ES2556490T3 - Laundry detergent compositions comprising polyalkoxylated polyethyleneimine - Google Patents

Abstract

A laundry detergent composition containing from 5 to 30% by weight of detersive surfactant selected from nonionic and anionic surfactants and from 0.05 to 4% by weight of polyalkoxylated polyethyleneimine polymer, in which the polyalkoxy chains are directly bound to the nitrogens of the PEI and each chain has a terminal group with a molecular weight of less than 100, and in which the polymer is a PEI that has a molar ratio of polyalkoxyl chains, including the laminar group, to equal PEI or less than 3, resulting in 3 or less, preferably 2 or less, most preferably 1 nitrogen, bonded to polyalkoxyl chains, and in which the PEI has an Mw of at least 500, preferably 1000 to 2000, more preferably less than 1500 and even about 1300.

Description

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DESCRIPTION

Laundry detergent compositions comprising polyalkoxylated polyethyleneimine Technical field

The invention relates to laundry detergent compositions comprising an alkoxylated polyethyleneimine, anti-redeposition polymer (APR), and detergency surfactants, in particular anionic and non-ionic detergent surfactants.

Background

Ethoxylated PEI (PEI = polyethyleneimine) is known as an antiredeposition polymer by CA 121 0009. PEI material (600) 20EO with all primary and secondary amino groups completely substituted by polyalkoxylation with EO20 is not a good APR for detergents of laundry These alkoxylated PEIs are usually formed by direct reduction of ethylene oxide and / or propylene oxide and the PEI is described in CA 1210009,

EP 2050792 (DIC Corp) discloses the preparation of PEI plus PEG monomethyl ether tosylated as intermediate in the preparation of a PEG-PEI epoxy resin structure. This preparation is repeated in EP 2147733.

JP 2007/099929 (Dainippon Ink & Chem.) Also reports the addition of mono-methyl ether PEG to tosylated PEI followed by the addition of a styrene monomer.

S. Xu et al. (Macromolecular Bioscience vol. 7, pages 968-74, 2007) use tosylated mono-methyl ether PEG as intermediate to prepare an aromatically substituted PEI with PEG groups attached to the benzyl ring.

In the above documents, the molar ratio of mPEG to PEI used is at least 3: 1, which must give an average of at least 3 polyalkoxyl chains attached to each PEI.

Zhang & Lonnie (Chinese J. Chem., Vol. 21, pages 460-5, 2003) describe the preparation of PEI-PEG block copolymers and their clay dispersion. Polymers are triblock polymers formed by PEG (dimesyl) modified divalently. This forms a PEO grid between two PEI groups. Such crosslinked PEI is not desirable due to its lower weight efficiency.

Formulations that do not contain nonionics are widely used in laundry, especially for low-soap formulations suitable for automatic front-loading washing machines.

PEI tends to deposit dirt on fabrics based on nylon elastane. EPEI does not suffer from the same negatives of nylon elastane as PEI and consequently laundry washing compositions have been widely used. However, it would be desirable to improve the behavior of EPEI as a suspending polymer of the dirt to solve the problem of redeposition on the total range of fabrics found in a total laundry load: cotton, polyalgodon, polyester and nylon-elastane.

Summary of the invention

According to a first aspect of the present invention there is provided a laundry detergent composition containing from 5 to 30% by weight of a surfactant selected from non-ionic and anionic detergents and from 0.05 to 4% by weight, preferably from 0.1 to 2% by weight of an alkoxylated polyethyleneimine polymer in which the polymer is a PEI having a mole ratio of polyalkoxyl chains to PEI of less than or equal to 3, resulting in 3 nitrogen or less , preferably 2 or less nitrogen, very preferably 1 nitrogen, bound to polyalkoxyl chains, and in which the PEI has a Mw of at least 500. preferably from 1000 to 2000, more preferably less than 1500 and even of approximately 1300. Mw is the average weight molecular weight. Molecular weights are preferably determined by dynamic light scattering using a Zetasizer Nano (Malvern).

Suitably, when there is more than one polyalkoxy chain per PEI there is only one polyalkoxy chain per PEI nitrogen.

Preferably, the fraction of (% by weight of anionic surfactant) is 0.6 to 2.0, preferably 0.90 to 1.2.

Also according to the present invention a washing method is provided in which the composition according to the first aspect is diluted to a level of 0.3 to 1 g / l of surfactant and 5 to 150 ppm, preferably from 10 to 80 ppm of polymer according to the first aspect and used for fabrics to be washed.

Each polyalkoxy chain is composed of ethoxy and / or propoxy groups. Most preferably, it is a polyethoxy chain. Preferably the polyalkoxy chain contains from 5 to 60 repeated alkoxy units more preferably from 8 to 20, most preferably from 10 to 14. The chains may be capped with alkyl,

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preferably with methyl. To facilitate the union of the polyalkoxyl capped chain with the PEI chain, preferably a reactive group is provided at the end to be attached to the PEI. Suitable reactive groups can be selected from epoxides, alkenes, a sulfoxiethylsulfonyl reactive group (-SO2CH2CH2OSO3Na), heterocyclic reactive groups and leaving groups such as tosylate. Heterocyclic reactive groups are preferably nitrogen containing aromatic rings attached to a halogen or an ammonium group that react with NH2 or NH groups forming a covalent bond. To avoid crosslinking reactions, preferably the alkoxy chain contains only one reactive group, the other chain end being typically capped. Each chain has a terminal group with a molecular weight of less than 100. The terminal group in the polyalkoxy chain may be a C1-4 alkyl group, preferably a methyl group.

An example structure of the polyalkoxylated PEI polymer in which the alkoxylation is ethoxylation, the end cap is methyl and the number of EO units is 13, is the structure (i)

image 1

Detailed description of the invention

Detergent compositions may have any suitable form. For example, they may be powders, tablets, liquids or gels and, in the case of liquids, they may be contained in a water soluble capsule for ease of use. Preferred compositions are liquid due to the compatibility of ethoxylated PEI ARP materials with the ingredients typically found in liquid detergents.

Surfactants

Surfactants help remove dirt from textile materials and also in the maintenance of dirt removed in solution or suspension in the wash liquor. Mixtures of anionic and non-ionic surfactants are a preferred feature of the compositions. The amount of anionic surfactant is 5% by weight at least 5% by weight, more preferably at least 10% by weight.

Anionics

Preferred anionic surfactants are alkyl sulfonates, especially alkyl benzenesulfonates, in particular linear alkyl benzenesulfonates having a length of the C8-15 alkyl chain. The counterion of the anionic surfactants can be an alkali metal, typically sodium, or another counterion, for example, MEA, TEA or ammonium can be used.

Among the linear alkylbenzenesulfonates surfactants are retail LAS with an alkyl chain length of 8 to 15, more preferably 12 to 14.

It is also desirable that the composition comprises an anionic polyethoxylated alkyl sulfate surfactant of the formula (II)

RO (C2H4O) xSO3-M + (II)

wherein R is an alkyl chain having 10 to 22 carbon atoms, saturated or unsaturated, M is a cation

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which makes the compound soluble in water, especially an alkali metal, ammonium or a substituted ammonium cation, and x is on average 1 to 15.

Preferably R is an alkyl chain having from 12 to 16 carbon atoms, M is sodium and x averages from 1 to 3, preferably x is 3. This is the anionic surfactant lauryl ether sodium sulfate, (SLES). It is the sodium salt of lauryl ether sulfonic acid, in which the predominant group C12 lauryl alkyl has been ethoxylated with an average of 3 moles of ethylene oxide per mole.

Non ionic

Non-ionic surfactants include ethoxylates of primary and secondary alcohols, especially ethoxylated Cs-20 aliphatic alcohol with an average of 1 to 20 moles of ethylene oxide per mole of alcohol and, more especially, C10-15 primary and secondary aliphatic alcohols. ethoxylated with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglucosides, glycerol monoethers and polyhydroxyamides (glucamide). Mixtures of non-ionic surfactants can be used. When included, the composition contains from 0.1 to 20% by weight, preferably from 1% by weight to 15% by weight, more preferably from 5 to 15% by weight of a non-ionic surfactant, for example, ethoxylated alcohol , nonylphenol ethoxylate, alkyl polyglucoside, alkyldimethylamine oxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethenolamide, polyhydroxy fatty acid amide, or N-acyl derivatives N-alkyl glucosamine ("glucamides").

Among the non-ionic surfactants that can be used are ethoxylates of primary and secondary alcohols, especially C8-20 aliphatic alcohols ethoxylated with an average of 1 to 35 moles of ethylene oxide per mole of alcohol and, more spatially, C10 aliphatic alcohols -15 primary and secondary ethoxylates with an average of 1 to 10 moles of ethylene oxide per mole of alcohol.

Amine oxide

The composition may comprise up to 10% by weight of an amine oxide of the formula (III):

R1N (O) (CH2R2) 2 (III)

in which R1 is a long chain remainder each CH2R2 being a short chain remainder. R2 is preferably selected from hydrogen, methyl and -CH2OH. In general R1 is a primary or branched hydrocarbyl moiety that can be saturated or unsaturated, preferably R1 is a primary alkyl moiety. R1 is a hydrocarbyl moiety having a chain length of about 8 to about 18.

In the preferred amine oxides R1 is C8-18 alkyl and R2 is H. These amine oxides can be illustrated with C12-14 alkyldimethyl oxide, hexadecyldimethylamine oxide, octadecylamine oxide.

A preferred amine oxide material is dimethylamine lauryl oxide, also known as dodecyldimethylamine oxide or DDAO. This amine oxide material is commercially available from Hunstam under the trade name Empigen® OB. Other suitable amine oxides can also be purchased from Akzo Chemie and Ethyl Corp. See McCutcheon's compilation and review article from Kirk-Othmer for other amine oxide manufacturers.

While in preferred embodiments R2 is H, it is possible to have R2 slightly greater than H. Specifically, R2 may be CH2OH, for example hexadecylbis (2.hydroxyethyl) amine oxide, sebobis (2-hydroxyethyl) amine oxide, stearylbis oxide (2-hydroxyethylamine) and oleylbis (2-hydroxyethyl) amine oxide

Preferred amine oxides have the formula (IV)

O '- N + (Me) 2R1 (IV)

wherein R1 is C12-16 alkyl, preferably C12-14 alkyl; Me is a methyl group.

Ionicohfbrids

A hybrid ionic material is an affordable carbobetaphine from Hunter under the name Empigen ® BB. Beatones or amine oxides improve the detergency of particulate dirt in the compositions.

Additional surfactants

Other surfactants other than LAS, SLES, non-ionic and amine oxide / carbobetaphines may be added to the mixture of detersive surfactants. However, preferably the cationic surfactants are substantially not present.

Although less preferred, some alkyl sulfate surfactant (PAS) may be used, especially the C12-15 primary and secondary non-ethoxylated alkyl sulfates. A particularly preferred commercially available material of BASF is Sulfopon 1214G.

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Polymers

Polyester dirt-release polymer

The compositions may include 0.5% by weight or more of a soil-releasing polymer that is substantive to polyester fabric. Such polymers typically have a substantive fabric triblock formed by repeated units of poly (propylene terephthalate) and one or two final blocks of capped polyalkylene oxide, typically from PEG 750 to 2000 with a methyl final finish.

Other types of polymer

In addition to a polyester soil-releasing polymer, dye transfer inhibitor polymers, and soil-releasing cotton polymers, especially those based on modified cellulosic materials, can be used,

Hydrotrope

A hydrotrope is a solvent that is not water or a conventional surfactant that contributes to the solubilization of the surfactants and other components in an aqueous liquid to make it hydrotrope. Among the suitable hydrotrops there may be mentioned as preferred: MPG (monopropylene glycol), glycerol, sodium cumenesulfonate, ethanol, other glycols, for example dipropylene glycol dieters and urea.

Enzymes

It is preferable that at least one or more enzymes may be present in the compositions. Preferably at least two enzymes are used in combination, more preferably at least three different classes of enzymes. Enzyme combinations are selected from the group comprising lipase, phospholipase, protease, cutinase, amylase, cellulase, peroxidases / oxidase, Pectate Liasa and Mannanasa.

Any enzyme present in the composition can be stabilized using conventional stabilizing agents, for example a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid or a boric acid derivative, for example an aromatic borate ester, or a phenylboronic acid derivative, for example 4-formylphenylboronic acid, and the composition can be formulated as described in, for example, WO 92/19709 and WO 92/19708. Alternatively or additionally, enzymes can be protected by encapsulation.

When a lipase enzyme is included, a lignin compound can be used in the composition. Preferably, the lignin compound comprises a lignin polymer and more preferably is a modified lignin polymer. As used in this context, a modified lignin polymer is lignin that has undergone a chemical reaction to covalently bind chemical moieties to lignin. Preferably, the chemical residues are randomly substituted.

Fluorescent agents

A fluorescent agent can be advantageously included in the compositions. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally 0.005 to 2% by weight, more preferably 0.01 to 5% by weight.

Preferred classes of flowering agents are di-styrylbiphenyl compounds, for example Tinopal (trade mark) CB5-X, diaminostilbene disulfonic compounds, for example Tinopal DMS pure Xtra, Tinopal 5BMGX and Blankopohor (trade mark) RHM, and pyrazoline compounds by example Blankophor SN.

Preferred classes of fluorescent agents are 2 (4-styryl) -3-sulfophenyl) -2H-naphthol [1,2-d] sodium triazole, 4,4'-bis {[(4- anilino-6- (N-methyl) -N-2-hydroxyethyl) amino 1,3,5-triazin-2-yl)] amino} stilbene-2,2'-disodium disodium, 4,4'-bis {[(4- anilino-6-morpholino -1,3,5-triazin-2-yl)] amino} stilbene-2,2'-disulfonate disodium and 4,4'-is (2-sulfoesliryl) bophenyl.

Bleaching catalyst

The compositions may comprise an efficient weight of a bleaching system, typically such systems do not use the conventional percarbonate approach and bleaching activator. An air bleach catalyst system is preferred. Suitable complexes and precursors (of ligand) of organic molecules for complexing are available for the skilled operator, for example, considered in WO 98/39098, WO 98/39406, WO 97/48787, WO 00/29537, WO 00 / 52124 and WO 00/60045. An example of a preferred catalyst is a MeN4 Py ligand (N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -aminoethane) transition metal complex. Suitable bispidon catalyst materials and their action are described in WO 02/48301. The bleach catalyst can be encapsulated to reduce interaction with other liquid components during storage.

Photo bleachers can also be used. A "whitener" is any chemical species that forms a

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kind of reactive bleaching when exposed to sunlight and preferably not consumed permanently in the reaction. Photoblankers include singlet oxygen photobleach and radical photobleach. The singlet oxygen photobleach can be selected from water-soluble phthalocyanine compounds, in particular metallized phthalocyanine compounds in which the metal is Zn or Al-1, Z1 being a halide, sulfate, nitrate, carboxylate, alkanolate or hydroxyl ion. Preferably, the phthalocyanine has 1-4 SO3X groups covalently bonded to it, X being an alkali metal or ammonium ion. Such compounds are described in WO 2005/014769 (Ciba).

When present, the bleach catalyst is typically incorporated at a level of about 0.001 to about 10% by weight, preferably about 0.001 to about 5% by weight.

Fragrance

Normally the composition will include one or several perfume components. Oil-free perfumes and encapsulated perfumes can be used.

A particularly preferred way to ensure that the perfume is used effectively is to use an encapsulated perfume. The use of a perfume that is encapsulated reduces the amount of perfume vapor produced by the composition before diluting it. This is important when the perfume vapor concentration is increased by washing to keep it at a reasonably high level.

It is even more preferable that the perfume is not only encapsulated, but that the encapsulated perfume be provided with a means of deposit in order to increase the efficiency of the perfume tank and its retention on the fabric. The storage medium is preferably attached to the encapsulation by means of a covalent bond, lock or strong adsorption.

Other optional ingredients

The compositions may contain one or more other ingredients. Such ingredients include viscosity modifiers, foaming promoters, preservatives (for example bactericides), buffering agents, polyelectrolytes, anti-wrinkle agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, wave imparting agents, anti-static agents and ironing aids. The compositions may also comprise dyes, agents that impart a pearly and / or opacifying appearance and a dye for screening.

Colorings for shades

A hue dye can be used in order to improve the behavior of the compositions. Preferred dyes are violet or blue. It is believed that the deposit on fabrics of a low level of these shades masks the yellowing of fabrics. Another advantage of hue dyes is that they can be used to mask any yellow dye in the sL composition. Examples of hue dyes, alkoxylated thiophene dyes, acid violet 50, direct violet 35, direct violet 99, direct violet 9, solvent violet 13, dispersed violet 28, dispersed blue 165.

Hue dye may be used in the absence of a fluorescent agent, but it is especially preferred to use a hue dye in combination with a fluorescent agent, for example in order to reduce yellowing due to chemical changes in the adsorbed fluorescent agent,

Detergency aids and kidnappers

The detergent compositions may optionally also contain low levels of organic detergency builder or sequestering material. Examples include alkali metals, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetalcarboxylates. Specific examples include sodium, potassium, and lithium salts of oxydisuccinic acid, melphic acid, benzenepolycarboxylic acids, and citric acid. Other examples are DEQUESTMC, organic phosphonate sequestering agents sold by Monsanto and alkanohydroxyphosphonates.

Other suitable organic detergency builders include high molecular weight polymers and copolymers known as having detergency builder properties. For example, among such materials are suitable polynolic, polymaleic and polyamino / polyamleic acids and their salts, for example, those sold by BASF under the name SOKOLAN MC.

If used, organic adjuvant materials may comprise from about 5% to 20% by weight, preferably from 1% by weight to 10% by weight of the composition. Preferred detergency builder levels are less than 10% by weight and preferably less than 5% by weight of the composition. A known sequestrant is HEDP (1-hydroxyethylidene-1,1-diphosphonic acid), for example, sold as Dequest 2010. It is also suitable, although less preferred since it gives lower cleaning properties, Dequest ® 2066

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(diethylenetriamine penta acid (methylene phosphonium or Heptasodium DTPMP).

Tampons

For pH control, the presence of some buffer is preferred, with MEA and TEA buffers being preferred. If present, they are preferably used in the composition at levels of 1 to 15% by weight.

External Structuring

The compositions may have their technology modifier using a material, or materials, that form a structuring network within the composition. Structuring agents include castor oil, microfibrous cellulose and natural structuring agents, for example, cftric pulp fiber. In particular, cftric pulp fiber is preferred, especially if lipase enzyme is included in the composition.

Visual arid

The composition may comprise a visual component of solid material that is not dissolved in the composition. Preferably they are used in combination with an external structurant that remains in suspension. Among such structuring components laminar elements formed of a polyethylene film and possibly comprising functional ingredients that may not be stable if exposed to alkaline liquid. Examples of such components are enzymes and bleach catalysts. Also perfumes, in particular encapsulated perfume.

The invention will now be described more with reference to non-limiting examples.

Examples

Synthesis of polymers.

Step (a): Tosylation of methyl terminated polyethylene glycol

Materials Quantities used

CH3 (O-CH2CH2) nOH (Mn = 550) 110 g

Tosyl Chloride 38 g

Triethylamine 20.2 ml

150 ml dichloromethane

Tosyl chloride was added, over 45 min, to a stirred mixture of polyethylene glycol methyl ether and triethylamine in dichloromethane at 0 ° C-5 ° C. The mixture was then allowed to warm to room temperature and stirred at room temperature for 16 h, after which all the tosyl chloride had been consumed, according to thin layer chromatography. The reaction gave a suspension (192 g) of tosylated PEG.

Stage (b): "PolyethoxyNation" of Polyethyleneimine

The tosylated PEG suspension from step (a) was mixed with a 50% by weight solution of Poletilenimine (Mw = 1300) at pH 10.5. The molar ratio of tosylated PEG to Polyethyleneimine was 1: 1. The mixture was stirred overnight (16 h) at room temperature after which the formation of para-toluenesulfonic acid was completed as measured by TLC; the pH was adjusted to 7.0 with conc. hydrochloric acid. And he got bottled. Synthesis was repeated with different molar ratios of PEG tosylated to Polyethyleneimine, obtaining a series of polymers as detailed in Table 1. P10 and P30 have been comparatively marked because they resemble the alkoxylated polyethyleneimines of the prior art.

Table 1

 Polymer Code

 Molar ratio of PEG tosylated to Polyethyleneimine

 P1

 1: 1

 P2

 2: 1

 P3

 3: 1

 P10 (refer)

 10: 1

 P30 (refer)

 30: 1

Wash test

The base composition of laundry detergent used for the laundry test is given in Table 2.

 % by weight (solids)

 Nalas

 4.9

 NL (7EO)

 7.3

 SLES (3EO)

 2.4

 Alkyl betafna

 0.9

 12-propanediol

 15.0

 Triethanolamine

 2.0

 Oil free perfume

 1.4

 Water

 to 100

NaLAS is C11-15 alkyl sodium benzenesulfonate Nl (7EO) is R- (OCH2CH2) nOH, where R is C12-15 alkyl and n = 7.

5 SLES (3EO) is sodium lauryl ether sulfate with an average of 3 ethoxy groups.

Alkyl Betafna is Empigen®BB (from Hunstman).

The composition was used to wash a mixture of white fabrics: woven cotton, microfiber polyester, woven polyalgodon, and knitted nylon-elastane with a ratio of liquor to fabric of 10: 1 in a Linetester. The fabrics were of equal surface. Water of 26 ° of French hardness was used. Each wash lasted 20 min followed by two rinses in 10 75 ml of water. The procedure was repeated twice in a base composition given in Table 2 (that is, without

polymer) and then the fabric dried.

The washing procedure was repeated three more times, now without adding dirt strips to each wash to simulate dirt. The weight ratio of strips and dirt to white fabrics was 8.6; 1. The dirt strips were SBL 2004 Soil Ballast Fabrics (from wfk Testgewebe GMBH) and a Stanley Clay strip (from Warwick Equest UK) in a 1: 1 weight ratio. For each of these repetitions, 3.5% by weight of polymer was also included in the composition, correspondingly correcting the water balance. The compositions were used at 2.3 g / l.

The fabrics were removed, dried and the reflectance spectrum was measured using a reflectometer. The cleaning increase was measured according to R460, given by R460R = R460 (polymer) -R460 (control).

The cleaner the fabric, the higher the reflectance, so the larger R is the greater the cleaning of the fabric compared to the control. The results are given in Table 3.

Table 3

 ■ R 460

 Polyester cotton Polyester nylon-elastane

 PEI (1300) (reference)

 7.6 2, 4 9.8 -9.1

 P1

 6.5 4, 6 11.1 -2.1

 P2

 3.4 1, 7 6.9 -3.1

 P3

 3.4 1, 4 1.6 -2.6

 P10 (reference)

 1.3 1, 3.4 3.4 0.8

 P30 (reference)

 0.9 1, 2.5 2.5 1.4

 PEI (1300) is non-ethoxylated PEI

The polymers P1 (with 1 ethoxylated chain) and P2 (with 2 ethoxylated chains) have the best overall performance, with good effects on cotton, polyalgodon and polyester, without negative behavior

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large in nylon-elastane, as seen in the completely non-alkoxylated PEI.

Note that in the following examples 2 and 4 the data for P1 and P30 are the sum data of this test and not repeated data.

Example 2

The synthesis and experiments of Example 1 were repeated for the 1: 1 molar ratio for PEG tosylated polyethyleneimine. The Poly (ethylene glycol) methyl ether used was changed to:

CH3 (OCH2CH2) nO (Mn = 750) and the resulting alkoxylated PEI polymer encoded P1-750; and CH3 (O-CH2CH2) nOH (Mn = 2000) and the resulting alkoxylated PEI polymer encoded P1-2000.

The washing results are given in Table 4

Table 4

 ■ R460

 P1

 20.1

 P1-750

 15.9

 P-1-2000

 12.3

 PEI (1300) (reference)

 10.7

 P30 (reference)

 6.4

 ■ R460 is the sum of R450 for each fabric

P1, P1-750 and P1-2000 provided improved results on the P30 and the PEI reference polymer (1300). The best results were given by the shorter alkoxylated chain PEI.

15 Example 3

The experiments of Example 1 were repeated for P1 at a level of 0.4377% by weight (10 ppm in the wash solution). The results are given in Table 5

Table 5

 ■ R460

 P1 (10 ppm)

 15.9

20 The polymers of the invention provide benefits at low levels Example 4

The synthesis and experiments of Example 1 were repeated for the 1: 1 molar ratio for tosylated PEG: polyethyleneimine. Polyethyleneimine was changed to Polyethyleneimine (Mw = 800) and Q1 was coded. The washing results are given in Table 6.

Table 6

 ■ R460

 P1

 20.1

 Q1

 15.3

Example 5

Table 7 is another detergent composition according to the invention.

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 % weight, solids

 Nalas

 4.9

 Nl (7EO)

 7.3

 SLES (3EO)

 2.4

 Alkyl betafna

 0.9

 1,2-propane-

 15.0

 diol

 Trietanol-

 2.0

 amine

 Perfume without

 1.4

 oil

 P1

 0.3 0.002

 Lipase

 0.002

 Cellulase

 0.002

 Amylase

 0.002

 Acid violet

 fifty

 0.1

 Fluo agent

 rescent

 to 100

 Water

Enzyme levels are expressed as pure protein. The lipase used was LipocleanMC (Novozymes); The cellulase used was CellucleanMC (Novozymes); The amylase used was StainzymeMC (Novozymes).

Claims (10)

5 10 fifteen twenty 25 1. A laundry detergent composition containing from 5 to 30% by weight of detersive surfactant selected from non-ionic and anionic surfactants and from 0.05 to 4% by weight of polyalkoxylated polyethyleneimine polymer, in which the chains of polyalkoxy are directly linked to the PEI nitrogen and each chain has a terminal group with a molecular weight of less than 100, and in which the polymer is a PEI that has a mole ratio of polyalkoxy chains, including the laminar group, to PEI equal to or less than 3, resulting in 3 or less, preferably 2 or less, most preferably 1 nitrogen, bound to polyalkoxyl chains, and in which of the PEI has a Mw of at least 500, preferably 1000 to 2000, more preferably less than 1500 and even about 1300. 2. A composition according to claim 1, wherein the fraction of (% by weight, non-ionic surfactant) / (% by weight, anionic surfactant) is 0.6 to 2.0. 3. A composition according to claim 2, wherein the fraction of (% by weight, non-ionic surfactant) / (% by weight, anionic surfactant) is 0.90 to 1.2. 4. A composition according to any preceding claim, which is a liquid. 5. A composition according to any one of claims 1 to 3 which is a solid. 6. A composition according to any preceding claim which also includes perfume. A composition according to any preceding claim, wherein the terminal group of the polyalkoxyl chain is a C1-4 alkyl group, preferably a methyl group. 8. A composition according to any preceding claim, wherein the polyalkoxylation consists of polyethoxylation. 9. A composition according to claim 8, wherein the average number of ethylene oxide units in the polyethoxylated PEI is 5 to 50, preferably 8 to 20, more preferably 10 to 14. 10. A composition according to any preceding claim comprising ethoxylated nonionic surfactant. 11. A laundry procedure, in which a composition according to any one of the claims 1 to 10 are diluted to a level of 0.3 to 1 g / l of detersive surfactant and 5 to 150 ppm, preferably 10 to 80 ppm polyethyleneimine polyethoxylated polymer and is used for casting a mixed load of fabrics comprising nylon-elastane and at least one other fabric selected from the group comprising cotton, polyalgodon and polyester.