Cleaning compositions with alkoxylated polyalkylenimines

[0001] The present invention relates to washing compositions and cleaning compositions comprising amphiphilic, water-soluble alkoxylated polyalkyleneimines having an internal polyethylene oxide block and an external polypropylene oxide block.

SUMMARY OF THE INVENTION [0002] A laundry detergent or cleaning composition that contains an amphiphilic, water-soluble alkoxylated polyalkyleneimine of general formula I

<img file="PL1869154T3_D0001.tif" />

in which variables are defined as follows:

R are identical or different, linear or branched C2-C6-alkylene radicals; B is a branch; E is an alkyleneoxy unit of formula

<img file="PL1869154T3_D0002.tif" />

R¹ is 1,2-propylene, 1,2-butylene and / or 1,2isobutylene; R² it's ethylene; R³ it's 1,2-propylene; R⁴ identical or different radicals: hydrogen; C1-C4-alkyl; x, y, z are from 2 to 150, with the sum of x + y + z representing the number of alkyleneimine units corresponding to the average molecular weight MW of the polyalkyleneimine before alkoxylation from 300 to 10,000; m is a rational number from 0 to 2; n is a rational number from 6 to 18; p is a rational number from to 12, where 0.8 &lt;n / p &lt;1.0 (x + y + z)^1/2 and products of their quaternization.

DETAILED DESCRIPTION OF THE INVENTION [0003] The present invention relates to laundry detergents and cleaning compositions that contain new amphiphilic, water-soluble alkoxylated polyalkyleneimines of general formula I:

<img file="PL1869154T3_D0003.tif" />

in which the variables are defined as follows:

R are identical or different, linear or branched C2-C6-alkylene radicals;

B is a branch;

E is an alkyleneoxy unit of formula

<img file="PL1869154T3_D0004.tif" />

R¹ is 1,2-propylene, 1,2-butylene and / or 1,2isobutylene;

R² it's ethylene;

R³ it's 1,2-propylene;

R⁴ identical or different radicals: hydrogen; Cl-C4 alkyl;

x, y, z are from 2 to 150, with the sum of x + y + z representing the number of alkyleneimine units corresponding to the average molecular weight Mw of the polyalkyleneimine before alkoxylation from 300 to 10,000;

m is a rational number from 0 to 2; n is a rational number from 6 to 18;

p is a rational number from 3 to 12, where 0.8 &lt;n / p &lt;

1.0 (x + y + z)^1/2;

and products of their quaternization.

[0004] Furthermore, the invention relates to the use of these alkoxylated polyalkyleneimines as additives to facilitate soil removal for laundry detergents and cleaning compositions.

[0005] In addition to surfactants, polymers are also used as additives to facilitate soil removal for laundry detergents and cleaning compositions. Known polymers are very useful, for example as soil pigment dispersants, such as clay minerals or carbon black, or as additives to prevent the redeposition of soil previously removed. Such dispersants, however, especially at low temperatures, generally ineffectively remove greasy dirt from the surface.

[0006] WO-A-99/67352 describes hydrophobic soil dispersants that can be used with peroxide-based bleaches and are intended to prevent re-deposition on cleaned fabrics of greasy soil removed during washing; they contain alkoxylated polyethyleneimines having an internal polypropylene oxide block and an external, much larger polyethylene oxide block.

[0007] US-A-5 565 145 recommends the use of neutral electrically alkoxylated polyethyleneimines, which may contain up to 4 propylene oxide units per active NH group connected directly to the nitrogen atom as dispersants for non-polar solids. A preferred and confirmed example, however, are polyethyleneimines which are only ethoxylated or at most weakly propoxylated (i.e. not more than 1 mol of propylene oxide per NH group).

[0008] Such alkoxylated polyethyleneimines are also good dispersants for hydrophilic soil pigments, however they do not give satisfactory washing results in the case of greasy stains.

[0009] Polyethyleneimines having an inner polyethylene oxide block and an outer polypropylene oxide block have hitherto not been used in washing or cleaning compositions.

[0010] US-A-4 076 497 discloses the use of initially ethoxylated and then propoxylated polyethyleneimines which have been reacted with a total of 30 moles of alkylene oxide, including at least 15 moles of propylene oxide per mole of active groups

NH to support the dyeing of polyester and cellulose fibers with dispersion dyes. However, the alkyleneoxy chains of the polyalkyleneimines of the invention contain at most 12 propyleneoxy units.

[0011] DE-A-22 27 546 discloses, in addition to polyethyleneimines having an reverse alkylene oxide sequence, also polyethyleneimines which were initially ethoxylated and then propoxylated to break up contaminated oily emulsions. However, compared to the polyalkyleneimines of the invention, these polyethyleneimines have a too high overall degree of alkoxylation of at least 105 mol of alkylene oxide per mole of alkoxylated NH groups and too high molar ratio of propylene oxide to ethylene oxide from 1.9 to 4: 1 (or conversely too low molar ratio of ethylene oxide to propylene oxide from 0.53 to 0.25).

[0012] JP-A-2003-020585 describes the use of alkoxylated polyethyleneimines in deinking processes. In addition to polyethyleneimines, which are preferably exclusively ethoxylated or optionally initially ethoxylated and subsequently alkoxylated by a mixture of ethylene oxide and propylene oxide, a product based on polyethyleneimine with an average molecular weight Mw 600 is also disclosed, which is reacted initially with 100 moles of ethylene oxide, and then with 100 moles propylene oxide per mole of alkoxylated NH groups, therefore, the amount of alkylene oxide is much higher than with the polyethyleneimines of the present invention.

[0013] Finally, EP-A-359 034 discloses agents supporting the preparation and stabilization of non-aqueous pigment dispersions based on at least two polyethyleneimines containing polyalkylene oxide blocks. If polyethyleneimines having an external higher alkylene oxide block are used, they are always initially ethoxylated and then butoxylated compounds, some of which contain a small central polypropylene oxide block. Polyethyleneimines having an internal polyethylene oxide block and an external polypropylene oxide block are always additionally reacted with at least one mole per mole of active NH groups of αolefin oxide (aC oxide₁₂/ C₁₄-, C.₁₆/ C₁₈- or C.₂₀-C₂₈olefins).

[0014] The object of the invention is to disclose polymers suitable as an additive to facilitate the removal of greasy soil from fabrics and hard surfaces for laundry detergents and cleaning compositions. In particular, polymers should have a significant greasy soil removal effect even at low washing temperatures.

[0015] Thus, amphiphilic, water-soluble, alkoxylated polyalkyleneimines of the general formula I were invented:

<img file="PL1869154T3_D0005.tif" />

in which the variables are defined as follows

R are identical or different, linear or branched C2-C6-alkylene radicals;

B is a branch;

E is an alkyleneoxy unit of formula

<img file="PL1869154T3_D0006.tif" />

R¹ is 1,2-propylene, 1,2-butylene and / or 1,2isobutylene;

R² it's ethylene;

R³ it's 1,2-propylene;

R⁴ identical or different radicals: hydrogen; C1-C4-alkyl;

x, y, z are from 2 to 150, wherein the sum of x + y + z is the number of alkyleneimine groups corresponding to the average molecular weight Mw of the polyalkyleneimine before alkoxylation from 300 to 10,000;

m is a rational number from 0 to 2; n is a rational number from 6 to 18;

p is a rational number from 3 to 12, where 0.8 &lt;n / p &lt;

1.0 (x + y + z)^1/2;

and products of their quaternization.

[0016] An essential property of the alkoxylated polyalkyleneimines of the invention is their amphiphilicity, i.e. they have a balanced ratio of hydrophobic and hydrophilic structural elements, so they are firstly sufficiently hydrophobic to absorb greasy soils and remove them together with surfactants and other washing syntaxes of laundry detergents and cleaning compositions, but secondly also sufficiently hydrophilic to maintain removed dirt greasy in the liquid for washing and cleaning and prevent their re-deposition on the surface.

[0017] This effect is achieved due to the fact that the alkoxylated polyethyleneimines have an internal polyethylene oxide block and an external polypropylene oxide block, the degree of ethoxylation and degree of propoxylation being not greater or less than certain limit values ​​with a ratio of at least 0.8 and in the range whose upper value according to the empirical formula n / p &lt;1.0 (x + y + z)^1/2 depends on the molecular weight of the polyalkyleneimine used.

[0018] Alkoxylated polyethyleneimines according to the invention have a basic backbone containing nitrogen atoms of primary, secondary and tertiary amines connected by R alkylene radicals in the form of the following groups in random order:

- primary amine moieties terminating the main chain and side chains of the basic skeleton, whose hydrogen atoms are then replaced by alkyleneoxy groups:

<img file="PL1869154T3_D0007.tif" />

- secondary amine moieties whose hydrogen atom is then replaced by alkyleneoxy units:

<img file="PL1869154T3_D0008.tif" />

tertiary amine moieties that are a branching of the main chain and side chains:

<img file="PL1869154T3_D0009.tif" />

[0019] Prior to alkylation, the polyalkyleneimine has an average molecular weight Mw of 300 to 10,000. The sum of x + y + of the repeating units of the primary, secondary and tertiary amines means the total number of alkyleneimine units corresponding to this molecular weight.

[0020] Preferably, the molecular weight Mw of the polyalkyleneimine is from 500 to 7500 and more preferably from 1000 to 6000.

[0021] The R radicals joining the amine nitrogen atoms can be identical or different, linear or branched C 2 -C 6 alkylene radicals. Preferred branched alkylene is 1.2 propylene. Ethylene is a particularly preferred alkylene radical.

[0022] Since cyclization is possible in forming the basic polyalkyleneimine skeleton, it is also possible for the basic skeleton to have a small amount of cyclic amine groups, which are obviously alkoxylated in the same way as the non-cyclic primary and secondary amino groups.

[0023] The hydrogen atoms of the primary and secondary amino groups of the basic polyalkyleneimine backbone are replaced with alkyleneoxy units of formula

<img file="PL1869154T3_D0010.tif" />

In this formula, variables are defined as follows:

R¹ is 1,2-propylene, 1,2-butylene or 1,2-isobutylene, preferably 1,2-propylene;

R² it's ethylene;

R³ it's 1,2-propylene;

R⁴ is hydrogen or C1-C4-alkyl, preferably hydrogen;

m is a rational number from 0 to 2; when m X 0, preferably about 1;

n is a rational number from 6 to 18;

p is a rational number from 3 to 12, where 0.8 &lt;n / p &lt;

1.0 (x + y + z)^1/2.

n and n are preferably defined as follows: n is a rational number from 7 to 15;

p is a rational number from 4 to 10, where 0.9 &lt;n / p &lt;

0.8 (x + y + z)^1/2.

NIPs are more preferably defined as follows:

n is a rational number from 8 to 12;

p is a rational number from 5 to 8, where 1.0 &lt;n / p &lt;

0.6 (x + y + z)^1/2.

[0024] A significant proportion of these alkyleneoxy units are ethyleneoxy units - (R²-O) n- and propyleneoxy units - (R³-O) p-.

[0025] Alkyleneoxy units may further additionally contain a small percentage of propyleneoxy or butyleneoxy units - (R¹-O) m-, i.e. polyalkyleneimine can be reacted initially with a small amount up to 2 moles, in particular 0.5 to 1.5 moles, in particular 0.8 to 1.2 moles propylene oxide or butylene oxide per mole current NH groups, i.e. weakly alkoxylated.

[0026] This modification of the polyalkyleneimine allows, if necessary, to reduce the viscosity of the alkoxylation reaction mixture. However, this modification does not substantially affect the performance of the alkoxylated polyalkyleneimine and is therefore not beneficial.

[0027] The alkoxylated polyalkyleneimines of the invention can also be quaternized. A suitable degree of accommodation is up to 50%, in particular 5 to 40%. The quaternization is preferably carried out by introducing C 1 -C 4 alkyl groups in a conventional manner by reaction with the corresponding alkyl halides and dialkyl sulfates.

[0028] Quaternization may be beneficial in adapting the alkoxylated polyalkyleneimines to the particular composition of the laundry detergent and cleaning composition in which they are to be used, and for better compatibility and / or phase stability of the formulation. Preferably, the alkoxylated polyalkyleneimines are not quaternized.

[0029] Alkoxylated polyalkyleneimines according to the invention can be obtained in a known manner.

[0030] One preferred method initially consists only of the weak alkoxylation of the polyalkyleneimine in the first step.

[0031] At this stage, the polyalkyleneimine is reacted only with a portion of the total amount of ethylene oxide used, corresponding to about 1 mole of ethylene oxide per mole of NH groups, or if the polyalkyleneimine is to be initially modified with 2 moles of propylene oxide or butylene oxide per mole of groups NH, also initially only with no more than 1 mole of this alkylene oxide.

[0032] The reaction is carried out essentially without a catalyst in an aqueous solution at a temperature of 70 to 200 ° C, preferably 80 to 160 ° C, at a pressure of up to 1 MPa (10 bar), in particular up to 0.8 MPa (8 bar) ).

[0033] In the second step, further alkoxylation is then carried out in a subsequent reaction i) with the remaining amount of ethylene oxide or, if in the first step the modification has been carried out with higher alkylene oxide, with all ethylene oxide and ii) with propylene oxide.

[0034] Further alkoxylation is usually carried out in the presence of a basic catalyst. Examples of suitable catalysts are alkali and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, in particular sodium and potassium C1-C4 alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkali and alkaline earth metal hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Alkali metal hydroxides and alkali metal alkoxides are preferred, potassium hydroxide and sodium hydroxide are particularly preferred. The amounts typically used as the base are from 0.05 to 10% by weight, in particular from 0.5 to 2% by weight, based on the total amount of polyalkyleneimine and alkylene oxide.

[0035] Further alkoxylation can be carried out in bulk (variant a) or in an organic solvent (variant b). The following process conditions can be used for ethoxylation and subsequent propoxylation.

[0036] In variant a, the aqueous solution of the weakly alkoxylated polyalkyleneimine obtained in the first step is usually dehydrated after adding the catalyst. This can be done simply by heating to 80 to 150 ° C and by distilling water under a reduced pressure of 1 to 50 kPa (0.01 to 0.5 bar). Subsequent reaction with alkylene oxide is generally carried out at a temperature of 70 to 200 ° C, preferably 100 to 180 ° C and pressure up to 1 MPa (10 bar), in particular up to 0.8 MPa (8 bar) with a time of constant stirring. from 0.5 to 4 hours at a temperature of approximately 100 to 160 ° C and constant pressure in each case.

[0037] A suitable reaction medium in option b are particularly non-polar and polar aprotic organic solvents. Examples of particularly suitable non-polar aprotic solvents are aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, toluene and xylene. Examples of particularly suitable polar aprotic solvents are ethers, in particular cyclic ethers such as tetrahydrofuran and dioxane, N, N-dialkylamides such as dimethylformamide and dimethylacetamide, and N-alkyl lactams such as N-methylpyrrolidone. Of course, it is also possible to use mixtures of these aprotic solvents. Preferred solvents are xylene and toluene.

[0038] Also in variant b, the solution obtained in the first step after the addition of the catalyst and solvent is initially dehydrated, which is preferably done by separating the water at a temperature of 120 to 180 ° C, preferably under a small stream of nitrogen. Subsequent reaction with alkylene oxide can be carried out as in variant a.

[0039] In variant a, the alkoxylated polyalkyleneimine is obtained directly in bulk and can be converted into an aqueous solution if desired. In variant b, the organic solvent is usually removed and replaced with water. Of course, products can also be isolated in bulk.

[0040] The alkoxylated polyalkyleneimines of the invention in the form of a 1% by weight solution in distilled water have a cloud point usually &lt;70 ° C, preferably &lt;65 ° C. The melting point is more preferably in the range of 25 to 55 ° C.

[0041] The alkoxylated polyalkyleneimines of the invention are ideally suited as additives to facilitate soil removal for laundry detergents and cleaning compositions. They have a strong dissolving effect, especially greasy soiling. It is particularly advantageous to remove dirt even at low washing temperatures.

[0042] Similarly, laundry detergents and cleaning compositions contain generally from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight and more preferably from 0.25 to

2.5% by weight based on the specific general composition of the alkoxylated polyalkyleneimines of the invention.

[0043] Furthermore, the laundry detergents and cleaning compositions generally contain surfactants and, if desired, other polymers as washing substances, fillers and other common ingredients, for example co-fillers, complexing agents, bleaches, normalizers, anti-graying agents, anti-separation agents dyes, enzymes and perfumes.

[0044] The alkoxylated polyalkyleneimines of the present invention can be used in laundry detergents and cleaning compositions comprising a surfactant system comprising C10-C15 alkyl benzene sulfonates (LAS) and one or more co-surfactants selected from nonionic, cationic, anionic and mixtures thereof. The choice of co-surfactant, preferably the co-surfactant, may depend on the desired benefit. In one embodiment, the co-surfactant is selected as a nonionic surfactant, preferably C12-C18 alkyl ethoxylate. In another embodiment, the co-surfactant is selected as anionic surfactant, preferably C12-C18 alkyl alkoxysulfate (AExS), where x is 1-30. In another embodiment, dimethylhydroxyethyl lauryl ammonium chloride is selected as the cationic surfactant.

If the surfactant system contains C10-C15 alkyl benzene sulfonates (LAS), LAS is used at a level of from about 9% to about 25% or from about 15% about 25 or from about 13 to about 23% by weight of the composition .

[0045] The surfactant system may contain from about 0% to about 7% or from about 0.1% to about 5% or from about 1% to about 4% by weight of a cosurfactant composition selected from a non-ionic cosurfactant, cationic cosurfactant, or any anionic cosurfactant. mixture.

[0046] Non-limiting examples of non-ionic co-surfactants include: ethoxylated C12-C18 alkyls, for example, NEODOL® non-ionic surfactants from Shell; alkoxylated C6-C12 alkylphenols, wherein the alkoxylated units are a mixture of ethyleneoxy and propyleneoxy units; C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethoxylated ethylene oxide and propylene oxide block alkyl polyamines, for example PLURONIC® from BASF; medium chain, branched C14-C22, BA alcohols, discussed in US 6150322; medium chain branched alkoxylated C14-C22 alkyl, BAEx, with x being 1-30, discussed in US 6153577, US 6020303 and US 6093856; alkyl polysaccharides discussed in US 4565647 Llenado, issued on January 26, 1986; in particular alkylpolyglycosides discussed in US 4483780 and US 4483779; polyhydroxy fatty acid amides discussed in US 5332528 and ether terminated poly (oxyalkylated) alcohol surfactants discussed in US

6482994 and WO 01/42408.

Non-limiting examples of semi-polar nonionic co-surfactants include: water-soluble amine oxides containing one alkyl group having from about 10 to about 18 carbon atoms and 2 groups selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl group having from about 10 to about 18 carbon atoms and 2 groups selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms and sulfoxides soluble in water, containing one alkyl group having from about 10 to about 18 carbon atoms and a group selected from the group consisting of alkyl and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms. See WO 01/32816, US 4681704 and US 4133779.

[0048] Non-limiting examples of cationic co-surfactants include: carbon quaternary ammonium surfactants, such as: alkoxylated (AQA) surfactants discussed in US dimethyl hydroxyethyl quaternary ammonium in 6004922; chloride having up to 26 quaternary ammonium atoms 6136769;

dimethylhydroxyethyl lauryl ammonium discussed; polyamine cationic surfactants discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO

98/35005 and WO 98/35006; cationic ester surfactants discussed in US Patent Nos. 4228042, 4239660, 4260529 and US 6022844 and the amine surfactants discussed in US 6221825 and WO 00/47708, especially amidopropyl dimethylamine (APA).

Non-exclusive useful branched anionic include:

C10-C20 [0049] co-surfactants primary examples of the invention random in

and alkyl sulfates (AS); secondary (2.3) C10-C18 alkyl sulfates; C10-C18 alkylalkoxysulfates (AExS), wherein x is from 1 to 30; C10-C18 alkyl alkylalkoxycarboxylates containing 1-5 ethoxy mono-units; medium chain branched alkyl sulfates discussed in US 6020303 and US 6060443; medium chain branched alkyl alkoxy sulfates discussed in US 6008181 and US 6020303; modified alkyl benzene sulfonate (MLAS) discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES) and alpha-olefin sulfonate (AOS).

[0050] The present invention relates to compositions comprising the alkoxylated polyalkyleneimines of the invention and a surfactant system comprising a C8-C18 linear sulfonate surfactant and a co-surfactant. The compositions may be in any form, namely, in the form of liquids, solids, such as powder, granules, agglomerates, pastes, tablets, sachet, cubes, gel, emulsions, products delivered in two-part containers, spray or foam detergent, wet wipes ( ie. a cleaning composition in combination with a non-woven material, e.g. as discussed in US 6121165, Mackey, et al.), dry wipes (i.e. a cleaning composition in combination with a nonwoven fabric, e.g. as discussed in US 5980931, Fowler, et al.) activated by the consumer by water and in other homogeneous or multiphase forms of consumer cleaning products.

[0051] In one embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition. In another embodiment, the cleaning composition of the present invention is a solid surface cleaning composition, preferably wherein the solid surface cleaning composition soaks the nonwoven substrate. The term "soak" means that the composition for cleaning solid surfaces of the nonwoven composition is placed in contact with the nonwoven substrate, such that at least a portion of the nonwoven substrate is soaked by the solid surface cleaning composition, preferably for cleaning solid surfaces, saturates the substrate. The cleaning composition can also be used in vehicle care compositions for cleaning various surfaces, such as hardwood, tiles, ceramics, plastics, leather, metal, glass. The cleaning composition can also be formulated for use in personal hygiene or pet hygiene compositions, such as shampoo compositions, body washes, liquid and solid soaps, and other cleaning compositions in which the surfactant is in contact with free hardness and all compositions requiring a hardness-resistant surfactant system such as drilling compositions.

[0052] In another embodiment, the cleaning composition is a dishwashing composition, e.g., manual dishwashing compositions, solid compositions, liquid cube compositions / unit doses of automatic dishwashing, automatic dishwashing and automatic dishwashing compositions. [0053] typically the present cleaning compositions, such as laundry detergents, laundry detergent additives, hard surface cleaners, synthetic and soap washing cubes, fabric softeners and fabric fluids, solids and care products of all types, require a number of additives, although simple composition products such as bleach additives may only require, for example, an oxygen containing detergent and a surfactant featured in the document. A full list of suitable washing or cleaning additives is provided in WO 99/05242.

[0054] fillers,

Typical cleaning additives include those not mentioned above, similar other enzyme enhancers, bleach polymers, bleach activators, and catalysts in addition to the materials defined above. These cleaning additives include the production of suds, suds reducing agents (antifoams) and the like, various active substances or special materials such as dispersing polymers (e.g. from BASF Corp. or Rohm &amp; Haas) other than those described above, colored granules, silver containing agents, anti-tarnish and / or anti-corrosive agents, dyes, fillers, bactericides, sources of alkalinity, hydrotropes, antioxidants, enzyme stabilizing agents, production agents perfumes, solubilizers, carriers, processing aids, pigments and, for liquid preparations, solvents, chelating agents, anti-dye inhibitors, dispersants, brighteners, soap-reducing agents, dyes, elasticizers, fabric softeners, abrasion reducing agents, hydrotropes, processing aids and other fabric, surface and skin care products. Suitable examples of such other cleaning additives and levels of their use are given in US Patent Nos. 5576282, 6306812 B1 and 6326348 B1.

Method of application [0055] The present invention relates to a method of cleaning a suitable surface area. The term "suitable as used herein may include surfaces such as textiles, dishes, glass and other kitchen surfaces, hard surfaces, hair or skin. The term "hard surface" as used herein includes surfaces in a typical household, for example hard wood, tiles, ceramics, plastics, leather, metal, glass. Such a method comprises the steps of contacting a composition comprising a modified polyol pure or diluted in a wash liquid with at least part of a suitable surface, followed by optionally rinsing the appropriate surface. Preferably, a suitable surface is subjected to a washing step prior to the above optional rinsing step. the invention includes washing between wiping and mechanical mixing.

For the purposes of other scrubbing, [0056] The skilled person will know that the cleaning compositions of the present invention are well suited for use at home (hard surface cleaning compositions), for personal hygiene and / or laundry.

[0057] The pH of the composition solution is selected so that it best corresponds to the corresponding surface being cleaned; has a wide pH range from about 5 to about 11. Preferably, the pH of the personal care composition (e.g., for washing skin and hair) is from about 5 to about 8, and the laundry composition is from about 8 to about 10. Preferably, when the compositions are used in a concentration of from about 200 ppm to about 10,000 ppm in solution. The water temperature is preferably from about 5 ° C to about 100 ° C.

[0058] Preferably, the washing compositions are used in a concentration of from about 200 ppm to about 10,000 ppm in solution (or in the washing liquid). The water temperature is preferably from about 5 ° C to about 60 ° C. The water to fabric ratio is preferably from about 1: 1 to about 20: 1.

[0059] The method may include the step of contacting a nonwoven substrate soaked in an embodiment of the composition of the present invention. The term "non-woven substrate" may mean in the document any sheet or non-woven mesh of appropriate weight, thickness, absorbency and strength. Examples of suitable commercially available nonwoven substrates are products under the trade names SONTARA® from DuPont and POLYWEBC from James River Corp.

[0060] The skilled person will know that the cleaning compositions of the present invention are well suited for use in liquid dishwashing compositions. The method of using the liquid dishwashing composition of the present invention includes the steps of contacting dirty dishes with an effective amount, usually from about 0.5 ml to about 20 ml (on washed dishes) of the liquid dishwashing composition of the present invention diluted in water.

Examples [0061] Preparation of alkoxylated polyalkyleneimines according to the invention

Example 1

Poor ethoxylation [0062] In a 2 L autoclave, a 50% by weight aqueous solution of polyethyleneimine 5000 (average molecular weight MW 5000) was heated to 80 ° C and purged with nitrogen three times to 0.5 MPa (5 bar). The temperature was increased to 90 ° C and 461 g of ethylene oxide was added to a pressure of 0.5 MPa (5 bar). The mixture was stirred for another hour at 90 ° C under a constant pressure of 0.5 MPa (5 bar). Volatile fractions were removed by nitrogen purge.

[0063] 1345 g of a 68% by weight aqueous solution of polyethyleneimine 5000 containing 1 mole of ethylene oxide per mole of NH bond were obtained.

a) Ethoxylation and mass propoxylation [0064] In a 2 L autoclave, 163 g of the aqueous solution obtained in the low ethoxylation step and 13.9 g of a 40% by weight aqueous potassium hydroxide solution were heated to 70 ° C. After purging with nitrogen three times (to achieve a pressure of 0.5 MPa (5 bar)), the mixture was dehydrated at 120 ° C under a reduced pressure of 1 kPa (10 mbar) for 4 h. Then 506 g of ethylene oxide at 120 ° C was added to a pressure of 0, 8 kPa (8 bar). The mixture was stirred for 4 h at 120 ° C and 0.8 MPa (8 bar). After decompression and nitrogen purge, 519 g of propylene oxide were added at 120 ° C to a pressure of 0.8 kPa (8 bar). The mixture was again stirred for another 4 h at 120 ° C and 0.8 MPa (8 bar). Volatile fractions were removed by nitrogen purge.

[0065] 1178 g of polyethyleneimine 5000 containing 10 mole of ethylene oxide and 7 mole of propylene oxide per mole of NH bond were obtained in the form of a light brown viscous liquid (amine titer: 0.9276 mmol / g; pH of 1% by weight aqueous solution: 10.67) .

b) Ethoxylation and propoxylation in xylene [0066] In a 2 L autoclave 137 g of aqueous solution obtained in the low ethoxylation step, 11.8 g of a 40% by weight potassium hydroxide aqueous solution and 300 g of xylene was purged three times with nitrogen to a pressure of 0.5 MPa (5 bar). At a jacket temperature of 175 ° C, water was separated using a water separator in a small stream of nitrogen for 4 h. Then 428 g of ethylene oxide at 120 ° C was added to a pressure of 0.3 kPa (3 bar). The mixture was stirred for another 2 h at 120 ° C at a constant pressure of 0.3 MPa (3 bar). Then 439 g propylene oxide was added at 120 ° C to a pressure of 0.3 kPa (3 bar). The mixture was stirred for another 3 h at 120 ° C and 0.3 MPa (3 bar). After removal of the solvent under reduced pressure of 1 kPa (10 mbar), the alkoxylation product was removed with 0.4 MPa (4 bar) steam at 120 ° C for 3 h.

[0067] 956 g of polyethyleneimine 5000 containing 10 mole of ethylene oxide and 7 mole of propylene oxide per mole of NH bond were obtained in the form of a light brown viscous liquid (amine titer: 0.9672 mmol / g; pH of 1% by weight aqueous solution: 10.69).

Example 2 [0068] In a 2 L autoclave, 321 g of 69.2 wt% aqueous solution of polyethyleneimine 5000 (1 mole of ethylene oxide per mole of NH bonds) were heated to 80 ° C, obtained in the low ethoxylation step analogously to Example 1 and 28 g % by weight of aqueous potassium hydroxide solution. After purging with nitrogen three times (until a pressure of 0.5 MPa (5 bar) is obtained), the mixture was dehydrated at 120 ° C under 1 kPa (10 mbar) vacuum for 3 h. Then 1020 g of ethylene oxide was added at 120 ° C to a pressure of 0.8 kPa (8 bar). The mixture was stirred at 120 ° C and 0.8 kPa (8 bar) for another 4 h. The volatile fractions were removed by nitrogen purge.

[0069] 1240 g of polyethyleneimine 5000 containing 9.9 moles of ethylene oxide per mole of NH bonds were obtained in the form of a brown viscous solution (amine titer:

1.7763 mmol / g; pH 1% by weight of aqueous solution: 11.3).

[0070] Then, after purging with nitrogen three times (up to a pressure of 0.5 MPa (5 bar)), 239 g of the ethoxylation product was reacted at 120 ° C with approx. 87 g of propylene oxide (measurement precision +/- 15 g) to a pressure of 0 , 8 kPa (8 bar). The mixture was then stirred at 120 ° C and 0.8 kPa (8 bar) for 4 h. The volatiles were removed by purging with nitrogen at 80 ° C or under a poor vacuum of 50 kPa (500 mbar).

[0071] 340 g of polyethyleneimine 5000 was obtained, containing 9.9 moles of ethylene oxide and 3.5 moles of propylene oxide per mole of NH bonds as a light brown viscous liquid (amine titer: 1.2199 mmol / g; pH of 1% by weight aqueous solution: 11.05).

Example 3

Weak ethoxylation [0072] In a 2 L autoclave, a mixture of 516 g polyethyleneimine 600 (average molecular weight Mw 600) and

10.3 g of water was purged three times with nitrogen to a pressure of 0.5 MPa (5 bar) and heated to 90 ° C. Then 528 g ethylene oxide was added at 90 ° C. The mixture was stirred for another 1 h at 90 ° C at a constant pressure of 0.5 MPa (5 bar). Volatile fractions (especially water) were removed by nitrogen purge.

[0073] 1040 g of polyethyleneimine 600 containing 1 mole of ethylene oxide per mole of NH bond were obtained in the form of a brown liquid.

Ethoxylation and mass propoxylation [0074] In a 2 L autoclave, 86 g of poorly ethoxylated polyethyleneimine 600 and 10.8 40% by weight aqueous potassium hydroxide solution were heated to 80 ° C. After purging with nitrogen three times (to achieve a pressure of 0.5 MPa (5 bar)), the mixture was dehydrated at 120 ° C under 1 kPa (10 mbar) for 2.5 h. After removing the vacuum with nitrogen, 384 g of ethylene oxide in 120 was added ° C. The mixture was stirred for another 2 h at 120 ° C. After decompression and nitrogen purge, 393 g of propylene oxide were added at 120 ° C. The mixture was again stirred for another 2 h at 120 ° C. Volatile fractions were removed by nitrogen purge.

[0075] 865 g polyethyleneimine 600 containing mole ethylene oxide and 7 mole propylene oxide per mole of bonds were obtained.

NH as a light brown viscous liquid (amine titer: 1.0137 mmol / g; pH 1% by weight of aqueous solution: 11.15).

Example 4 7.3 g of dimethyl sulfate was added dropwise to 300 g of the alkoxylated polyethyleneimine 5000 obtained in Example 1b) and stirred at 60 ° C under nitrogen. During the reaction the temperature rose to 70 ° C. The mixture was stirred for another 3 h at 70 ° C and the mixture was cooled to room temperature.

[0077] 307 g of polyethyleneimine 5000 containing 10 moles of ethylene oxide and 7 moles of propylene oxide per mole of NH bonds with a quaternization degree of 22% was obtained in the form of a brown viscous liquid (amine titer: 0.7514 mmol / g).

Composition compositions

Example 5 - laundry detergent (granules)

<td></td><td>AND</td><td>B</td><td>C</td><td>D</td><td>E</td>

<td></td><td>wt%</td><td>wt%</td><td>wt%</td><td>wt%</td><td>wt%</td>

<td>Linear C.₁₁-₁₂alkyl benzene sulfonate</td><td> 13-25</td><td> 13-25</td><td> 13-25</td><td> 13-25</td><td> 9-25</td>

<td>Ethoxylated C.₁₂-₁₈ sulfate</td><td> —</td><td> —</td><td> 0-3</td><td> —</td><td> 0-1</td>

<td>Ethoxylated C.₁₄-₁₅ alkyl (EO = 7)</td><td> 0-3</td><td> 0-3</td><td> —</td><td> 0-5</td><td> 0-3</td>

<td>Chloride dimetylohydroksyetylolauryloamo cherry</td><td></td><td></td><td> 0-2</td><td> 0-2</td><td> 0-2</td>

<td>Sodium tripolyphosphate</td><td> 20-40</td><td> —</td><td> 18-33</td><td> 12-22</td><td> 0-15</td>

<td>Zeolite</td><td> 0-10</td><td> 20-40</td><td> 0-3</td><td> —</td><td> —</td>

<td>Silicate filler</td><td> 0-10</td><td> 0-10</td><td> 0-10</td><td> 0-10</td><td> 0-10</td>

<td>Carbonate</td><td> 0-30</td><td> 0-30</td><td> 0-30</td><td> 5-25</td><td> 0-20</td>

<td>Diethylenetriamine pentaacetate</td><td> 0-1</td><td> 0-1</td><td> 0-1</td><td> 0-1</td><td> 0-1</td>

<td>polyacrylate</td><td> 0-3</td><td> 0-3</td><td> 0-3</td><td> 0-3</td><td> 0-3</td>

<td>carboxymethylcellulose</td><td> 0,2-0,8</td><td> 0,2-0,8</td><td> 0,2-0,8</td><td> 0,2-0,8</td><td> 0,2-0,8</td>

<td>Polymer¹</td><td> 0,05-10</td><td> 0,05-10</td><td> 5,0</td><td> 2,5</td><td> 1,0</td>

<td>percarbonate</td><td> 0-10</td><td> 0-10</td><td> 0-10</td><td> 0-10</td><td> 0-10</td>

<td>nonanoyloxybenzenesulfonate</td><td> —</td><td> —</td><td> 0-2</td><td> 0-2</td><td> 0-2</td>

<td>tetraacetylethylenediamine</td><td> —</td><td> —</td><td> 0-0, 6</td><td> 0-0, 6</td><td> 0-0, 6</td>

<td>Zinc phthalocyanine tetrasulphonate</td><td> —</td><td> —</td><td> 0-0,005</td><td> 0-0,005</td><td> 0-0,005</td>

<td>brightener</td><td> 0, 05-</td><td> 0,05-</td><td> 0,05-</td><td> 0,05-</td><td> 0,05-</td>

<td></td><td> 0,2</td><td> 0,2</td><td> 0,2</td><td> 0,2</td><td> 0,2</td>

<td>MgSO₄</td><td> —</td><td> —</td><td> 0-0,5</td><td> 0-0,5</td><td> 0-0,5</td>

<td>enzymes</td><td> 0-0,5</td><td> 0-0,5</td><td> 0-0,5</td><td> 0-0,5</td><td> 0-0,5</td>

<td>Other substances (perfumes,</td><td>Down</td><td>Down</td><td>Down</td><td>Down</td><td>Down</td>

<td>dyes, suds stabilizers)</td><td> 100 %</td><td> 100 %</td><td> 100 %</td><td> 100 %</td><td> 100 %</td>

Ί ¹ The alkoxylated polyalkyleneimine polymer or any polymer mixture according to one of examples 1, 2, 3 or 4.

Example 6 - laundry detergent (liquid)

<td>Ingredient</td><td>AND</td><td>B</td><td>C</td><td>D</td><td>E</td><td>F</td>

<td></td><td>wt%</td><td>wt%</td><td>wt%</td><td>wt%</td><td>wt%</td><td>wt%</td>

<td>Sodium alkyl ether sulfate</td><td> 14,4 %</td><td> 14,4 %</td><td></td><td> 9,2 %</td><td> 5,4 %</td><td></td>

<td>Linear alkylbenzene sulfonic acid</td><td> 4,4 %</td><td> 4,4 %</td><td> 12,2 %</td><td> 5,7 %</td><td> 1,3 %</td><td></td>

<td>Ethoxylated alkyl</td><td> 2,2 %</td><td> 2,2 %</td><td> 8,8 %</td><td> 8,1 %</td><td> 3,4 %</td><td></td>

<td>Amine Oxide</td><td> 0,7 %</td><td> 0,7 %</td><td> 1,5 %</td><td></td><td></td><td></td>

<td>Citric acid</td><td> 2,0 %</td><td> 2,0 %</td><td> 3,4 %</td><td> 1,9 %</td><td> 1,0 %</td><td> 1,6 %</td>

<td>Fatty acid</td><td> 3,0 %</td><td> 3,0 %</td><td> 8,3 %</td><td></td><td></td><td> 16,0 %</td>

<td>protease</td><td> 1,0 %</td><td> 1,0 %</td><td> 0,7 %</td><td> 1,0 %</td><td></td><td> 2,5 %</td>

<td>amylase</td><td> 0,2 %</td><td> 0,2 %</td><td> 0,2 %</td><td></td><td></td><td> 0,3 %</td>

<td>lipase</td><td></td><td></td><td></td><td> 0,2 %</td><td></td><td></td>

<td>Borax</td><td> 1,5 %</td><td> 1,5 %</td><td> 2,4 %</td><td> 2,9 %</td><td></td><td></td>

<td>Calcium and sodium formate</td><td> 0,2 %</td><td> 0,2 %</td><td></td><td></td><td></td><td></td>

<td>Formic acid</td><td></td><td></td><td></td><td></td><td></td><td> 1,1 %</td>

<td>Polymer¹</td><td> 1,8 %</td><td> 1,8 %</td><td> 2,1 %</td><td></td><td></td><td> 3,2 %</td>

<td>Sodium polyacrylate</td><td></td><td></td><td></td><td></td><td> 0,2 %</td><td></td>

<td>Sodium polyacrylate copolymer</td><td></td><td></td><td></td><td> 0,6 %</td><td></td><td></td>

<td>DTPA²</td><td> 0,1 %</td><td> 0,1 %</td><td></td><td></td><td></td><td> 0,9 %</td>

<td>DTPMP³</td><td></td><td></td><td> 0,3 %</td><td></td><td></td><td></td>

<td>EDTA⁴</td><td></td><td></td><td></td><td></td><td> 0,1 %</td><td></td>

<td>Fluorescent whitening agent</td><td> 0,15 %</td><td> 0,15 %</td><td> 0,2 %</td><td> 0,12 %</td><td> 0,12 %</td><td> 0,2 %</td>

<td>Ethanol</td><td> 2,5 %</td><td> 2,5 %</td><td> 1,4 %</td><td> 1,5 %</td><td></td><td></td>

<td>propanediol</td><td> 6,6 %</td><td> 6,6 %</td><td> 4,9 %</td><td> 4,0 %</td><td></td><td> 15,7 %</td>

<td>sorbitol</td><td></td><td></td><td></td><td> 4,0 %</td><td colspan="2"></td>

<td>ethanolamine</td><td> 1,5 %</td><td> 1,5 %</td><td> 0,8 %</td><td> 0,1 %</td><td></td><td> 11,0 %</td>

<td>Sodium hydroxide</td><td> 3,0 %</td><td> 3,0 %</td><td> 4,9 %</td><td> 1,9 %</td><td> 1,0 %</td><td></td>

<td>Sodium cumene sulfonate</td><td></td><td></td><td> 2,0 %</td><td></td><td></td><td></td>

<td>Silicone soap-inhibiting agent</td><td></td><td></td><td> 0, 01 %</td><td></td><td></td><td></td>

<td>Perfume</td><td> 0,3 %</td><td> 0,3 %</td><td> 0,7 %</td><td> 0,3 %</td><td> 0,4 %</td><td> 0,6 %</td>

<td>opacifier⁵</td><td></td><td></td><td> 0,30 %</td><td> 0,20 %</td><td></td><td> 0,50 %</td>

<td>Water</td><td>Down</td><td>Down</td><td>Down</td><td>Down</td><td>Down</td><td>Down</td>

<td></td><td> 100,0 %</td><td> 100,0 %</td><td> 100,0 %</td><td> 100,0 %</td><td> 100,0 %</td><td> 100,0 %</td>

Ί ¹ The alkoxylated polyalkyleneimine polymer or any polymer mixture according to one of examples 1, 2, 3 or 4.

² Diethylenetriaminepentaacetic acid, sodium salt ³ Diethylenetriaminepentacismethylene phosphonic acid, sodium salt 5 ⁴ Diethylenediamine tetraacetic acid, sodium salt ⁵ Acusol OP 301

Example 7 - dishwashing detergents (liquid)

<td>Composition</td><td>AND</td><td>B</td>

<td>C₁₂-₁₃ natural AE0.6S</td><td> 29,0</td><td> 29,0</td>

<td>Medium branched oxide C₁₀-₁₄ amine</td><td> —</td><td> 6,0</td>

<td>Linear oxide C₁₂-₁₄ amine</td><td> 6,0</td><td> —</td>

<td>SAFOL® amine oxide 23</td><td> 1,0</td><td> 1,0</td>

<td>₂C₁₁E₉ nonionic</td><td> 2,0</td><td> 2,0</td>

<td>Ethanol</td><td> 4,5</td><td> 4,5</td>

<td>Polymer¹</td><td> 5,0</td><td> 2,0</td>

<td>Sodium cumene sulfonate</td><td> 1,6</td><td> 1,6</td>

<td>2000 polypropylene glycol</td><td> 0,8</td><td> 0,8</td>

<td>NaCl</td><td> 0, 8</td><td> 0, 8</td>

<td>1.3 BAC diamine³</td><td> 0,5</td><td> 0,5</td>

<td>Polymer increasing the production of suds⁴</td><td> 0,2</td><td> 0,2</td>

<td>Water</td><td>Up to 100%</td><td>Up to 100%</td>

¹ Alkoxylated polyalkyleneimine polymer or any polymer blend according to one of examples 1, 2, 3 or 4.

² Nonionic: C11 alkyl ethoxylated surfactant containing 9 ethoxy groups ³ 1,3, BAC is 1,3 bis (methylamino) -cyclohexane ⁴ (N, N-dimethylamino) ethyl methacrylate homopolymer

Example 8 - automatic dishwashing detergent

<td></td><td>AND</td><td>B</td><td>C</td><td>D</td><td>E</td>

<td>Polymer - dispersant²</td><td> 0,5</td><td> 5</td><td> 6</td><td> 5</td><td> 5</td>

<td>Carbonate</td><td> 35</td><td> 40</td><td> 40</td><td> 35-40</td><td> 35-40</td>

<td>Sodium tripolyphosphate</td><td> 0</td><td> 6</td><td> 10</td><td> 0-10</td><td> 0-10</td>

<td>Silicate filler</td><td> 6</td><td> 6</td><td> 6</td><td> 6</td><td> 6</td>

<td>Bleach and bleach activators</td><td> 4</td><td> 4</td><td> 4</td><td> 4</td><td> 4</td>

<td>Polymer¹</td><td> 0,05-10</td><td> 1</td><td> 2,5</td><td> 5</td><td> 10</td>

<td>enzymes</td><td> 0,3-0,6</td><td> 0,3-0,6</td><td> 0,3-0,6</td><td> 0,3-0,6</td><td> 0,3-0,6</td>

<td>Disodium citrate dihydrate</td><td> 0</td><td> 0</td><td> 0</td><td> 2-20</td><td> 0</td>

<td>Nonionic surfactant³</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0,8-5</td>

<td>Water, sulfate, perfumes, dyes and other ingredients</td><td>down 100%</td><td>down 100%</td><td>down 100%</td><td>down 100%</td><td>down 100%</td>

Ί ¹ The alkoxylated polyalkyleneimine polymer or any polymer mixture according to one of examples 1, 2, 3 or 4.

² For example, ACUSOL® 445N from Rohm &amp; Haas or ALCOSPERSE® from Alco.

³ For example, SLF-18 POLY TERGENT from Olin Corporation.

Example 9 - use of the alkoxylated polyalkyleneimines according to the invention for laundry [0078] To test the dirt removal efficiency of the alkoxylated polyalkyleneimines, they were added to the washing liquid in three series of experiments together with surfactants and fillers specified in Table 1 as model laundry detergents or with laundry detergent available in sales. Then, the test fabrics from table 2 were washed under the washing conditions given in tables 3a, 4a and 5a.

[0079] Removal of soils from test fabrics was determined by subjecting test fabrics to a reflectance measurement at 460 nm before and after washing. Soil removal was calculated based on the reflectance value R before and after washing, as well as the value for the reference white cotton fabric using the following formula (in%):

Soiling removal [%] = R (after washing) - R (before washing) x

100

R (white cotton) - R (before washing) [0080] All washes were carried out twice. The soil removal values ​​in the washing results in Tables 3b, 4b and 5b correspond to the average measured values ​​obtained under the same conditions. Values ​​obtained respectively without the addition of a polymer are given for comparison purposes.

[0081] All amounts are based on 100% active substance.

Table 1: Surfactants and filler

<td>Surfactant 1</td><td>Lutensit® A-LBN 50 (BASF; linear C12alkylbenzenesulfonate (Na salt))</td>

<td>Surfactant 2</td><td>Plurafac® LF 401 (BASF; alkoxylated fatty alcohol)</td>

<td>extender</td><td>Sodium tripolyphosphate</td>

Table 2: Test fabrics

<td>TG 1</td><td>Triolein dyed with Sudanese red: 0.2 g stains per 5 g of white cotton fabric</td>

<td>TG 2</td><td>Olive oil stained with Sudanese red: 0.2 g stain on 5 g of white cotton fabric</td>

<td>TG 3</td><td>WFK 10D (sebum and pigment dirt from WFK *)</td>

<td>TG 4</td><td>EMPA118 (tallow and pigment dirt from EMPA **)</td>

<td>TG 5</td><td>Tallow Scientific Services ***</td>

<td>TG 6</td><td>WFK 10PF (fabric contaminated with vegetable fat and WFK pigment)</td>

<td>TG 7</td><td>CFT-CS10 (colored butter on cotton fabric with CFT ****)</td>

<td>TG 8</td><td>CFT-CS 62 (colored pork fat on CFT cotton fabric)</td>

<td></td><td></td>

<td> *</td><td>Cleaning Technology Research Institute, Krefeld</td>

<td> **</td><td>Swiss Institute of Materials Research, St. Gallen, CH</td>

<td> ***</td><td>Scientific Services S / D, Inc., Sparrow Bush, NY, USA</td>

<td> ****</td><td>Center for Test Materials BV, Vlaardingen, NL</td>

Table 3a: Washing conditions

<td>Device</td><td>Launder-O-Meter (Atlas, Chicago, USA)</td>

<td>Washing temperature</td><td>25 ° C</td>

<td>Polymer dose</td><td>30 mg / l</td>

<td>Laundry detergent</td><td>Model laundry detergent: surfactant 1 / filler</td>

<td>Surfactant dose</td><td>300 mg / l</td>

<td>Dose of filler</td><td>200 mg / l</td>

<td>Water hardness</td><td>2.5 mmol / l Ca: Mg 3: 1</td>

<td>Liquid ratio</td><td> 12,5:1</td>

<td>Washing time</td><td>30 minutes</td>

<td>Fabrics tested</td><td>TG 1 and TG 2 Each test fabric was washed separately with another 5 g of white cotton fabric per dish.</td>

Table 3b: Washing results

<td rowspan="2">Polymer</td><td colspan="2">Removing dirt [%]</td>

<td>TG 1</td><td>TG 2</td>

<td>from example 3</td><td> 42,6</td><td> 38,4</td>

<td>no additions</td><td> 38,5</td><td> 32,4</td>

Table 4a: Washing conditions

<td>Device</td><td>Launder-O-Meter (Atlas, Chicago, USA)</td>

<td>Washing temperature</td><td>25 ° C</td>

<td>Polymer dose</td><td>25 mg / l</td>

<td>Laundry detergent</td><td>Model laundry detergent: surfactant 1 / filler 2</td>

<td>Surfactant dose 1</td><td>150 mg / l</td>

<td>Surfactant dose 2</td><td>50 mg / l</td>

<td>Water hardness</td><td>1.0 mmol / l Ca: Mg 3: 1</td>

<td>Liquid ratio</td><td> 12,5:1</td>

<td>Washing time</td><td>30 minutes</td>

<td>Fabrics tested</td><td>TO 3, TG 4, TG 6, TG 7 and TG 8 4 x 4 cm pieces were cut from the soiled fabrics and sewn to white cotton. In every case 2 cotton fabrics sewn on fabrics TG 3, TG 4 and TG 6, as well as 2 fabrics cotton with sewn fabrics TG 7 and TG 8 were washed together. Added to each wash 5 g of white cotton fabric.</td>

Table 4b: Washing results

<td rowspan="2">Polymer</td><td colspan="5">Removing dirt [%]</td>

<td>TG 3</td><td>TG 4</td><td>TG 6</td><td>TG 7</td><td>TG 8</td>

<td>from example 3</td><td> 29,7</td><td> 8,2</td><td> 48,1</td><td> 6, 6</td><td> 3,9</td>

<td>no additions</td><td> 29,4</td><td> 6,8</td><td> 47,4</td><td> 5,9</td><td> 2,5</td>

Table 5a: Washing conditions

<td>Device</td><td>Launder-O-Meter (Atlas, Chicago, USA)</td>

<td>Washing temperature</td><td>25 ° C</td>

<td>Polymer dose</td><td>(1) 20 mg / l; (2) 40 mg / l</td>

<td>Laundry detergent</td><td>Tide liquid (Procter &amp; Gamble)</td>

<td>A dose of laundry detergent</td><td>1 g / l</td>

<td>Water hardness</td><td>1.0 mmo1 / l Ca: Mg 3: 1</td>

<td>Liquid ratio</td><td> 12,5:1</td>

<td>Washing time</td><td>30 minutes</td>

<td>Fabrics tested</td><td>TG 3, TG 4, TG 5 and TG 6 4x4 cm pieces were cut from the soiled fabric and sewn to white cotton. In each case 2 cotton fabrics with sewn dirty fabric were washed together. In addition, 5 g of white cotton fabric was added to each wash.</td>

Table 5b: Washing results

<td>Polymer</td><td colspan="3">Removing dirt</td><td> [%]</td>

<td></td><td>TG 3</td><td>TG 4</td><td>TG 5</td><td>TG 6</td>

<td>from example 3 (20 mg / l)</td><td> 39, 6</td><td> 7,6</td><td> 31, 4</td><td> 50, 0</td>

<td>from example 3 (40 mg / l)</td><td> 40,2</td><td> 8,2</td><td> 32,1</td><td> 50,6</td>

<td>no additions</td><td> 37,2</td><td> 5,4</td><td> 28,5</td><td> 44, 4</td>

[0082] The results of the washing tests indicate that the addition of alkoxylated polyalkyleneimines according to the invention leads to a significant improvement in the removal of soiling from the cotton fabric in relation to oily and oily stains.

[0083] Unless otherwise stated, all levels of ingredients or compositions refer to the active level of the ingredient or composition and do not take into account impurities, for example residual solvents or by-products, which may be in commercially available products.

[0084] Unless otherwise specified, all percentages and ratios were calculated by weight. Unless otherwise specified, all percentages and ratios were calculated relative to the total composition.

[0085] It should be understood that each maximum numerical limit specified herein includes any lower numerical limit, as if such lower numerical limits were explicitly stated. Any minimum numerical limit specified in the description includes any higher numerical limit, as if such higher numerical limitations were explicitly stated. Each numerical range given in the description includes every narrower numerical range within a wider range, as if all such narrower ranges were explicitly stated.

[0086] Although specific embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the scope of the invention.

The appended claims are therefore intended to cover all changes and modifications within the scope of the present invention.