amount ranging from 0.1 to 10 wt%, preferably 0.5 to 8 wt%, more preferably 1 to 5 wt%.

[0088] In some cases, the compositions of the present invention may contain one or more fatty acids and / or salts thereof.

[0089] In the context of the present invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, most preferably 12 to 18 carbon atoms and 0 or 1 double bonds. Preferred examples of such materials include saturated C12-18 fatty acids, such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures, wherein 50-100 wt% (based on the total weight of the mixture) consists of saturated C12 to 18 fatty acids. Such mixtures are typically derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow). The fatty acids may be present in the form of their sodium, potassium or ammonium salts and / or in the form of soluble salts of organic bases such as mono-, di- or triethanolamine. Mixtures of any of the above materials may also be used.

[0090] When included, fatty acids and / or their salts may be present in an amount ranging from 0.25 to 15 wt%, more preferably from 0.5 to 5 wt%, most preferably from 0.75 to 4 wt%.

[0091] For the purpose of formulation calculation, fatty acids and / or their salts (as defined above) are not included in the level of surfactant or in the level of builder in the formulation.

[0092] The compositions of the present invention preferably include one or more soil release polymers (SRPs) which help improve the release of soils from fabrics by modifying the fabric surface during the wash process. The adsorption of SRPs on fabric surfaces is promoted by the affinity between the chemical structure of the SRPs and the target fibers.

[0093] The SRPs used in the present invention may include a variety of charged (e.g., anionic) and uncharged monomer units, and the structure may be linear, branched, or star-shaped. The SRP structure may also include cOPPIng groups to control molecular weight or change polymer properties such as surface activity. The weight average molecular weight (M) of the SRP is w ) may suitably be in the range of about 1000 to about 20,000, preferably in the range of about 1500 to about 10,000.

[0094] The SRP used in the present invention can be suitably selected from copolyesters of dicarboxylic acids (e.g. adipic acid, phthalic acid or terephthalic acid), diols (e.g. ethylene glycol or propylene glycol) and polyglycols (e.g. polyethylene glycol or polypropylene glycol). The copolyesters can also include monomer units substituted with anionic groups, such as sulfonated isophthaloyl units. Examples of such materials include oligoesters produced by transesterification / oligomerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and poly(ethylene glycol") ("PEG"); partially and fully anionically terminated oligoesters, such as oligomers of ethylene glycol ("EG"), PG, DMT, and Na-3,6-dioxa-8-hydroxyoctanesulfonic acid; non-ionically terminated block polyester oligomeric compounds, such as those produced by a combination of DMT, Me-terminated PEG, and EG and / or PG, or DMT, EG and / or PG, Me-terminated PEG, and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

[0095] Other types of SRPs useful in the present invention include cellulose derivatives, such as hydroxyether cellulose polymers, C1-C4 alkyl celluloses, and C4 hydroxyalkyl celluloses; polymers having poly(vinyl ester) hydrophobic segments, such as graft copolymers of poly(vinyl esters), such as C1-C6 vinyl esters (e.g., poly(vinyl acetate)) grafted onto a polyalkylene oxide backbone; poly(vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.

[0096] Preferred SRPs for use in the present invention include terephthalate esters and glycols, preferably 1,2-propylene glycol, condensed and also include end-capped copolyesters formed from alkyl-terminated alkylene oxide repeating units. Examples of such materials have structures corresponding to formula (III):

[0097]

[0098] Where R 1 and R 2Independently of each other, X-(OC2H4) W -(OC3H6) Z ;

[0099] Where X is C 1-4 Alkyl, preferably methyl;

[0100] w is a number from 12 to 120, preferably from 40 to 50;

[0101] z is a number from 1 to 10, preferably from 1 to 7; and

[0102] a is a number from 4 to 9.

[0103] Because they are average values, w, z, and a are not necessarily integers for a large number of polymers.

[0104] Mixtures of any of the above materials may also be used.

[0105] When included, the compositions of the present invention will typically contain from 0.05 to 5 wt%, preferably from 0.1 to 2 wt%, of one or more SRPs (eg, copolyesters of formula (III) as described above).

[0106] The compositions of the present invention may include one or more rheology modifiers. Examples of such materials include polymeric thickeners and / or structurants, such as hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the present invention include linear or crosslinked copolymers prepared by addition polymerization of a monomer mixture comprising at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e., methacrylic acid and / or acrylic acid), and at least one associative monomer. In the context of the present invention, the term "associative monomer" refers to a monomer having an ethylenically unsaturated portion (for addition polymerization with other monomers in the mixture) and a hydrophobic portion. A preferred type of associative monomer includes a polyoxyalkylene portion between the ethylenically unsaturated portion and the hydrophobic portion. Preferred HASE copolymers for use in the present invention include those prepared by addition polymerization of (meth)acrylic acid with (i) at least one selected from a linear or branched C8-C 40 Alkyl (preferably straight chain C 12 -C 22The compositions of the present invention are preferably prepared by addition polymerization of (i) an associative monomer of (i) a C1-C4 alkyl) polyethoxylated (meth)acrylate; and (ii) at least one other monomer selected from C1-C4 alkyl (meth)acrylates, polyacidic vinyl monomers (e.g., maleic acid, maleic anhydride and / or salts thereof), and mixtures thereof. The polyethoxylated portion of the associative monomer (i) typically contains from about 5 to about 100, preferably from about 10 to about 80, and more preferably from about 15 to about 60 ethylene oxide repeating units. Mixtures of any of the foregoing materials may also be used. When included, the compositions of the present invention will preferably contain from 0.1 wt% to 5 wt% of one or more polymeric thickeners, such as the HASE copolymers described above.

[0107] The compositions of the present invention may also have their rheology modified by the use of one or more external structurants that form a structured network within the composition. Examples of such materials include hydrogenated castor oil, microfibrous cellulose, and citrus pulp fibers. The presence of an external structurant may provide shear-thinning rheology and may also allow materials such as encapsulates and visual cues to be stably suspended in the liquid.

[0108] Preferably, the composition of the present invention may also be free of rheology modifiers and / or structurants. Typically, the composition may be free of polymeric thickeners and / or structurants, such as hydrophobically modified alkali swellable emulsion (HASE) copolymers. HASE copolymers are described above. Herein, "free of" refers to a composition containing less than 0.1 wt%, preferably less than 0.01 wt%, and more preferably 0 wt% of a modifier and / or structurant.

[0109] The composition of the present invention may comprise an effective amount of one or more enzymes selected from the group consisting of pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzymes are preferably present together with a corresponding enzyme stabilizer.

[0110] The composition of the present invention may include other optional ingredients to enhance performance and / or consumer acceptance. Examples of such ingredients include foam boosters, preservatives, polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosive agents, drape imparting agents, antistatic agents, ironing aids, colorants, pearlescent agents and / or sunscreens, and sunscreen dyes. Each of these ingredients will be present in an amount that effectively achieves its purpose. Typically, these optional ingredients are included individually in an amount of up to 5wt%.

[0111] The composition of the present invention can be packaged as a single dose in a polymer film adapted to be insoluble before addition to water. In this context, "insoluble" is understood to mean that the film has a solubility in water of at most 0.1 g / 100 ml, preferably at most 0.01 g / 100 ml, more preferably at most 0.001 g / 100 ml, measured at 20°C. Alternatively, the composition of the present invention can be provided in a multi-dose package. The multi-dose package can have a top or bottom closure. The metering means can be provided with the multi-dose package, either as part of a cover or an integrated system.

[0112] The composition of the present invention can be used to remove soil, especially particulate soil, from fabrics. A corresponding method comprises diluting a dose of the composition of the present invention to obtain a washing liquor and washing fabrics with the washing liquor so formed. The removal of soil can be suitably carried out in a top-loading or front-loading automatic washing machine, or can be carried out manually.

[0113] In automatic washing machines, the dosage of the detergent composition is usually placed in a dispenser and flushed from the dispenser into the washing machine by the water flowing into the washing machine, thereby forming a washing liquid. The dosage for a typical front-loading washing machine (using 10 to 15 liters of water to form a washing liquid) can be from about 10g to about 100g, preferably from about 15 to 75g. The dosage for a typical top-loading washing machine (using 40-60 liters of water to form a washing liquid) can be higher, such as 100g or higher. Lower dosages of detergent (such as 50g or less) can be used for hand-washing methods (using about 1 to 10 liters of water to form a washing liquid). It is preferred that the subsequent water rinsing step and drying of the clothes.

[0114] In order to effectively remove dirt, the dosage of the composition of the present invention can be diluted in such a way that the washing liquor obtained contains 0.01-5 g / L surfactant and 1-100 ppm of the amphiphilic modified oligopropylene imine ethoxylate conforming to formula (I). Preferably, the washing liquor obtained contains 0.035 to 0.8 g / L of non-soap anionic surfactant and 1 to 50 ppm of the oligomer conforming to formula (I).

[0115] The composition of the present invention can be prepared by adding the low polypropylene imine ethoxylate of the amphiphilic modification conforming to formula (I) to the surfactant aqueous solution at the desired level. The mixture is stirred under the environment until uniform, i.e. without any visible lumps. If a rheology modifier is used, the modifier is preferably first diluted with water to obtain a solution. Preferably, this solution is at least partially neutralized before being added to the mixture of the low polypropylene imine and the surfactant. This pre-neutralization can make manufacturing easy in terms of short batch cycle time and / or reduced mixing energy. Alternatively, neutralization can be carried out after this solution is added to the mixture. Other optional ingredients are then added under mixing until a liquid with homogeneity is obtained. The resulting liquid laundry composition is filled in a selected packaging, such as a unit dose or a multi-dose package.

[0116] The invention is illustrated by the following non-limiting examples.

[0117] Example

[0118] Preparation of anti-redeposition agents of amphiphilically modified oligopropyleneimine ethoxylates (I) and comparative anti-redeposition agents Preparation

[0119] Synthesis of bis-(3,3'-aminopropyl)amine (dipropylenetriamine, DPTA): Acrylonitrile (7.8 kg, 0.15 kmol, 1.0 equiv) was introduced dropwise to an excess of 1,3-diaminopropane (27.0 kg, 0.36 kmol, 2.5 equiv) in a reaction vessel at 60°C and kept below 65°C. After the addition reaction was complete, the reaction was stirred at 60°C for 2 hours and then cooled to room temperature. The crude mixture was then analyzed by GC chromatography and found to give a distribution of 45% (GC area-%) unreacted starting material, 47% (GC area-%) desired monocyanoethylated compound and 7% (GC area-%) dicyanoethylated compound (34.8 kg). Subsequently and without any further purification, the above crude mixture was subjected to hydrogenation catalyzed by [Co]-catalyst in a fixed bed pressure reactor at 90°C and 200 bar hydrogen pressure. The crude oligoamine mixture was fractionated under reduced pressure (140 to 20 mbar) and elevated temperature (120-220°C column temperature) to give DPTA (134°C; 20 mbar; purity>99%) as a colorless liquid. GC-analysis (30 m RTX5Amin column; injection temperature 60°C, then heated to 280°C at 10°C / min): R t =11.39min (DPTA) and R t =17.25min(TPTA). 1 H-NMR (500MHz,CDCl3): (m,8H),1.59(m,4H),1.09(bs,5H)ppm. 13 C-NMR (125MHz,CDCl3): 39.9,39.7,37.6,37.4,37.3ppm.

[0120] Synthesis of bis-(3,3'-aminopropyl)-1,3-propanediamine (tripropylenetetramine, TPTA): Acrylonitrile (795 g, 15.0 mol, 2.05 eq.) was introduced dropwise into 1,3-diaminopropane (542 g, 7.3 mol, 1.0 eq.) in a reaction vessel at 13°C over 4 hours and kept below 15°C. After the addition reaction was complete, the reaction was stirred at 15°C for another 2 h and then warmed to room temperature. Subsequently and without any further purification, the crude mixture was hydrogenated in a batch pressure reactor catalyzed by Raney-Ni catalyst (5 wt%) at 100°C and 200 bar hydrogen pressure and stirred for 12 hours. After the reaction was complete, the reaction was quenched by purging the vessel with nitrogen, removing the catalyst by filtration and removing the volatiles under reduced pressure. The desired target compound was obtained after distillation under reduced pressure (3 mbar) and elevated temperature (170°C column temperature), and TPTA (130°C; 3 mbar; >99% purity) was obtained as a colorless liquid. GC-analysis (30 m RTX5 Amin column; injection temperature 60°C, then heating to 280°C at 10°C / min): R t =17.25min(TPTA). 1 H-NMR (500MHz, MeOD): (m,6H),2.7-2.6(m,12H),1.7-1.6(bs,6H)ppm. 13 C-NMR (125MHz, MeOD): 48.9,48.8,48.7,48.5,48.3,40.6,33.6,30.1ppm.

[0121] Synthesis of tri-(3,3',3"-aminopropyl)-1,3-propylenediamine (tetrapropylenepentamine, TPPA): Acrylonitrile (339 g, 6.4 mol, 2.0 equiv) was introduced dropwise into a mixture of tripropylenetetramine (TPTA, 598 g, 3.2 mol, 1.0 equiv) in THF (750 mL) in a reaction vessel at 50°C. After the addition reaction was complete, the reaction was stirred at 50°C for another 2 hours and then cooled to room temperature. Subsequently and without any further purification, the reaction mixture was heated to 40 ℃ and heated to 100 ℃ under a Raney-Co catalyst (5 wt%) at 120°C and 100 bar hydrogen pressure. , the crude mixture was hydrogenated in a batch pressure reactor and stirred for 8 hours. After completion of the reaction, the reaction was quenched by purging the reaction vessel with nitrogen, the catalyst was removed by filtration and the solvent was removed under reduced pressure. After distillation under reduced pressure (2 mbar) and at elevated temperature (270°C column temperature), the desired target compound was obtained after pentapropylene hexamine (PPHA), and TPPA (147°C; 2 mbar; 93% purity) was given as a yellow oil. GC-analysis (30mRTX5Amin column; injection temperature of 80°C, then heated to 280°C at 15°C / min): R t =20.23min(TPPA).

[0122] Synthesis of oligomer 1 (P1) according to formula (I): 96.03 g of dipropylenetriamine (DPTA, 0.83 mol, 1 eq.) and 10 g of water were charged into a steel pressure reactor. The reactor was purged with nitrogen to remove air and the nitrogen pressure was set to 1 bar. The reactor was heated to 100° C. and 130 g of ethylene oxide (2.95 mol, 3.56 eq.) were fed into the reactor over 7 hours. Thereafter, the reaction mixture was kept at 100° C. for post-reaction. Volatile compounds were removed under vacuum and 221.5 g of a transparent and highly viscous product was removed from the reactor. 39.8 g of the previously obtained product was filled into a steel pressure reactor and 2.4 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air and the nitrogen pressure was set to 1 bar. The reactor was heated to 120°C and 548 g of ethylene oxide (12.4 mol, 99.7 equivalents) were added over 6 hours. Volatile compounds were removed under vacuum to give 589 g of a brown solid. 200 g of the resulting ethoxylate (0.044 mol, 1 equivalent) were heated to 60°C and filled into a glass reactor under a nitrogen atmosphere. 16.2 g of dimethylsulfate (0.13 mol, 2.9 equivalents) were fed into the reactor in a manner that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70°C. After the addition was complete, the mixture was post-reacted at 70°C for 2 hours. 3.6 g of sulfuric acid (0.036 mol, 0.9 equivalents) were added to the reactor and the temperature was raised to 90°C, and the reactor was set under vacuum (15 mbar) for three hours. After the reaction was complete, 5.4 g of sodium hydroxide (50% aqueous solution) and 40 g of demineralized water were added, and the orange liquid product was removed from the reactor.

[0123] Synthesis of oligomer 2 (P2) according to formula (I): 297.9 g of tripropylenetetramine (TPTA, 1.58 mol, 1 equivalent) and 29.8 g of water were loaded into a steel pressure reactor. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2.5 bar. The reactor was heated to 100 ° C and 335 g of ethylene oxide (7.61 mol, 4.81 equivalents) were fed into the reactor within 10 hours. Thereafter, the reaction mixture was kept at 100 ° C for 6 hours for post-reaction. Volatile compounds were removed under vacuum, and 626.4 g of a transparent and highly viscous product was removed from the reactor. 100 g of the previously obtained product was filled into a steel pressure reactor, and 5.5 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2 bar. The reactor was heated to 120°C and 1270 g of ethylene oxide (28.8 mol, 115.2 eq.) was added over 16 hours. Volatile compounds were removed under vacuum to give 1374.2 g of a brown solid. 705.1 g of the resulting ethoxylate (0.13 mol, 1 eq.) was heated to 60°C and filled into a glass reactor under a nitrogen atmosphere. 62.1 g of dimethyl sulfate (0.49 mol, 3.8 eq.) was added to the reactor in a manner that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70°C. After the addition was complete, the mixture was subjected to a post-reaction at 70°C for 2 hours. 8.0 g of sulfuric acid (0.08 mol, 0.6 eq.) was added to the reactor, the temperature was raised to 90°C and the reactor was set under vacuum (15 mbar) for three hours. After the reaction was complete, 11.0 g of sodium hydroxide (50% aqueous solution) and 650 g of demineralized water were added. The liquid product was removed from the reactor.

[0124] Synthesis of oligomer 3 (P3) according to formula (I): 138.9 g of tripropylenetetramine (TPTA, 0.74 mol, 1 equivalent) and 13.9 g of water were charged into a steel pressure reactor. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 1 bar. The reactor was heated to 100 ° C and 156 g of ethylene oxide (3.54 mol, 4.81 equivalents) was fed into the reactor within 10 hours. Thereafter, the reaction mixture was kept at 100 ° C for 5 hours for post-reaction. Volatile compounds were removed under vacuum, and 290 g of a transparent and highly viscous product was removed from the reactor. 63 g of the previously obtained product was filled into a steel pressure reactor and 3.0 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 1 bar. The reactor was heated to 120°C and 696 g of ethylene oxide (15.8 mol, 100.3 eq.) was added over 10 hours. Volatile compounds were removed under vacuum to give 754.8 g of a brown solid. 556 g of the resulting ethoxylate (0.12 mol, 1 eq.) was heated to 60°C and filled into a glass reactor under a nitrogen atmosphere. 57.4 g of dimethyl sulfate (0.49 mol, 3.8 eq.) was fed into the reactor in a manner that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70°C. After the addition was complete, the mixture was post-reacted at 70°C for 2 hours. 7.0 g of sulfuric acid (0.07 mol, 0.6 eq.) was added to the reactor, the temperature was raised to 90°C and the reactor was set under vacuum (15 mbar) for three hours. After the reaction was complete, 10.0 g of sodium hydroxide (50% aqueous solution) and 500 g of demineralized water were added and the orange liquid product was removed from the reactor.

[0125] Synthesis of oligomer 4 (P4) according to formula (I): 173.8 g of tripropylenetetramine (TPTA, 0.92 mol, 1 eq.) and 17.3 g of water were charged into a steel pressure reactor. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2.5 bar. The reactor was heated to 100 ° C and 195 g of ethylene oxide (4.43 mol, 4.81 eq.) was fed into the reactor over 10 hours. Thereafter, the reaction mixture was kept at 100 ° C for 6 hours for post-reaction. Volatile compounds were removed under vacuum, and 366.8 g of a transparent and highly viscous product was removed from the reactor. 60 g of the previously obtained product was filled into a steel pressure reactor and 4.9 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 1 bar. The reactor was heated to 120°C and 1159 g of ethylene oxide (26.2 mol, 174.6 eq.) was added over 15 hours. The volatile compounds were removed under vacuum to give 1233 g of a brown solid. 488.1 g of the resulting ethoxylate (0.06 mol, 1 eq.) was heated to 60°C and filled into a glass reactor under a nitrogen atmosphere. 29.3 g of dimethyl sulfate (0.23 mol, 3.87 eq.) was fed into the reactor in such a way that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70°C. After the addition was complete, the mixture was post-reacted at 70°C for 2 hours. 6.7 g of sulfuric acid (0.07 mol, 0.6 eq.) was added to the reactor, the temperature was raised to 90°C and the reactor was set under vacuum (15 mbar) for three hours. After the reaction was complete, 8.5 g of sodium hydroxide (50% aqueous solution) and 488.1 g of demineralized water were added and the orange liquid product was removed from the reactor.

[0126] Synthesis of oligomer 5 (P5) according to formula (I): 83.3 g of tripropylenetetramine (TPTA, 0.44 mol, 1 eq.) and 8.3 g of water were charged into a steel pressure reactor. The reactor was purged with nitrogen to remove air and the nitrogen pressure was set to 2.5 bar. The reactor was heated to 120° C. and 93.5 g of ethylene oxide (2.12 mol, 4.83 eq.) was fed into the reactor in such a way that the internal pressure did not exceed 5.5 bar. Thereafter, the reaction mixture was kept at 120° C. for 6 hours for post-reaction. 9.1 g of potassium hydroxide (50% aqueous solution) was added and water was removed under reduced pressure. The reactor was purged with nitrogen to remove air and the nitrogen pressure was set to 2.5 bar. The reactor was heated to 140° C. and 844 g of ethylene oxide (19.2 mol, 43.6 eq.) was added in such a way that the internal pressure did not exceed 5.5 bar. The mixture was post-reacted for 6 hours. The volatile compounds were removed under vacuum to give 952.2 g of a brown viscous liquid. 494 g of the previously obtained alkoxylate were charged into a steel pressure reactor, inerted with nitrogen and heated to 140° C. A nitrogen prepressure of 2.5 bar was set and 667.4 g of ethylene oxide (15.15 mol, 34.4 equivalents) were added to the reactor in such a way that the internal pressure remained below 5.5 bar. The mixture was post-reacted for 6 hours. The volatile compounds were removed under vacuum to give 1060.8 g of a brown solid as product. 326.3 g of the obtained ethoxylate (0.06 mol, 1 equivalent) were heated to 60° C. and filled into a glass reactor under a nitrogen atmosphere. 29.9 g of dimethyl sulfate (0.24 mol, 3.9 equivalents) were fed into the reactor in such a way that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70° C. After the addition was complete, the mixture was post-reacted at 70° C. for 2 hours. 4.0 g of sulfuric acid (0.04 mol, 0.68 eq.) was added to the reactor, the temperature was raised to 90° C. and the reactor was set under vacuum (15 mbar) for three hours. After the reaction was complete, 9.14 g of triethanolamine and 143.1 g of demineralized water were added and the orange liquid product was removed from the reactor.

[0127] Synthesis of oligomer 6 (P6) according to formula (I): 62.9 g of tetrapropylene pentamine (TPPA, 0.26 mol, 1 eq.) and 6.3 g of water were charged into a steel pressure reactor. The reactor was purged with nitrogen to remove air and a nitrogen pressure of 3.5 bar was set. The reactor was heated to 100° C. and 60 g of ethylene oxide (1.36 mol, 5.2 eq.) was fed into the reactor over 7 hours. Thereafter, the reaction mixture was kept at 100° C. for post-reaction. Volatile compounds were removed under vacuum and 6.2 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air and a nitrogen pressure of 1.5 bar was set. The reactor was heated to 120° C. and 1435 g of ethylene oxide (32.575 mol, 125 eq.) was added over 12 hours. Volatile compounds were removed under vacuum to give 1589.2 g of a brown solid. 314.2 g of the resulting ethoxylate (0.05 mol, 1 eq) were heated to 60° C. and filled into a glass reactor under a nitrogen atmosphere. 31.4 g of dimethyl sulfate (0.25 mol, 4.9 eq) were added to the reactor in a manner that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70° C. After the addition was complete, the mixture was post-reacted at 70° C. for 2 hours. 3.5 g of sulfuric acid (0.036 mol, 0.7 eq) was added to the reactor, the temperature was raised to 90° C. and the reactor was set under vacuum (15 mbar) for three hours. After the reaction was complete, 5.0 g of sodium hydroxide (50% aqueous solution) and 300 g of demineralized water were added and the orange liquid product was removed from the reactor.

[0128] Synthesis of Comparative Example (CP1): 297.9 g of tripropylenetetramine (TPTA, 1.58 mol, 1 equivalent) and 29.8 g of water were loaded into a steel pressure reactor. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2.5 bar. The reactor was heated to 100 ° C, and 335 g of ethylene oxide (7.61 mol, 4.81 equivalents) was fed into the reactor within 10 hours. Afterwards, the reaction mixture was kept at 100 ° C for 6 hours for post-reaction. Volatile compounds were removed under vacuum, and 626.4 g of a transparent and highly viscous product was removed from the reactor. 100 g of the previously obtained product was loaded into a steel pressure reactor, and 5.5 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2 bar. The reactor was heated to 120°C and 1270 g of ethylene oxide (28.8 mol, 115.2 eq.) was added over 16 hours. The volatile compounds were removed under vacuum to give 1374.2 g of a brown solid.

[0129] Synthesis of Comparative Example 2 (CP2): 99.1 g of tripropylenetetramine (TPTA, 0.53 mol, 1 equivalent) and 9.9 g of water were loaded into a steel pressure reactor. The reactor was purged with nitrogen to remove air and a nitrogen pressure of 1.0 bar was set. The reactor was heated to 100 ° C and 112 g of ethylene oxide (2.54 mol, 4.83 equivalents) was fed into the reactor within 6 hours. Afterwards, the reaction mixture was kept at 100 ° C for 6 hours for post-reaction. Volatile compounds were removed under vacuum and 210 g of a transparent and highly viscous product was removed from the reactor. 39.2 g of the previously obtained product was filled into a steel pressure reactor and 1.1 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air and a nitrogen pressure of 1 bar was set. The reactor was heated to 120 ° C and 498 g of ethylene oxide (11.3 mol, 115.2 equivalents) was added within 10 hours. The volatile compounds were removed under vacuum to give 536 g of a brown solid. 115 g of the resulting ethoxylate (0.02 mol, 1 eq) was heated to 60 ° C and filled into a glass reactor under a nitrogen atmosphere. 10.3 g of dimethyl sulfate (0.08 mol, 3.9 eq) was added to the reactor in a manner that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70 ° C. After the addition was complete, the mixture was post-reacted at 70 ° C for 2 hours. Sodium hydroxide (50% aqueous solution) was added to set the pH to 8.2. The product was obtained as a light brown solid.

[0130] Synthesis of Comparative Example 3 (CP3): 500 g of polypropylene imine and 17 g of water were loaded into a steel pressure reactor. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2.5 bar. The reactor was heated to 120 ° C and 348 g of ethylene oxide was fed into the reactor within 6 hours. Thereafter, the reaction mixture was kept at 120 ° C for 6 hours for post-reaction. Volatile compounds were removed under vacuum, and 825 g of yellow and highly viscous product was removed from the reactor. 90 g of the previously obtained product was filled into a steel pressure reactor and 3.5 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2 bar. The reactor was heated to 120 ° C and 783 g of ethylene oxide (17.8 mol) was added within 16 hours. Volatile compounds were removed under vacuum to obtain 875 g of brown solid.

[0131] Synthesis of Comparative Example (CP4): 500 g of polypropylene imine and 17 g of water were loaded into a steel pressure reactor. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2.5 bar. The reactor was heated to 120 ° C and 348 g of ethylene oxide was added to the reactor within 6 hours. Thereafter, the reaction mixture was kept at 120 ° C for 6 hours for post-reaction. Volatile compounds were removed under vacuum, and 825 g of yellow and highly viscous product was removed from the reactor. 90 g of the previously obtained product was filled into a steel pressure reactor, and 3.5 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2 bar. The reactor was heated to 120 ° C and 783 g of ethylene oxide (17.8 mol) was added within 16 hours. Volatile compounds were removed under vacuum to obtain 875 g of brown solid. 78.1 g of the resulting ethoxylate was heated to 60 ° C and filled into a glass reactor under a nitrogen atmosphere. 6.6 g of dimethyl sulfate (0.05 mol) was fed into the reactor in a manner that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70° C. After the addition was complete, the mixture was post-reacted at 70° C. for 2 hours and neutralized with 5.4 g of sodium hydroxide (50% aqueous solution) to obtain 82.2 g of a brown solid. 33.0 g of the brown solid was heated to 60° C. and 1.2 g of sulfuric acid was added to the reactor, the temperature was raised to 90° C. and the reactor was set under vacuum (15 mbar) for three hours. After the reaction was complete, 2.7 g of sodium hydroxide (50% aqueous solution) was added. The product obtained was a brown solid.

[0132] Synthesis of Comparative Example 5 (CP5): 98.9 g of 1,3-propylenediamine (1,3-PDA, 1.33 mol, 1 equivalent) and 9.9 g of water were loaded into a steel pressure reactor. The reactor was purged with nitrogen to remove air, and a nitrogen pressure of 1.0 bar was set. The reactor was heated to 100 ° C and 189 g of ethylene oxide (4.29 mol, 3.23 equivalents) was fed into the reactor within 6 hours. Thereafter, the reaction mixture was kept at 100 ° C for 6 hours for post-reaction. Volatile compounds were removed under vacuum, and 210 g of a transparent and highly viscous product was removed from the reactor. 50.05 g of the previously obtained product was filled into a steel pressure reactor and 3.3 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 1 bar. The reactor was heated to 120° C. and 788 g of ethylene oxide (17.9 mol, 76.9 eq.) were added over 10 hours. The volatile compounds were removed under vacuum to give 838.1 g of a brown solid. 200 g of the resulting ethoxylate (0.06 mol, 1 eq.) were heated to 60° C. and filled into a glass reactor under a nitrogen atmosphere. 13.8 g of dimethyl sulfate (0.11 mol, 1.9 eq.) were fed into the reactor in such a way that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70° C. After the addition was complete, the mixture was post-reacted at 70° C. for 2 hours. 3.6 g of sulfuric acid (0.04 mol, 0.6 eq.) were added to the reactor, the temperature was raised to 90° C., and the reactor was set under vacuum (15 mbar) for 3 hours. After the reaction was complete, 5.0 g of sodium hydroxide (50% aqueous solution) and 40 g of demineralized water were added, and the orange liquid product was removed from the reactor.

[0133] Synthesis of Comparative Example (CP6): 364g hexamethylenediamine (HMDA, 3.13mol, 1 equivalent) and 36.4g water are loaded into a steel pressure reactor. The reactor is purged with nitrogen to remove air, and the nitrogen pressure is set to 2.0bar. The reactor is heated to 100°C and 442g ethylene oxide (10.0mol, 3.19 equivalents) is fed into the reactor within 6 hours. Thereafter, the reaction mixture is kept at 100°C for 6 hours for post-reaction. Volatile compounds are removed under vacuum, and 795.2g of transparent and highly viscous product is removed from the reactor. 80g (0.43mol, 1.0 equivalents) of the previously obtained product are filled into a steel pressure reactor and 3.3g potassium hydroxide (50% aqueous solution) is added. Water is removed under reduced pressure. The reactor is purged with nitrogen to remove air, and the nitrogen pressure is set to 1bar. The reactor was heated to 130° C. and 1053 g of ethylene oxide (23.9 mol, 55.7 eq.) were added over 15 hours. The volatile compounds were removed under vacuum to give 1149.4 g of a brown solid. 364 g of the resulting ethoxylate (0.1 mol, 1 eq.) were heated to 60° C. and filled into a glass reactor under a nitrogen atmosphere. 24.8 g of dimethyl sulfate (0.20 mol, 1.9 eq.) were fed into the reactor in such a way that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70° C. After the addition was complete, the mixture was post-reacted at 70° C. for 2 hours. 3.4 g of sulfuric acid (0.03 mol, 0.3 eq.) were added to the reactor, the temperature was raised to 90° C., and the reactor was set under vacuum (15 mbar) for 3 hours. After the reaction was complete, 3.27 g of sodium hydroxide (50% aqueous solution) and 384 g of demineralized water were added and the liquid product was removed from the reactor.

[0134] Synthesis of Comparative Example 7 (CP7): 97.9 g of ethylenediamine (EDA, 1.63 mol, 1 equivalent) and 9.7 g of water were loaded into a steel pressure reactor. The reactor was purged with nitrogen to remove air, and a nitrogen pressure of 1.0 bar was set. The reactor was heated to 100 ° C and 230 g of ethylene oxide (5.22 mol, 3.2 equivalents) was fed into the reactor within 6 hours. Thereafter, the reaction mixture was kept at 100 ° C for 6 hours for post-reaction. Volatile compounds were removed under vacuum, and 327 g of a transparent and highly viscous product was removed from the reactor. 42.6 g (0.21 mol, 1.0 equivalent) of the previously obtained product was filled into a steel pressure reactor and 3.0 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and a nitrogen pressure of 1 bar was set. The reactor was heated to 130° C. and 717 g of ethylene oxide (16.3 mol, 77.5 equivalents) were added over 15 hours. The volatile compounds were removed under vacuum to give 752.8 g of a brown solid. 200 g of the resulting ethoxylate (0.06 mol, 1 equivalent) were heated to 60° C. and filled into a glass reactor under a nitrogen atmosphere. 13.9 g of dimethyl sulfate (0.11 mol, 1.9 equivalents) were fed into the reactor in such a way that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70° C. After the addition was complete, the mixture was post-reacted at 70° C. for 2 hours. 4.2 g of sulfuric acid (0.04 mol, 0.6 equivalents) were added to the reactor, the temperature was raised to 90° C., and the reactor was set under vacuum (15 mbar) for 3 hours. After the reaction was complete, 7.8 g of sodium hydroxide (50% aqueous solution) and 40 g of demineralized water were added and the orange liquid product was removed from the reactor.

[0135] Synthesis of Comparative Example 8 (CP8): 96.7 g of diethylenediamine (DETA, 0.94 mol, 1 equivalent) and 9.7 g of water were charged into a steel pressure reactor. The reactor was purged with nitrogen to remove air, and a nitrogen pressure of 1.0 bar was set. The reactor was heated to 100° C. and 136 g of ethylene oxide (3.08 mol, 3.3 equivalents) was fed into the reactor over 6 hours. Thereafter, the reaction mixture was kept at 100° C. for 6 hours for post-reaction. Volatile compounds were removed under vacuum, and 231 g of a transparent and highly viscous product was removed from the reactor. 45.9 g (0.16 mol, 1.0 equivalent) of the previously obtained product was filled into a steel pressure reactor and 2.9 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and a nitrogen pressure of 1 bar was set. The reactor was heated to 130° C. and 696 g of ethylene oxide (15.8 mol, 98.8 eq.) were added over 15 hours. The volatile compounds were removed under vacuum to give 732.7 g of a brown solid. 200 g of the resulting ethoxylate (0.04 mol, 1 eq.) were heated to 60° C. and filled into a glass reactor under a nitrogen atmosphere. 16.5 g of dimethyl sulfate (0.13 mol, 2.9 eq.) were fed into the reactor in such a way that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70° C. After the addition was complete, the mixture was post-reacted at 70° C. for 2 hours. 3.9 g of sulfuric acid (0.04 mol, 0.8 eq.) were added to the reactor and the temperature was raised to 90° C. and the reactor was set under vacuum (15 mbar) for 3 hours. After the reaction was complete, 6.8 g of sodium hydroxide (50% aqueous solution) and 40 g of demineralized water were added and the orange liquid product was removed from the reactor.

[0136] Synthesis of Comparative Example 9 (CP9): 233.6 g of triethylenetetramine (TETA, 1.60 mol, 1 equivalent) and 23.3 g of water were added to a steel pressure reactor. The reactor was purged with nitrogen to remove air, and a nitrogen pressure of 1.0 bar was set. The reactor was heated to 100 ° C and 338 g of ethylene oxide (7.67 mol, 4.8 equivalents) was fed to the reactor within 6 hours. Thereafter, the reaction mixture was kept at 100 ° C for 6 hours for post-reaction. Volatile compounds were removed under vacuum, and 571 g of a transparent and highly viscous product was removed from the reactor. 46.3 g (0.13 mol, 1.0 equivalent) of the previously obtained product was filled into a steel pressure reactor and 2.8 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and a nitrogen pressure of 1 bar was set. The reactor was heated to 130° C. and 658 g of ethylene oxide (14.9 mol, 114.9 eq.) were added over 15 hours. The volatile compounds were removed under vacuum to give 694 g of a brown solid. 200 g of the resulting ethoxylate (0.04 mol, 1 eq.) were heated to 60° C. and filled into a glass reactor under a nitrogen atmosphere. 17.4 g of dimethyl sulfate (0.14 mol, 3.75 eq.) were fed into the reactor in such a way that 1 ml of DMS was added per minute. During the addition, the temperature was increased to 70° C. After the addition was complete, the mixture was post-reacted at 70° C. for 2 hours. 3.0 g of sulfuric acid (0.03 mol, 0.8 eq.) were added to the reactor, the temperature was raised to 90° C., and the reactor was set under vacuum (15 mbar) for 3 hours. After the reaction was complete, 7.6 g of sodium hydroxide (50% aqueous solution) and 40 g of demineralized water were added and the viscous liquid product was removed from the reactor.

[0137] Synthesis of Comparative Example (CP10): Synthesized according to WO9532272 or US9738754 (PEI600+20EO / NH).

[0138] Synthesis of Comparative Example 11 (CP11): 400 g of tripropylenetetramine (TPTA, 2.12 mol, 1 equivalent) and 40 g of water were charged into a steel pressure reactor. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2.5 bar. The reactor was heated to 100 ° C and 450 g of ethylene oxide (10.22 mol, 4.8 equivalents) was fed into the reactor within 10 hours. Thereafter, the reaction mixture was kept at 100 ° C for 6 hours for post-reaction. Volatile compounds were removed under vacuum, and 945 g of a transparent and highly viscous product was removed from the reactor. 50.0 g (0.13 mol, 1.0 equivalent) of the previously obtained product was filled into a steel pressure reactor and 3.0 g of potassium hydroxide (50% aqueous solution) was added. Water was removed under reduced pressure. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set to 2 bar. The reactor was heated to 130°C and 337g of ethylene oxide (7.65mol, 61.1 equivalents) was added within 6 hours. The mixture was post-reacted for 6 hours. Afterwards, 87g of propylene oxide (1.50mol, 12.0 equivalents) was fed into the reactor within 2 hours. The mixture was post-reacted for 6 hours at 130°C. Subsequently, 264g of ethylene oxide (5.99mol, 48.0 equivalents) was fed into the reactor at 130°C and the mixture was post-reacted for 6 hours. The volatile compounds were removed under vacuum to obtain 755g of a yellow viscous liquid. 451.6g of the resulting ethoxylate (0.08mol, 1 equivalent) was heated to 60°C and filled into a glass reactor under a nitrogen atmosphere. 39.1g of dimethyl sulfate (0.31mol, 3.9 equivalents) was fed into the reactor in a manner that 1ml of DMS was added per minute. During the addition, the temperature was increased to 70°C. After the addition was complete, the mixture was post-reacted at 70° C. for 2 hours. 5.80 g of sulfuric acid (0.06 mol, 0.7 equivalent) was added to the reactor, the temperature was raised to 90° C., and the reactor was set under vacuum (15 mbar) for 3 hours. After the reaction was complete, 7.9 g of sodium hydroxide (50% aqueous solution) and 440 g of demineralized water were added, and the orange liquid product was removed from the reactor.

[0139] Synthesis of Comparative Example 12 (CP12): Synthesized as described in WO2020 / 030469 (PEI2000+32.5EO / NH, polymer P.2).

[0140] Characterization of the present invention and comparative structures: The molecular weight of the examples was determined by gel permeation chromatography (GPC). The conditions used were hexafluoroisopropanol and 0.05% potassium trifluoroacetate as solvents. The column box temperature was set at 35°C and the flow rate was 1 mL / min. 50 μL of sample was injected, and the concentration of the sample was set to 1.5 mg / mL. After the polymer was dissolved, the sample was filtered using a Millipore Millflex FG (0.2 μm) filter to avoid column clogging. The following columns were used: HFIP guard column (diameter: 8 mm, length: 5 cm), PL HFIP gel column (separation material styrene-divinylbenzene, diameter: 7.5 mm, length: 30 cm) and PL HFIP Gel column (separation material styrene-divinylbenzene, diameter: 7.5 mm, length: 30 cm, exclusion size: 100-100000 g / mol). The GPC system was calibrated using PMMA standards with a molecular weight range between 800 and 2200000 g / mol. The eluate was detected using a refractive index (RI) detector (DRI Agilent 1000).

[0141] Table 1. Chemical properties of the examples

[0142]

[0143]

[0144] $ Mw=523 g / mol, Mn=349 g / mol, PDI 1.5. The Mw of the main chain is as described in EP2961821 and is higher than the Mw of the main chain of the oligomer conforming to formula (I).

[0145] The backbone is aziridine based polyethyleneimine, Mw 600 g / mol, as described in WO9532272 or US9738754.

[0146] *The backbone is an aziridine-based polyethyleneimine, Mw 2000 g / mol, as described in WO2020 / 030469. Mw was determined by MALLS detector.

[0147] Measurement of cleaning performance and viscosity

[0148] Table 2. Liquid laundry compositions (for cleaning performance)

[0149]

[0150]

[0151] Table 3. Liquid laundry compositions (for viscosity)

[0152] Element wt% <![CDATA[Linear C 12-14 alkylbenzenesulfonic acid]]> 2.72 <![CDATA[C 12 Fatty Alcohol x 3EO Sulfate]]> 2.04 <![CDATA[C 12-15 Fatty Alcohol x 7EO]]> 2.04 <![CDATA[C 12-18 Fatty Acids]]> 0.40 HASE Thickening Polymer 0.85 1-Hydroxyethane-1,1-diphosphonic acid (HEDP) 0.70 Triethanolamine 3.52 Fragrance 0.65 preservative 0.03 Examples of Anti-redeposition Agents 0.50 or 1.45 Demineralized water Add to 100 pH 7.5

[0153] The cleaning performance on round red clay and yellow clay stains on polyester fabric (polyester and cotton ballast, each experiment produced a 1:1 ratio of polyester / cotton fabric, Warwick Equest, Consett, UK) was measured by measuring the color difference (ΔE) between the washed stain and the unstained white fabric using a reflectometer (Datacolor SF600 plus). Four round red clay and four yellow clay stains (i.e., 2 pieces of polyester test fabric containing 2 round red clay and 2 yellow clay stains) were used in 1 experiment, and each experiment was repeated 3 times, thereby obtaining a total of 12 washed stains of red clay and yellow clay under each test condition to calculate the average ΔE value. By using these ΔE values, the so-called "normalized cleaning performance" (ΔΔE) was calculated. The "normalized cleaning performance" (ΔΔE) is the difference in performance of the detergent containing the anti-redeposition agent of the present invention and the comparative anti-redeposition agent, respectively, and the detergent not containing any anti-redeposition agent, respectively. The larger the sum of the ΔΔE values, the greater the positive impact of the corresponding anti-redeposition agent on the cleaning performance. During each wash, 200 mL of wash liquor was used in a Linitest+ washing unit (SDL Atlas Rock Hill, USA) with a fabric to liquid ratio of 1:10. The liquid detergent concentration was 3.0 g / L. The wash time was 30 minutes at 40°C and the water hardness was 12° fH. After washing, the fabrics were rinsed twice and then dried overnight in an ambient environment before being measured with a reflectometer.

[0154] The viscosity of the compositions was measured at room temperature (23° C.) using a rotational rheometer Rheolab QC (Anton Paar Ostfildern, Germany) using spindle CC 27. The measurements were carried out at shear rates of 0 to 1200 1 / s.

[0155] Table 4. Cleaning performance results

[0156]

[0157] **For the sum of ΔΔE, the 95% confidence interval of the applied method is + / - 1.5.

[0158] It can be seen that when the oligomer is not amphiphilically modified, the cleaning performance of the corresponding compositions is significantly worse (CP1) or directed to be worse (CP2) than those containing amphiphilically modified oligomers according to formula (I). It can also be seen that when the main chain propylene imine has a molecular weight that is higher (CP3 and CP4) or lower (CP5) than the molecular weight corresponding to formula (I), the cleaning performance is also adversely affected, even independently of the modification type (non-ionic polymer: CP3; amphiphilically modified polymer: CP4 and CP5). It can further be seen that if the main chain structure is different from the required propylene imine (CP6-9), the cleaning performance shows a significant decrease. Finally, when the anti-redeposition agent is based on polyethylene imine (PEI) known in the prior art (CP10 and CP12), even at higher concentrations, the corresponding compositions still show significantly worse performance.

[0159] Table 5. Viscosity results

[0160]

[0161] The results of viscosity measurements clearly confirm the advantages of the oligomers according to formula (I). All compositions comprising the oligomers show significantly higher viscosities than the compositions comprising the comparative examples except CP12. However, CP12 needs to be included at a much higher level, and even so, its cleaning performance is also poorer than the oligomers of the present invention (see Table 4). Compositions comprising CP11 (with side chains of mixed EO / PO, rather than EO) show comparable cleaning performance (see Table 4), but the viscosity is significantly worse.

[0162] The combination of the results of Table 4 and Table 5 clearly shows that only the oligomers conforming to formula (I) can result in improved soil removal while maintaining the viscosity characteristics of the composition.

Claims

1. A liquid laundry composition comprising: (i) 1 to 60 wt% of one or more surfactants selected from non-soap anionic surfactants, nonionic surfactants and mixtures thereof; and (ii) 0.05 to 10 wt% of an amphiphilically modified oligopropylene imine ethoxylate having the following formula (I): Where E is the formula corresponding to -(RO) n -R' ethoxy side chain, wherein the R unit is ethylene; n has an average value of 5 to 50; the R' units are each independently selected from hydrogen and SO3 - , wherein at least 30% of the R' units are SO3 - ; The Q units are each independently selected from C1-C4 alkyl, H and a free electron pair, wherein at least 50% of the Q units are C1-C4 alkyl; and x is 1 to 3.

2. The composition according to claim 1, wherein n has an average value of 10 to 40.

3. The composition according to claim 1, wherein at least 50% of the R' units are SO3 - .

4. The composition of claim 1, wherein at least 80% of the Q units are C1-C4 alkyl groups.

5. The composition of claim 1, wherein at least 90% of the Q units are C1-C4 alkyl groups.

6. The composition of claim 1, wherein x is 1, 2 or 3; at least 80% of the Q units are C1-C4 alkyl; and Q = C1-C4 alkyl and R' = SO3 - The ratio is 1:1 to 1:0.

8.

7. The composition according to any one of claims 1 to 6, wherein x is 2 or 3 and at least 90% of all Q units are methyl groups.

8. The composition according to claim 7, wherein x is 2 and n has an average value of 15 to 30.

9. A composition according to any one of claims 1 to 6, wherein x is 2, and the composition further comprises one or more isomeric compounds of the following formula (II) Where E corresponds to the formula -(RO) n -R' ethoxy side chain, wherein the R unit is ethylene; n has an average value of 5 to 50; the R' units are each independently selected from hydrogen and SO3 - , wherein at least 30% of the R' units are SO3 - ; and Q units are each independently selected from C1-C4 alkyl, H and a free electron pair, wherein at least 50% of the Q units are C1-C4 alkyl.

10. The composition according to claim 9, wherein in formula (II), at least 50% of the R' units are SO3 - .

11. The composition of claim 9, wherein in formula (II), at least 80% of the Q units are C1-C4 alkyl groups.

12. The composition of claim 9, wherein in formula (II), at least 90% of the Q units are C1-C4 alkyl groups.

13. The composition of claim 9, wherein the molar ratio of the amphiphilically modified oligopropyleneimine ethoxylate of formula (I) to the isomeric compound of formula (II) is at least 10:

1.

14. The composition according to any one of claims 1 to 6, further comprising a sulfate of an alkali metal and / or a sulfate of an amine.

15. A composition according to any one of claims 1 to 6 comprising 0.10 to 5 wt% of an amphiphilically modified oligopropyleneimine ethoxylate of formula (I).

16. A composition according to any one of claims 1 to 6 comprising 0.15 to 3 wt% of an amphiphilically modified oligopropyleneimine ethoxylate of formula (I).

17. A composition according to any one of claims 1 to 6 comprising from 5 to 30 wt% of one or more non-soap anionic surfactants.

18. A composition according to any one of claims 1 to 6 comprising from 0.05 to 5 wt% of one or more soil release polymers selected from copolyesters of dicarboxylic acids, diols and polyglycols.

19. A composition according to any one of claims 1 to 6, comprising: (i) 2 to 25 wt% of one or more linear alkylbenzene sulfonates; (ii) 2 to 20 wt% of one or more alkyl ether sulfates and / or 2 to 25 wt% of one or more nonionic surfactants which are fatty alcohol ethoxylates; (iii) 0.10 to 5 wt% of an amphiphilically modified oligopropyleneimine ethoxylate of formula (I); and (iv) 0.1 to 2 wt% of one or more soil release polymers selected from copolyesters of dicarboxylic acids, diols and polyglycols.

20. The composition of claim 19, wherein the composition comprises 0.15 to 3 wt% of the amphiphilically modified oligopropyleneimine ethoxylate of formula (I).

21. The composition according to any one of claims 1 to 6, further comprising 0.25% to 15 wt% of one or more fatty acids, said fatty acids being aliphatic carboxylic acids having a straight or branched alkyl or alkenyl chain containing 6 to 24 carbon atoms.

22. Use of a composition according to any one of claims 1 to 21 for removing soils from fabrics.

23. A method for removing soil from fabrics, comprising the following steps in sequence: (a) diluting a dose of a composition according to any one of claims 1 to 21 to obtain a wash liquor, wherein the dose is from 10 to 100 g; and (b) washing fabrics with the wash liquor thus formed.

24. A laundry product comprising a laundry composition according to any one of claims 1 to 21, wherein the composition is contained in a multi-dose package, or wherein the composition is contained in a unit dose package made of a polymer film adapted to be insoluble prior to addition to water.

25. The laundry product of claim 24, wherein the multi-dose package is a multi-dose package with dosing means.

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