KR100225998B1 - Composition comprising ethoxylated/ propoxylated polyalkyleneamine polymers soil dispersing agents - Google Patents

Abstract

The present invention relates to wash and soil dispersion compositions comprising ethoxylated / propoxylated polyalkyleneamine polymers. Thus, detergent compositions comprising ethoxylated / propoxylated polyalkyleneamine polymers, such as poly (ethyleneimine) having an ethoxylation degree of 1.0, provide dirt dispersion performance in wash liquor and brighten and brighten fabrics, hard surfaces or dishes. And / or provide cleaning benefits.

Description

[Name of invention]

Compositions Containing Alkoxylated Polyalkyleneamine Polymers As Soil Dispersants

Detailed description of the invention

[Technical Field]

The present invention relates to cleaning and dirt suspension compositions using alkoxylated, in particular ethoxylated and / or propoxylated polyalkyleneamine polymers to enhance dirt dispersion performance. Fabric laundry, dish cleaning and hard surface cleaning compositions with improved dirt dispersion performance are provided.

[Background of invention]

Detergent formulators face the challenge of designing products to remove a wide range of dirt and stains from fabrics. Chemically and physicochemically, the diversity of dirt and stains ranges from polar dirt such as proteins, clays and inorganic dirt to nonpolar dirt such as soot, carbon black, incomplete combustion products of hydrocarbons and organic dirt. Detergent compositions have become more complex because they seek to provide products that handle all forms accompanied by formulators.

Formulators have succeeded in developing conventional dispersants that are particularly useful for suspending highly charged polar hydrophilic particles such as clays. However, it is still difficult to develop a dispersant for dispersing and suspending nonpolar hydrophobic dirt and fine particles. Without being limited by theory, the first step to forming a dispersant is to adsorb the dirt dispersant to the dirt. In the case of clay type soils, the soil dispersant should be adsorbed on the surface with a negative charge or with a positively charged edge. In the case of organic particulates, the soil dispersant has to be adsorbed onto a hydrophobic surface which carries little or no charge. Thus, in the case of polar soils, such as clays, certain charged dispersants, for example charged high ethoxylated polyamines, are used. However, these charged dispersants do not adsorb to organic nonpolar particulates.

It is now possible to provide effective and improved soil dispersion (particularly to nonpolar soils) in the wash liquor using compositions which actually comprise uncharged alkoxylation, in particular ethoxylated / propoxylated polyalkyleneamine polymers. It turned out. In addition, the ethoxylated / propoxylated polyalkyleneamine polymers whiten / wash fabrics and increase the cleaning performance of hard surfaces and dishwashing compositions.

Accordingly, it is an object of the present invention to provide an improved cleaning and dirt dispersion composition that utilizes an uncharged ethoxylated / propoxylated polyalkyleneamine polymer. Yet another object is to provide means for dispersing dirt and providing brightening / washing benefits to fabrics and dishes using the waste dispersing system of the present invention. The above and other objects are obtained in the present invention as can be seen from the following description.

[Background]

The use of ethoxylated amines is described in US Pat. Nos. 4,891,160, 4,676,921 and 4,597,898. Further use of polyalkyleneamine polymers is described in US Pat. Nos. 5,183,601, 4,654,043, 4,645,611, 4,643,544 and 4,171,278. See also European Patent Application Nos. 206,513 A1 and 042,187 A1.

[Summary of invention]

The present invention encompasses a soil dispersion composition comprising actually uncharged alkoxylated, preferably ethoxylated and / or propoxylated polyalkyleneamine polymers.

As used herein, the term ethoxylate / propoxylate means an alkoxylate unit within the scope of the invention as defined hereinafter. Ethoxylated / propoxylated polyalkyleneamine polymers are used in effective amounts in the compositions and processes of the present invention. By effective amount is meant an amount sufficient to increase the dispersion of dirt in the wash liquor and to provide brightening and / or wash to the desired substrate using any comparative test conditions. Thus, in a fabric laundry operation the target substrate will typically be, for example, a stained fabric with various food stains. In the case of automatic dishwashing, the target substrate may be, for example, a magnetic cup stained with tea or a polyethylene dish stained with coasters or gravy. Test conditions will vary depending on the cleaning apparatus used and the habits of the user. Thus, the front-loading washing machine, a type generally used in Europe, uses less water and more detergent than the American top-loading washing machine. Certain washing machines have considerably longer wash cycles than others. Some users use very hot water while others use hot or cold water. Of course, the performance of the dirt dispersant is affected by these conditions and the amount used in the fully formulated detergent and dirt dispersion composition can be controlled appropriately.

Preferably, the soil dispersion composition comprises at least about 0.1%, preferably about 0.1 to about 15%, more preferably about 0.5 to about 10% of the ethoxylated / propoxylated polyalkyleneamine polymer. . Polyalkyleneamines comprise a nitrogen containing backbone having an average molecular weight of about 600 to about 10,000, preferably about 1,000 to about 3,000. The average degree of alkoxylation of the polymer is from about 0.5 to about 10, preferably from about 0.7 to about 8, most preferably from about 0.7 to about 4 per nitrogen. In addition, the alkoxylated polyalkyleneamine polymers may comprise up to about 4, preferably up to 1 propoxylate or longer alkoxylate units per useful nitrogen position. Useful nitrogen site sugars mean that each H of the NH moiety may be substituted by up to about 4 propoxylates or longer alkoxylate units. Thus, up to eight propoxylates or longer alkoxylate units after the alkoxylation of the NH ₂ position can be bonded to nitrogen. Preferably, propoxylate or longer alkoxylate units in the alkoxylate system are first added to the polyalkyleneamine before adding to the ethoxylate units.

The invention also includes about 1% to about 55% detergent surfactant and ethoxylated / propoxylated polyalkyleneamine polymer.

The present invention also includes detergents including laundry formulations, solid soaps, automatic dishwashing detergents, and hard surface cleaners comprising conventional surfactants and other detergent ingredients.

The present invention also includes a method for improving dirt dispersion performance of a detergent composition, which comprises adding an effective amount of an ethoxylated / propoxylated polyalkyleneamine polymer. The present invention provides a method of brightening and / or cleaning a fabric, light surface or tableware comprising contacting the fabric, light surface or tableware with an aqueous medium comprising the composition. In addition, unless limited by theory, the benefits of brightening / cleaning are obtained by preventing the suspension of dirt and particulate matter in the wash liquor to re-deposit onto fabric or other surfaces in the wash liquor. This benefit comes after repeated dirt / wash cycles. The number of cycles required for this to be visible depends on the amount of dirt dispersant used in the wash cycle, the amount of dirt present in the wash liquor and the overall efficacy of the base detergent to which the dirt dispersant is applied.

As a practical matter, the compositions and processes of the present invention can be adjusted so that the active ethoxylated / propoxylated polyalkyleneamine polymer species in the aqueous laundry medium is at least 1 part per million and the active ethoxylated / propoxylated poly in the medium. The alkyleneamine polymer species is preferably provided from about 0.1 to about 700 ppm, more preferably from about 0.5 to about 500 ppm, most preferably from about 1 to about 100 ppm.

All percentages, ratios, and ratios herein are by weight unless otherwise indicated. All documents mentioned in the relevant part of this application are incorporated by reference.

Detailed description of the invention

Unlike charged polymers in the art, the ethoxylated / propoxylated polyalkyleneamine polymers of the present invention are low molecular weight, water-soluble, alkoxylated, preferably ethoxylated / propoxylated polymers that are not actually charged. Light weight means that the average alkoxylation degree per nitrogen of the polymer of the invention is from about 0.5 to about 10. In fact uncharged means that there are up to about 2 positive charges for every 40 nitrogens present in the backbone of the polyalkyleneamine polymer.

Preferred ethoxylated / propoxylated polyalkyleneamines of the invention are compounds of formula

[Formula 1]

In Chemical Formula 1,

P ¹ is each independently C ₂ -C ₁₂ alkylene, alkenylene, arylene or alxarylene, and R 2 is each independently H, straight, branched or cyclic C ₁ -C ₈ alkyl moiety, phenyl, benzyl, C ₁ -C ₈ aroyl or alkanoyl moiety, especially benzoyl, or the moiety -LX ^- [wherein, X may be a nonionic group, especially H, an anionic group, such as sulfate, L is the polyoxyalkylene moiety [(R ⁵ O) _{m '} (CH ₂ CH ₂ O) _n' -(R ⁵ O) _m (CH ₂ CH ₂ O) _n ] (wherein R ⁵ are each independently H, C ₃ -C ₄ alkylene or hydride Oxyalkylene, m '+ m is m, n' + n is n, m is 0 to about 4, n is 0 to about 16, preferably about 0 to about 10, m + n is Hydrophilic chains containing from about 1 to about 16, preferably from about 1 to about 10), provided that at least 0.5 R ² residues per nitrogen is -LX, w is 1 or 0, and x + y + z is 14 or more, B represents the continuation of the structure by branching. Serve

Side chained backbones are preferred, but straight chain and cyclic polymer backbones are also possible. The relative proportions of primary, secondary and tertiary amine groups present in the polymer prior to the alkoxylation may vary depending on the method of preparation. The distribution of amine groups is typically -CH ₂ CH ₂ -NH ₂ 25%, -CH ₂ CH ₂ -NH-50% and -CH ₂ CH ₂ -N-25%.

In formula 1, R ¹ is a straight or branched chain [eg, —CH ₂ CH ₂ , —CH ₂ —CH ₂ —CH ₂ —, CH ₂ —C (C ₆ H ₅ ) H—] alkylene, alkenylene or al Xylene. R ¹ is preferably C ₂ -C ₆ alkylene. However, especially for high molecular weight ethoxylated polyalkyleneamines and polyalkyleneimines, C ₂ -C ₃ alkylene (ethylene, propylene) is preferred as R ¹ and ethylene is most preferred.

At least 0.5 R ² residues per nitrogen are preferably residues -LX. Hydrophilic chain L in formula (1) usually consists entirely of polyoxyalkylene moieties [(R ⁵ O) _{m '} (CH ₂ CH ₂ O) _n' -(R ⁵ O) _m (CH ₂ CH ₂ O) _n ] . The residues-(R ⁵ O) _{m 'or m} -and-(CH ₂ CH ₂ O) _{n' or n} -of the polyoxyalkylene moiety are mixed together (e.g. randomly) or preferably-(R ⁵ O) _{n 'or m} -and-(CH ₂ CH ₂ O) _{n' or n} -can be formed a block. R ⁵ is preferably C ₃ H ₆ (propylene). In the case of the present invention, m is preferably 0 to about 4, most preferably 0 so that the polyoxyalkylene moiety consists entirely of residues — (CH ₂ CH ₂ O) _{n ′ or n} −. The residue-(CH ₂ CH ₂ O) _{n 'or n} -is preferably comprised on average of at least about 85% by weight, most preferably 100% by weight of the polyoxyalkylene moiety (ie when m is 0). .

In formula (1), X may be any compatible anionic group, in particular a sulfate or a nonionic group. Suitable nonionic groups include C ₁ -C ₄ alkyl or hydroxyalkyl esters or ether groups, preferably acetate esters or methyl ethers, hydrogen (H) or mixtures thereof. Particularly preferred nonionic group is H.

Particularly preferred ethoxylated / propoxylated polyalkylamine polymers are ethoxylated C ₂ -C ₃ polyalkyleneamines and polyalkyleneimines such as ethoxylated polyethyleneamine (PEA) and polyethyleneimine (PEI). These preferred compounds are exemplified by the following structures with an average degree of ethoxylation of 1.0:

Other polymers are exemplified by the following structure:

[Wherein, R each independently represent a _{-CH 2 (C 6 H 5)} , - C (O) (C 6 H 5), - (CH 2 CH 2 O) nH, - (CH 2 CH 2 O) n H ,-(CH ₂ CH ₂ CH ₂ O) (CH ₂ CH ₂ O) _n OCH _3, -(CH (CH ₃ ) CH ₂ CH ₂ O) (CH ₂ CH ₂ O) _n OCH _3- (where n Is about 1 to about 16) and -CH ₂ CH (OH) CH ₃ ].

In polyalkyleneimines and polyalkyleneamines, each hydrogen atom bonded to each nitrogen atom represents an active site for subsequent ethoxylation. Such PEA can be obtained by a reaction involving ammonia and ethylene dichloride. See Dickson, US Pat. No. 2,792,372 (May 14, 1957), which describes the manufacture of PEA.

PEI used in the preparation of the compounds of the present invention has a molecular weight of about 600 iso before ethoxylation and represents at least about 14 units. Such a polymer backbone of PEI can be illustrated by the following structure:

Each hydrogen atom bonded to each nitrogen atom of the PEI represents an active site for subsequent alkoxylation. Such PEI can be prepared, for example, by polymerizing ethyleneamine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid and the like. Specific methods for making PEIs are described in U.S. Patent Nos. 2,182,306 to Ulrich et al., Dec. 5, 1939, MayIe et al., US Pat. No. 3,033,746 to May 1962, which is incorporated herein by reference. 8., US Pat. No. 2,208,095 to Esselmann et al. (July 16, 1940), Crowther et al. US Pat. No. 2,806,839 to Sept. 17, 1957, and Wilson. US Pat. No. 2,533,696 (May 21, 1951).

[Method for Preparing Ethoxylated Amine]

The ethoxylated compounds of the present invention can be prepared by standard methods for ethoxylating amines. In the case of polyamines such as polyalkyleneamines and polyalkyleneimines, preferably the initial step is a condensation reaction of ethylene oxide sufficient to provide 2-hydroxyethyl groups at each reactive position (hydroxyethylation). A suitable amount of ethylene oxide is then condensed with 2-hydroxyethylamine using an alkali metal (eg sodium or potassium) hydride or hydroxide as catalyst to provide each ethoxylated amine. If desired, an alkali metal catalyst can be added when the hydroxyethylation step is not complete. This makes the distribution of the ethoxylation degree of the reactive sites less uniform than when the catalyst is added after the end of hydroxylethylation. The total degree of ethoxylation for each position (NH) can be determined according to the following formula:

Ethoxylation degree = E / (AR)

[Where E is the total moles of condensed ethylene oxide (including hydroxyethylation), A is the moles of starting amine, and R is the number of reactive sites for the starting amine]

As noted above, the alkoxylated polyalkyleneamines of the present invention have a limited number of positively charged positions in the polymer but are not actually charged. Thus, the invention includes polymers having up to about 2 charged positions per 40 nitrogen positions. Charged sites can be formed by quaternization or hydrogen quantization. However, the preferred pH range of the present invention allows the soil dispersant of the present invention to remain essentially uncharged in the wash liquor. When using the soil dispersant of the invention, optimum performance is obtained with a wash liquid having a pH of at least about 9, preferably about 9.5 to 12. Such pH can be obtained using materials commonly known as buffers, which are any component of the bleaching system of the present invention.

[Assistant Ingredients]

The compositions of the present invention may optionally aid or enhance one or more other detergent aids or cleaning performance, treat the substrate to be washed or otherwise improve the aesthetic aspect of the detergent composition (eg, use of perfumes, colorants, dyes, etc.). It may include a substance. The following are examples of such auxiliary substances.

[Detergent detergent]

Non-limiting examples of useful surfactants typically used in the present invention in amounts of about 1 to about 55% by weight include conventional C ₁₁ -C ₁₈ alkyl benzene sulfonates (LAS) and primary, branched and random C ₁₀ -C ₂₀ alkyl sulfates _{(AS), CH 3 (CH} 2) × (CHOSO 3 - M +) CH 3 and _{CH 3 (CH 2) Y (} CHOSO 3 - M +) for _{CH 2 CH 3 C 10 -C 18} 2 -class (2, 3) alkyl sulfates, where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is an unsaturated sulfate such as a water solubilizing cation, in particular sodium, oleyl sulfate; C ₁₀ -C ₁₈ alkyl alkoxy sulfates (AExS, in particular ethoxy sulfates of EO 1 to 7), C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (particularly ethoxycarboxylates of EO 1 to 5), C ₁₀ -C ₁₈ glycerol Ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C ₁₂ -C ₁₈ α-sulfonated fatty acid esters. If desired, C ₁₂ -C ₁₈ comprising so-called narrow peaked alkyl ethoxylates and C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy) Conventional nonionic and amphoteric surfactants such as alkyl ethoxylates (AE), C ₁₂ -C ₁₈ betaines and sulfobetaines (sultaines), C ₁₀ -C ₁₈ amine oxides and the like can also be included in the overall composition. have. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amines may also be used. C ₁₀ -C ₁₈ N-alkylpolyhydroxy fatty acid amines can also be used. Typical examples include C ₁₂ -C ₁₈ N-methylglucamide (see W09,206,154). Other sugar derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamide can be used for generating a small amount of foam. Conventional soaps of C ₁₀ -C ₂₀ can also be used. If large amounts of foam are required, branched C ₁₀ -C ₁₆ soaps can be used. Especially useful are mixtures of anionic and nonionic surfactants. Other common useful surfactants are listed in the standard booklet.

[Enhancer]

Detergent enhancers can optionally be included in the compositions for controlling mineral hardness. Inorganic and organic enhancers can be used. Enhancers are typically used in fabric laundry compositions to remove particulate dirt.

The amount of enhancer can vary greatly depending on the end use of the composition and the desired physical form. The composition typically comprises at least about 1% of an enhancer. Liquid formulations typically comprise about 5 to about 50 weight percent, more typically about 5 to about 30 weight percent detergent enhancer. Granular formulations typically comprise about 10 to about 80 weight percent, more typically about 15 to about 50 weight percent detergent enhancer. However, less or greater amounts of enhancers are not excluded.

Inorganic detergent enhancers or P-containing detergent enhancers include polyphosphates such as tripolyphosphate, pyrophosphate and glassy polymeric metaphosphates, phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminos Silicate alkali metal salts, amnonium salts and alkanolammonium salts are included, but are not limited to these. However, nonphosphate enhancers are needed in certain cases. Importantly, the composition works surprisingly even in the presence of weak enhancers (relative to phosphates) such as citrate or in the absence of a zeolite or laminated silicate enhancer.

Examples of silicate enhancers include alkali metal silicates, especially silicates and H, in which the ratio of SiO ₂ : Na ₂ O is 1.6: 1 to 3.2: 1. blood. Laminated silicates, such as Laminated Sodium Silicate, described in HP Rieck, US Pat. No. 4,664,839 (May 12, 1987). NaSKS-6 is a trade name (usually abbreviated as SKS-6) of the crystalline laminated silicate sold by Hoechst. Unlike zeolite enhancers, NaSKS-6 silicate enhancers do not contain aluminum. NaSKS-6 is the δ-Na ₂ SiO ₅ form of laminated silicates. It may be prepared by the methods described in DE-A 3,417,649 and 3,742,043. SKS-6 is a very preferred laminated silicate for use in the present invention, but other laminated silicates, for example silicates such as NaMSi × O _{2 × 1} · _Y H ₂ O, wherein M is sodium or hydrogen, x Is 1.9 to 4, preferably 2, and y is 0 to 20, preferably 0). Various other laminated silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in α, β and γ forms. As mentioned above, δ-Na ₂ SiO ₅ (NaSKS-6 form) is most preferably used in the present invention. In addition, other silicates, such as magnesium silicate, which may be provided as crisps in granular formulations, may be useful, for example, as stabilizers for oxygen bleach and components of soap bubble control systems.

Examples of carbonate enhancers are alkaline earth metals and alkali metal carbonates described in German Patent Application No. 2,321,001 (published November 15, 1973).

Aluminosilicate enhancers are useful in the present invention. Aluminosilicate enhancers are important in heavy granular detergent compositions currently commercially available and may also be important enhancer components in liquid detergent formulations. Aluminosilicate enhancers include compounds of M _z (zAlO ₂ ) _y · _x H ₂ O where z and y are integers greater than or equal to 6 and the molar ratio of z to y ranges from 1.0 to about 0.5 and x is about An integer from 15 to about 264).

Useful aluminosilicate ion exchange materials are commercially available. Such aluminosilicates are structurally crystalline or amorphous and may be natural aluminosilicates or derived synthetically. Methods for preparing aluminosilicate ion exchange materials are described in US Pat. No. 3,985,669 (Kulmel et al., Oct. 12, 1976). Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are commercially available under the trade names Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is a substance of Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] _x H ₂ O, wherein x is from about 20 to about 30, in particular about 27 )to be. This material is known as zeolite A. Dehydrated zeolites (x = 0 to 10) can also be used. Preferably the particle size of the aluminosilicate is about 0.1-10 μm in diameter.

Organic detergent enhancers suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. Polycarboxylates refer to compounds having multiple, preferably three or more carboxylate groups. Polycarboxylate enhancers are generally added to the composition in acid form but may also be added in neutralized salt form. When used in salt form, alkali metal salts or alkanolammonium salts such as sodium salts, potassium salts and lithium salts are preferred.

Polycarboxylate enhancers include various categories of useful materials. One important category of polycarboxylate enhancers is described in Berg, U.S. Patent No. 3,128,287 (April 7, 2003) and Lamberti, U.S. Patent No. 3,635,830 (January 18, 1972). As is mentioned, ether polycarboxylates including oxydisuccinates are included. See also US Pat. No. 4,663,071 (May 5, 1987) to Bush et al., TMS / TDS enhancer. Suitable ether polycarboxylates also include the cyclic compounds described in US Pat. Nos. 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903, in particular alicyclic compounds.

Other useful wash enhancers include ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, carboxymethyloxy Various alkali metal salts, ammonium salts and substituted ammonium salts of polyacetic acid, such as succinic acid, ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as melic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5, Polycarboxylates such as -tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof.

Citrate enhancers such as citric acid and soluble salts thereof (particularly sodium salts) are polycarboxylate enhancers of particular importance for heavy liquid detergent formulations because of their utility due to regeneration sources and biodegradability. Citrate can also be used in granular compositions, in particular in combination with zeolites and / or laminated silicate enhancers. Oxydisuccinates are also particularly useful in combination with such compositions.

Also suitable for the detergent compositions of the present invention are compounds associated with 3,3-dicarboxy-4-oxa-1,6-hexanedioate described in Bush's US Pat. No. 4,566,984 (January 28, 1986). . Useful succinic acid enhancers include C ₅ -C ₂₀ alkyl and alkenyl succinic acid and salts thereof. Particularly preferred compounds of this type are dodecenyl succinic acid. Specific examples of succinate enhancers include lauryl succinate, myristyl succinate, palmity succinate, 2-dodecenyl succinate (preferably), 2-pentadecenyl succinate, and the like. Laurylsuccinate is a preferred enhancer and is described in European Patent Application No. 86200690.5 / 0,200,263 published Nov. 5, 1986.

See other suitable polycarboxylate Crutchfield et al. US Pat. No. 4,144,226 (March 13, 1979) and Diehl US Pat. No. 3,723,322.

For example, fatty acids such as C ₁₂ -C ₁₈ monocarboxylic acids may also be incorporated into the composition alone or in combination with enhancers, in particular citrate and / or succinate enhancers, to provide additional enhancement properties. The use of such fatty acids generally results in lowered soap lathering, which the formulator should consider.

When using phosphorus enhancers and especially when formulating soaps used in hand washes, various alkali metal phosphates such as the well-known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate enhancers such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates can also be used (US Pat. Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148). And 3,422,137).

[enzyme]

Enzymes can be included in the formulations for a variety of fabric laundering purposes, including removal of protein based, carbohydrate based or triglyceride based stains, as well as for the protection of escaped dye transfer and for fabric recovery. Enzymes to be introduced include proteases, amylases, lipases, cellulases and peroxidases as well as mixtures thereof. In addition, other types of enzymes may be included. It may have any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. However, it is selected according to several factors, such as pH activity and / or stability optimum conditions, thermal stability, stability to the active ingredient, enhancers and the like. In this respect, bacterial or fungal enzymes such as bacterial amylases and proteases, and fungal cellulase are preferred.

The enzyme is usually introduced in an amount sufficient to provide up to about 5 mg, more typically about 0.01 to about 3 mg, of active enzyme per gram of composition. In other words, the composition typically comprises from about 0.001 to about 5 weight percent, preferably 0.01 to 1 weight percent of a conventional enzyme formulation. Protease enzymes are usually present in conventional formulations in an amount sufficient to provide between 0.005 and 0.1 Anson units (AU) of activity per gram of composition.

Suitable examples of proteases are subtilisin obtained from certain strains of Bacillus subtilis and Bacillus liqueniforms. Other suitable proteases are obtained from Bacillus strains that exhibit maximal activity over pH 8-12 and are commercially available from Novo Industries A / S (Denmark) under the trade name ESPERASE. Methods for preparing enzymes similar to this enzyme are described in Novo's British Patent Application No. 1,243,784. Enzymes commercially available as proteolytic enzymes suitable for removing protein stains include Novo Industries A / S brand names Alcalase and SAVINASE, and International Bio-Synthetics, Inc. International Bio-Synthetics, Inc., Netherlands). Other proteases include Protease A (see European Patent Application No. 130,756 (published Jan. 9, 1985)) and Protease B (European Patent Application No. 87303761.8 (filed Apr. 28, 1987)) and Bot et al. Patent Application No. 130,756 (published Jan. 9, 1985). Most preferred are alkaline serine protease variants from Bacillus, in particular Bacillus lentus, arginine at position 27 to lysine, tyrosine at position 104 to valine, serine to position 123 to asparagine, and alanine to position 274 Protease C replaced with threonine. Protease C is described in European patents 90915958.4, US Pat. Nos. 5,185,250 and 5,204015. Also preferred are pending US patent application Ser. No. 08 / 136,797, entitled Protease-Containing Cleaning Composition, and Bleaching Compositions Comprising Protease Enzymes, incorporating the protease enzyme. Described in pending US patent application Ser. No. 08 / 136,626, which is incorporated herein by reference. In particular, genetically modified modifications of protease C may also be included.

Amylases include, for example, International Buyer-Synthetics, Incorporated RAPIDASE, and TERMAMYL from Novo Industries A / S, described in British Patent Application No. 1,296,839 (Novo). This includes.

Cellulase useful in the present invention includes both bacterial and fungal cellases. Preferably, its pH optimum is 5 to 9.5. Suitable cellulases are described in US Pat. No. 4,435,307 (March 6, 1984) to Barbesgoard et al., Which are fungal cellases or subtypes prepared from Fumicola insolelens and Fumicola strain DSM 1800. Cellulase 212 produced fungi belonging to the genus Eromonas and cellulase extracted from the liver pancreas of marine molluscs (Dolabella auricula solander). Suitable cellulases are also described in British Patent Publication Nos. 2,075,028, and 2,095,275 and DE-OS 2,247,832. Carrezyme is particularly useful.

Lipase enzymes suitable for use in detergents include enzymes produced by microorganisms of the Pseudomonas group, such as Pseudomonas stuttgeri ATCC 19.154, described in British Patent No. 1,372,034. See also Lipase in Japanese Patent Application No. 53-20487 (published on February 24, 1978). This lipase is commercially available from Amano Pharmaceutice I Co., Ltd. of Nagoyaken, Japan under the trade name Lipase P Amano (hereinafter referred to as Amano-P). Other commercially available lipases include Amano-CES, such as Chromobacter Biskosum variant Lipolitumum NRRLB 3673, by Toyo Jozo Co. of Dagataken, Japan, Lipase from Chromobacter Biskosum, Lipases from Chromobacter biskosum lipase and Pseudomonas gladiolus from Biochemical Corp. of the United States and Deisoynth Co. of the Netherlands. A lipase derived from Humicola ranuginosa and Novo commercially available LIPOLASE enzyme (see EPO 341,947) is the preferred lipase for use.

Peroxidase enzymes are used in combination with oxygen sources such as, for example, percarbonates, perborates, persulfates, hydrogen peroxide, and the like. This is used to prevent solution bleaching, i.e. dyes or pigments removed from the substrate during the laundry operation, from transferring to other substrates in the wash liquor. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxy, such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are, for example, assigned to Novo Industries A / S. PCT International Application No. W089 / 099813 (published October 19, 1989) by O. Kirk.

A wide range of enzymatic materials and means of introduction for introduction into synthetic detergent compositions is also described in US Pat. No. 3,553,139 (March 1, 1971) to McCarty et al. Enzymes are also described in both Place et al. US Pat. No. 4,101,457 (July 18, 1978) and Hughes US Pat. No. 4,507,219 (March 26, 1985). Enzyme materials useful for liquid detergent formulations and their introduction into formulations are described in US Pat. No. 4,261,868 (April 14, 1981) to Hora et al. Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques include Gedge et al. US Patent No. 3,600,319 (August 17, 1971) and European Patent Publication No. 0 199 405, Venegas European Patent Application No. 86200586.5 (October 1986). 29. Disclosure). Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570.

[Enzyme Stabilizer]

Enzymes used in the present invention are stabilized by the presence of water-soluble sources of these ions in the final composition that provide calcium and / or magnesium ions to the enzyme (calcium ions are generally somewhat more effective than magnesium ions and only one type of cation Is preferred when used). Further stability may be provided in the presence of various other known stabilizers, in particular borate species (see US Pat. No. 4,537,706). Typical detergents, in particular liquid detergents, comprise about 1 to about 30 mmoles, preferably about 2 to about 20 mmoles, more preferably about 5 to about 15 mmoles, and most preferably about 8 to about 12 mmoles, per liter of the final composition. This may vary somewhat depending on the amount of enzyme present and the response to calcium or magnesium ions. The amount of calcium or magnesium ions should be chosen to be always at a minimum usefully useful for enzymes after complexing with enhancers, fatty acids and the like in the composition. Water-soluble calcium salts or magnesium salts, including calcium chloride, calcium sulfate, calcium maleate, calcium maleate, calcium hydroxide, calcium formate and calcium acetate, and corresponding magnesium salts, can be used as the source of calcium or magnesium ions, but are not limited thereto. no. Small amounts of calcium ions, generally about 0.05 to about 0.4 mmoles per liter of composition, may also be present in the composition due to the enzyme slurry and calcium in the preparation water. In the case of a solid detergent composition, the formulation may contain a sufficient amount of water soluble calcium ions so that the amount is provided in the wash liquor. Or natural water hardness may be sufficient.

It is understood that such amounts of calcium and / or magnesium ions are sufficient to provide enzyme stability. Higher amounts of calcium and / or magnesium ions may be added to the composition to provide additional means of gloss removal performance. Thus, in general, the composition typically comprises about 0.05 to about 2 weight percent of a water soluble source of calcium or magnesium ions or both. The amount may of course vary depending on the amount and type of enzyme used in the composition.

The composition may also optionally, but preferably contain various further stabilizers, in particular stabilizers of the borate type. Typically, such stabilizers are from about 0.25 to about 10 weight percent, preferably from about 0.5 to about 5 weight percent, more preferably boric acid or other borate compounds (calculated based on boric acid) capable of forming boric acid in the composition. Is used in the composition in an amount of about 0.75 to about 3% by weight. Other compounds such as borate oxides, borax and other alkali metal borate salts such as sodium ortho-, meta- and pyroborate salts, and sodium pentaborate are suitable, but boric acid is preferred. Substituted boric acids such as phenylboronic acid, butaneboronic acid and p-bromo phenylboronic acid may also be used in place of boric acid.

Bleach Compounds-Bleaches and Bleach Activators

It may optionally contain a bleach composition comprising a bleach or bleach and at least one bleach activator. Compositions should be considered by formulators when properly formulated by those skilled in the art, as the use of bleach compounds with the soil dispersants of the present invention generally degrades bleaching performance. Bleach is typically from about 1% to about 30%, especially of fabric laundry detergent compositions. More typically from about 5 to about 20%. The amount of bleach activator is typically about 0.1 to about 60%, more typically about 0.5 to about 40% of the bleach composition comprising bleach and bleach activator.

The bleach used in the present invention may be any bleach useful for fabric washing, hard surface cleaning or other cleaning detergent compositions known or known. This includes oxygen bleach as well as other bleaches. Perborate bleaches such as sodium perborate (eg monohydrate or tetrahydrate) can be used.

Other types of bleaches that can be used without limitation include percarboxylic acid bleaches and salts thereof. Suitable examples of bleaches of this kind include magnesium monoperoxyphthalate hexahydrate, magnesium salts of meta-chloro perbenzoic acid, 4-nonylamino-4-oxperoxybutyric acid and diperoxydodecanedioic acid. Such bleaches are described in US Pat. No. 4,483,781 (Hartmann, Nov. 20, 1984), Burns et al. US Patent No. 740,446 (Jun. 3, 1985), Banks et al. US Patent No. 4,412,934 (Nov. 1, 1983) to Patent Application Nos. 0,133,354 (published Feb. 20, 1985) and Chung et al. Highly preferred bleaches also include the 6-nonylamino-6-oxperoxycaproic acid described in Burns et al. US Pat. No. 4,634,551 (January 6, 1987).

Peroxygen bleach can also be used. Suitable peroxy bleach compounds include sodium carbonate peroxyhydrate and equivalent percarbonate bleach, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleaches such as OXONE sold by DoPont may also be used.

Preferred percarbonate bleaching agents include anhydrous particles having an average particle size range of about 500 to about 1,000 μm, wherein up to about 10 wt% of the particles are less than about 200 μm and less than about 10 wt% are greater than about 1,250 μm. Optionally, the percarbonate can be coated with a silicate, borate or water soluble surfactant. Percarbonates can be purchased from a variety of sources, such as FMC, Solvay and Tokai Denka.

Bleach mixtures can also be used.

Peroxy bleach, perborate, percarbonate and the like are preferably combined with the bleach activator, thereby producing an aqueous solution of peroxy acid corresponding to the bleach activator (ie during the washing process). Various non-limiting examples of activators are described in Mao et al. US Pat. No. 4,915,854 (April 10, 1990), and US Pat. No. 4,412,934. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical and mixtures thereof may also be used. In addition, US Pat. No. 4,634,551 describes other typical bleaches and useful activators.

Highly preferred amido induced bleach activators are compounds of R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O) L ( Wherein R ¹ is an alkyl group of about 6 to about 12 carbon atoms, R ² is an alkylene of 1 to about 6 carbon atoms, R ⁵ is H or an alkyl, aryl or alkaryl having about 1 to about 10 carbon atoms, L is all suitable leaving groups). Leaving groups are all groups leaving the bleach activator as a result of the nucleophilic attack of the bleach activator by the perhydrolyzed anion. Preferred leaving group is phenyl sulfonate.

Preferred examples of the above bleach activator include (6-octane amido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) as described in US Pat. No. 4,634,551, which is incorporated herein by reference. Oxybenzenefonate, (6-decaneamido-caproyl) oxybenzenesulfonate and mixtures thereof.

Another class of bleach activators includes benzoxazine type activators described in US Pat. No. 4,966,723 (October 30, 1990) to Hodge et al., Incorporated herein by reference. Highly preferred activators of the benzoxazine type

to be.

Another class of preferred bleach activators include acyl lactam activators, in particular

Acyl caprolactam and

Acyl valerolactam of wherein R ⁶ is H, an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to about 12 carbon atoms, or a substituted phenyl group having about 6 to about 18 carbon atoms. See pending US patent applications 08 / 064,562 and 08 / 082,270, which describe substituted benzoyl lactams. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, Benzoyl valerolactam, octanoyl valerolactam, tecanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof do. See US Pat. No. 4,545,784 to Oct. 8, 1985, which describes acyl caprolactam including benzoyl caprolactam, incorporated herein by reference and adsorbed on sodium perborate.

Bleaches other than oxygen bleaches are also known in the art and may be used herein. One type of non-oxygen bleach that is of particular interest includes photoactivating bleaches such as sulfonated zinc and / or aluminum phthalocyanine. See, eg, US Pat. No. 4,033,718 to Holcombe et al. When using such bleach, the detergent composition typically contains from about 0.025 to about 1.25% by weight of the bleach, in particular sulfonate zinc phthalocyanine,

If desired, the bleach compound can be catalyzed with a manganese compound. Such compounds are well known in the art and include, for example, US Pat. Nos. 5,246,621, 5,244,594, 5,194,416 and 5,114,606, and EP 549,271 A1, 549,272 A1, Manganese-based catalysts described in 544,440 A2 and 544,490 A1. Preferred examples of such catalysts include M _n IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , M _n III ₂ (uO) ₁ ( u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) _2- (ClO ₄ ) ₂ , M _n IV ₄ (uO) ₆ (1,4,7-triaza cyclo _{nonane) 4 (ClO 4) 4,} M n IIIM n IV 4 (uO) 1 (u-OAc) 2 - (1,4,7- trimethyl -1,4,7- triaza-bicyclo-nonane) ₂ (ClO ₄ ) ₃ , M _n IV (1,4,7-trimethyl-1,4,7-triazacyclononan)-(OCH ₃ ) ₃ (PF ₆ ) and mixtures thereof. Other metal based bleach catalysts include those described in US Pat. Nos. 4,430,243 and 5,114,611. The use of manganese with various complex ligands to enhance bleaching is reported in US Pat. Nos. 4,728,455, 5,284,944, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161, and 5,227,084. have.

In practice, the compositions and processes can be adjusted to provide at least one active bleach catalyst species per 10 million parts of aqueous laundry medium, preferably from about 0.1 to about 700 ppm, more preferably from about 1 to about 500 ppm of catalyst species in the wash liquor. do.

Polymeric Antifouling Agents In addition to the soil dispersants of the present invention, polymeric antifouling agents known to those skilled in the art can optionally be used in the compositions and fixation of the present invention. Polymeric antifouling agents are deposited on hydrophilic fractions and hydrophobic fibers to hydrophilize the surfaces of hydrophobic fabrics, such as polyester and nylon, and remain deposited until the wash and rinse cycles are complete to serve as anchors for the hydrophilic fraction. It is characterized by having both fractions. This allows stains after treatment with antifouling agents to be more easily cleaned during subsequent washing procedures.

Polymeric antifouling agents useful in the present invention particularly

Polyoxyethylene fraction (i) having a degree of polymerization of at least 2, an oxypropylene or polyoxypropylene fraction having a degree of polymerization of 2 to 10 (the hydrophilic fraction thus comprising oxypropylene units unless each end is bonded to an adjacent moiety by an ether bond) (Ii) or a mixture of oxyalkylene units comprising oxyethylene and 1 to about 30 oxypropylene units, wherein the mixture contains a sufficient amount of oxyethylene so that the hydrophilicity of the hydrophilic component is conventional Large enough to increase the hydrophilicity of the surface when antifouling agents are deposited on the fiber surface, the hydrophilic fraction preferably comprises at least about 25% oxyethylene units, more preferably from about 20 to about oxypropylene units 30) (iii) at least one nonionic hydrophilic component (a), or C ₃ Oxyalkylene terephthalate fraction (the hydrophobic component also includes oxyethylene terephthalate and the ratio of oxyethylene terephthalate to C ₃ oxyalkylene terephthalate units is about 2: 1 or less) (i), C ₄ -C ₆ alkylene or oxy C ₄ -C ₆ alkylene fractions or mixtures thereof (ii), poly (vinyl ester) fractions having a degree of polymerization of at least 2, preferably polyvinyl acetate (iii) or C ₁ -C ₄ alkyl ethers or C ₄ hydroxyalkyl ether substituents or mixtures thereof (wherein the substituents are in the form of C ₁ -C ₄ alkyl ethers or C ₄ hydroxyalkyl ether cellulose derivatives or mixtures thereof and the cellulose derivatives are amphiphilic poly sufficient amount of the C ₁ -C ₄ alkyl ether and / or C ₄ hydroxyalkyl ether units having the conventional synthetic fibers to be deposited on a polyester synthetic fiber surfaces Antifouling with one or more hydrophobic component (b) or a combination of component (a) and component (b), including (iv) a sufficient amount of hydroxyl to increase fiber surface hydrophilicity when adhered to cotton I include

Typically, the degree of polymerization of the polyoxyethylene fraction of component (a) (i) is about 200 but higher degrees of polymerization, preferably from 3 to about 150, more preferably from 6 to about 100, can be used. Suitable oxy C ₄ -C ₆ alkylene hydrophobic fractions include polymers such as MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O—, described in Gomellink, US Pat. No. 4,721,580 (January 26, 1988). End caps of antifouling agents, where M is sodium and n is an integer from 4 to 6;

Polymeric antifouling agents useful in the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, copolymerizable blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such formulations are commercially available and include hydroxyethers of cellulose such as Dow's METHOCEL. As used herein, cellulose antifoulings also include those selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyalkyl cellulose. See US Pat. No. 4,000,093 to Dec. 18, 1976 to Nicol et al.

Antifouling agents characterized by poly (vinyl ether) hydrophobic fractions include graft copolymers of poly (vinyl esters), for example C ₁ -C ₆ vinyl esters, preferably polyalkylene oxide backbones such as polyethylene oxide backbones Poly (vinyl acetate) grafted to the substrate. See European Patent Application No. 0 219 048 (published on April 22, 1987) to Kud et al. Commercially available antifouling agents of this kind include the SOKALAN type commercially available from BASF, for example Sokalan HP-22.

One type of preferred antifouling agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of the polymeric antifouling agent ranges from about 25,000 to about 55,000. See Hayes, U.S. Patent No. 3,959,230 (May 25, 1976) and Basadur, U.S. Patent No. 3,893,929 (July 8, 1975).

Other preferred polymeric antifouling agents are from polyoxyethylene glycols wherein the ethylene terephthalate repeat units contain 10 to 15 weight percent ethylene terephthalate units with 90 to 80 weight percent polyoxyethylene terephthalate units and have an average molecular weight of 300 to 5,000. Derived polyesters. Examples of such polymers include commercially available ZELCON 5126 (Dupont) and MILEASE T (ICI). See U.S. Patent 4,702,857 to October 27, 1987.

Another preferred polymeric antifouling agent is the sulfonated product of a substantially straight ester oligomer consisting of terephthaloyl and oxyalkyleneoxy repeat units and oligomeric esters of terminal residues covalently attached to the main chain. second. J. J. Scheibel, U.S. Patent No. 4,968,451 (Nov. 6, 1990), and the European patent of Goschlink. Other suitable polymeric antifouling agents include terephthalate polyesters of U.S. Pat. No. 4,711,730 (Dec. 8, 1987), such as Godsonlink, and anionic ends of U.S. Pat. Capped oligomeric esters and block polyester oligomeric compounds of U.S. Patent No. 4,702,857 (October 27, 1987).

Preferred polymeric antifouling agents also include antifouling agents of Maldonado et al. US Pat. No. 4,877,896 (October 31, 1989), which are anionic, in particular sulfoaroyl end capped terephthalate esters.

Another preferred antifouling agent is an oligomer having repeating units of terephthaloyl units, sulfoisophthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeating units form the backbone of the oligomer and are preferably terminated with modified isethionate end caps. Particularly preferred antifouling agents of this type include about 1 sulfoisophthaloyl units, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units with a ratio of about 1.7 to about 1.8, and sodium 2- Two end cap units derived from (2-hydroxyethoxy) ethanesulfonate are included. The antifouling agent also preferably includes from about 0.5 to about 20 weight percent of an oligomer of a crystal shrinkage stabilizer selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures thereof.

When antifouling agents are used, the detergent compositions generally comprise from about 0.01 to about 10.0 weight percent, typically from about 0.1 to about 5 weight percent, preferably from about 0.2 to about 3.0 weight percent.

Chelating Agents-The detergent composition may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, multifunctional substituted aromatic chelating agents, and mixtures thereof. Without being limited by theory, the advantage of these materials lies in their excellent ability to form soluble chelates to remove iron and manganese ions from the laundry solution.

Amino carboxylates useful from any chelating agent include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylene-diamine tetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate , Ethanol diglycine, alkali metal salts thereof, ammonium salts and substituted ammonium salts, and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least small amounts of total phosphorus can be contained in the detergent composition, including ethylenediaminetetrakis (methylenephospho) as DEQUEST. Nate). Preference is given to amino phosphonates which do not contain alkyl or alkenyl groups of at least about 6 carbon atoms.

Multifunctional substituted aromatic chelating agents are also useful in the compositions. See Conner et al., US Pat. No. 3,812,044 (May 21, 1974). Preferred compounds in this type of acid form are di-, such as 1,2-dihydroxy-3,5-disulfobenzene. Hydroxydisulfobenzene.

Preferred biodegradable chelating agents for use in the present invention are the ethylenediamine disuccinates (EDDS) described in US Pat. No. 4,704,233 to Hartkins and Perkins (Nov. 3, 1987), in particular [S, S ] Isomers.

When using such a chelating agent, it is included in about 0.1 to about 10% by weight of the detergent composition. More preferably the chelating agent is included in the detergent composition at about 0.1 to about 3.0 weight percent.

Clay Soil Remover / Anti-Sedimentation Agent-In addition to the soil dispersant of the present invention, the compositions of the present invention may also contain charged, water-soluble, high ethoxylated amines that are polar and have clay soil removal and anti-deposition properties. Granular detergent compositions containing such compounds typically contain from about 0.01 to about 10.0 weight percent of charged high ethoxylated amines and liquid detergent compositions typically contain from about 0.01 to about 5 weight percent.

Most preferred antifouling agents and antideposition agents useful in the present invention are quaternized ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in US Pat. No. 4,597,898 (July 1, 1986) to VanderMeer. Another group of preferred clay soil remover-antideposition agents is the cationic compounds described in Oh and Gohlink's European Patent Application No. 111,965 (June 27, 1984). Other clay soil removers / antideposition agents that may be used include ethoxylated amine polymers described in Gomellink's European Patent Application No. 111,984 (published on Jun. 27, 1984), Gomellink's European Patent Application No. 112,592 (1984). Zwitterionic polymers described in 7. 4.) and amine oxides described in US Pat. No. 4,548,744 (October 22, 1985) to Connor. Other charged clay soil removers and / or antideposition agents known in the art may also be used in the compositions. Other types of preferred antideposition agents include carboxy methyl cellulose (CMC) materials. Such materials are well known in the art.

Polymeric Dispersants-Optionally, additional polymeric dispersants may be used in the composition, especially in the presence of zeolites and / or laminated silicate enhancers, in amounts of about 0.1 to about 7 weight percent. If a polymeric dispersant is used in the composition, suitable are polymeric polycarboxylates and polyethylene glycols, but others known in the art can also be used. Without being limited by theory, it is believed that polymeric dispersants, when used in combination with other enhancers (low molecular weight polycarboxylates), enhance overall detergent enhancer performance by crystal growth inhibition, particulate antifouling peptidation and anti-sticking agents.

Polymeric polycarboxylate materials can be prepared by polymerization or copolymerization in the form of suitable unsaturated monomers, preferably in acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. do. The presence of polymeric polycarboxylates or monomeric fractions that do not contain carboxylate radicals, such as vinylmethyl ether, styrene, ethylene, and the like, is suitable for the fraction to make up about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of these polymers in acid form is preferably about 2,000 to 10,000, more preferably about 4,000 to 7,000, most preferably about 4,000 to 5,000. Water soluble salts of such acrylic acid polymers may include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. Soluble polymers of this type are known materials. The use of this type of polyacrylate in detergent compositions is described, for example, in US Pat. No. 3,308,067 to Mar. 7, 1967.

Acrylic / maleic copolymers may also be used as preferred components of the dispersant / antideposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in acid form is preferably about 2,000 to 100,000, more preferably about 5,000 to 75,000, most preferably about 7,000 to 65,000. The range of ratio of acrylate to maleate fraction in such copolymers is generally from about 30: 1 to about 1: 1, preferably from about 10: 1 to 2: 1. Soluble salts of such acrylic acid / maleic acid copolymers may include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known from the known materials described in EP 66915 (published Dec. 15, 1982) and EP 193,360 (published Sep. 3, 1986). It is a polymer containing hydroxypropyl acrylate. Another useful dispersant includes maleic / acrylic acid / vinyl alcohol terpolymers. Such materials are also described in EP 193,360 and include 45/45/10 terpolymers of acrylic acid / maleic acid / vinyl alcohol.

Another polymeric material that may be included is polyethylene glycol (PEG). PEG not only exhibits dispersant performance but also acts as a clay dirt remover-antideposition agent. Typical molecular weights for this purpose range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartates and polyglutamate dispersants may also be used, in particular with zeolite enhancers. The average molecular weight of the dispersant, such as polyaspartate, is preferably about 10,000.

Brighteners—Optical brighteners or other brighteners or brighteners known in the art may be introduced into detergent compositions, typically in amounts of about 0.05 to about 1.2% by weight. Commercially available optical varnishes that may be useful in the present invention can be divided into subgroups, including stilbene derivatives, pyrazolines, coumarins, carboxylic acids, methine cyanines, dibenzotifen-5,5-dioxide, azoles, 5-membered rings. And 6-membered heterocycles and other heterogeneous agents. Examples of such brightening agents are described in The Production and Application of Fluorescent Brightening Agents, M. Zahradnik, Published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners useful in the present invention are described in Wixon, US Pat. No. 4,790,856 (Dec. 13, 1988). Such varnishes include Verona's PHORWHITE series. Other brighteners described in this document include Ciba-Geigy's Tinopal UNPA. Tinopal CBS and Tyropal 5BM, Artic White CC and Hilton White CWD from Hilton-Davis (Italy), 2- (4-Stryl-phenyl) -2H-naphthol [1,2 -d] triazole, 4,4'-bis (1,2,3-triazol-2-yl) -stilbene, 4,4'-bis (stryl) vinylphenyl and aminocoumarin. Specific examples of such brightening agents include 4-methyl-7-diethyl-amino coumarin, 1,2-bis (benzimidazol-2-yl) ethylene, 1,3-diphenyl-prazoline, 2,5-bis ( Benzoxazol-2-yl) thiophene, 2-strylnaph- [1,2-d] oxazole and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] tria Sol is included. See also Hamilton, US Pat. No. 3,646,015 (February 29, 1972). Anionic varnishes are preferred.

Suds suppressors—Compounds that reduce or inhibit the formation of suds can be incorporated into the compositions of the present invention. Suds suppression is particularly important in the so-called highly concentrated washing processes and front loading European washing machines described in US Pat. Nos. 4,489,455 and 4,489,574.

Various materials can be used as suds suppressors and suds suppressors are well known to those skilled in the art. See Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume, 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One class of suds suppressors of particular interest include monocarboxylic acid fatty acids and soluble salts thereof. See US Pat. No. 2,954,347 (September 27, 1960) by Wayne St. John. Monocarboxylic acid fatty acids and salts thereof used as suds suppressors typically have hydrocarbyl chains having 10 to about 24 carbon atoms, preferably 12 to about 18 carbon atoms. Suitable salts include alkali metal salts such as sodium salts, potassium salts and lithium salts, ammonium salts and alkanolamnonium salts.

The detergent composition may also contain a nonsurfactant suds suppressor. This includes, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones (eg stearone) and the like. Other suds suppressors include N, such as tri- to hexa-alkylmelamine or di- to tetra-alkyldiamine chlortriazine, produced as a product of cyanuric chloride with 2 or 3 mole of primary or secondary amines having 1 to 24 carbon atoms. Monostearyl phosphates such as alkylated amino triazines, propylene oxide and monostearyl aryl alcohol phosphate esters and monostearyl di-alkali metals such as K, Na and Li phosphates and phosphate esters. Hydrocarbons such as paraffin and haloparaffin can be used in liquid form. Liquid hydrocarbons are liquid at room temperature and atmospheric pressure, have a pour point in the range of about −40 to about 50 ° C. and a minimum boiling point of at least about 110 ° C. (atmospheric pressure). It is also known to use waxy hydrocarbons which preferably have a melting point of less than about 100 ° C. Hydrocarbons are a preferred class of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in US Pat. No. 4,265,779 (May 5, 1981) to Gandolfo et al. Hydrocarbons include aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having about 12 to about 70 carbon atoms. The term paraffin, used in suds suppressors, includes a mixture of true paraffins and cyclic hydrocarbons.

Another preferred class of nonsurfactant suds suppressors include silicone suds suppressors. This class includes dispersions or emulsions of polyorganosiloxane oils such as polydimethylsiloxane, polyorganosiloxane oils or resins, and combinations of polyorganosiloxanes with silica particles, wherein the polyorganosiloxanes are chemically absorbed or fused to silica. Use is included. Silicone suds suppressors are well known in the art and are described, for example, in U.S. Pat. Nos. 4,265,779 (May 5, 1981) to Gandolfo et al. s. European Patent Application No. 89307851.9 (published Feb. 7, 1990) by M. S. Starch.

Other silicone suds suppressors are described in US Pat. No. 3,455,839, which relates to compositions and methods for introducing small amounts of polydimethylsiloxane fluid to blister aqueous solutions.

Mixtures of silicon and silanized silica are described, for example, in German patent application DOS 2,124,526. Silicone antifoams and suds modifiers in granular detergent compositions are described in US Pat. No. 3,933,672 to Bartolota et al. And US Pat. No. 4,652,392 to Baginski et al. (March 24, 1987).

Examples of silicone suds suppressors used in the present invention include polydimethylsiloxane fluids (i), (i) having a viscosity of about 20 to about 1,500 cs at 25 ° C. of the suds suppressor (CH ₃ ) ₃ SiO Siloxane resin consisting of _1/2 unit and SiO ₂ unit [(CH ₃ ) ₃ ratio of SiO _1/2 unit to SiO ₂ unit is about 0.6: 1 to about 1.2: 1] (ii) about 5 to about 50 parts And (i) about 1 to about 20 parts of a solid silica gel (iii) per 100 parts by weight of a lather control agent.

For preferred silicone suds suppressors used in the present invention, the solvent for the continuous phase consists of a particular polyethylene glycol or polyethylene-polypropylene glycol copolymer or mixtures thereof (preferably), or polypropylene glycol. The primary silicone suds suppressors are those that are bleached / crosslinked and preferably not straight chain.

To further illustrate this point, a typical liquid laundry detergent composition adjusted with suds may optionally contain from about 0.001% to about 1% by weight of silicone suds suppressor, preferably from about 0.01% to about 0.7% by weight and most preferably about 0.05%. To about 0.5% by weight, wherein the silicone suds suppressor comprises polyorganosiloxane (a), resinous siloxane or silicone resin producing silicone compound (b), finely divided filler (c) and mixture components (a), (b) And a non-aqueous emulsion of main antifoaming agent (1), at least one nonionic silicone surfactant (2) and polyethylene glycol or in water at room temperature, which is a mixture with a catalyst (d) to accelerate the reaction of (c) to form silanolates. Polyethylene-polypropylene glycol copolymer (3) having a solubility of at least about 2% by weight. Similar amounts can be used for particulate compositions, gels and the like. Starch, U.S. Patent No. 4,978,471 (Dec. 18, 1990), Hober et al., U.S. Patent No. 4,983,316 (January 1, 1991), 5,288,431 (February 24, 1994) and Aizawa ( See also US Pat. Nos. 4,639,489 and 4,749,740, column 1, line 46 to column 4, line 35 of Aizawa et al.

The silicone suds suppressor preferably comprises a copolymer of polyethylene glycol and polyethylene glycol / polypropylene glycol having an average molecular weight of less than about 1,000, preferably from about 100 to 800. The solubility of polyethylene glycol and polyethylene / polypropylene copolymer in water at room temperature is at least about 2% by weight, preferably at least about 5% by weight.

Preferred solvents are polyethylene glycols and polyethylene glycols / polypropylene glycols, preferably PPG 200 / PEG 300, having an average molecular weight of less than about 1,000, more preferably from about 100 to 800, most preferably from 200 to 400. The weight ratio of the copolymer of polyethylene glycol: polyethylene-polypropylene glycol is preferably about 1: 1 to 1:10, preferably 1: 3 to 1: 6.

Preferred silicone suds suppressors used in the present invention do not contain polypropylene glycols having a molecular weight of 4,000 in particular. It also preferably does not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other silicone suds suppressors useful in the present invention include secondary alcohols (eg, 2-alkyl alkanols) and such alcohols and silicone oils, such as in US Pat. Nos. 4,789,679 and 4,047,118, and European Patent 150,872. Blends with silicone as described. Secondary alcohols include C ₆ -C ₁₆ alkyl alcohols having C ₁ -C ₁₆ chains. Preferred alcohols are 2-butyl octanol sold by Condea under the trade name ISOFOL 12. A mixture of secondary alcohols is commercially available from Enichem under the trade name ISALCHEM 123. Mixed suds suppressors typically comprise a mixture of alcohols and silicones in a weight ratio of 1: 5 to 5: 1.

For all detergent compositions used in automatic washing machines, the lather should not foam to the extent that the lather overflows the washing machine. If a suds suppressor is used, it is preferably present in a suds suppression amount. The suds suppression amount indicates that the formulator of the composition can sufficiently control the suds to select an amount of suds modifier that lowers the foamability of the laundry detergent used in the automatic washing machine.

The composition generally comprises 0-5% of the suds suppressor. When using monocarboxylic acid fatty acids and salts thereof as suds suppressors, they are typically present in amounts up to about 5% by weight of the detergent composition. Preferably, about 0.5 to about 3% of the fatty monocarboxylate suds suppressor is used. Silicone suds suppressors are typically used in amounts up to about 2.0% by weight of the detergent composition but higher amounts may be used. Its upper limit is practical in terms of efficiency in minimizing maintenance costs and effectively controlling foam lather in smaller amounts. Silicone suds suppressors are preferably used from about 0.01 to about 1%, more preferably from about 0.25 to about 0.5%. These weight percent values include all silicas that can be used in combination with the polyorganosiloxane, as well as auxiliary materials that can be used. Monostearyl phosphate suds suppressors are generally used in amounts of about 0.1 to about 2 weight percent of the composition. Hydrocarbon suds suppressors are typically applied in amounts of about 0.01% to about 5.0%, but higher amounts may be used. Alcohol suds suppressors typically use from 0.2 to 3% by weight of the final composition.

Fabric Softeners—Various laundry fabric softeners, in particular smectite clays of US Pat. No. 4,062,647 (Sec. 12, 1977) to Storm and Nischl, as well as other softener clays known in the art, are optionally exemplified in the composition. In amounts of about 0.5 to about 10% by weight to provide fabric softener benefits simultaneously with fabric washing. Clay softeners are cationic, as described in US Pat. No. 4,375,416 (April 1, 1983) to Amine and Crisp et al. And US Pat. No. 4,291,071 (April 22, 1981) to Harris et al. It can be used in combination with a softening agent.

Dye Transfer Inhibitors—In addition to a soil dispersant, the compositions of the present invention may also include one or more materials effective to inhibit the transfer of dye from one fabric to another during the washing process. Generally, such dye transfer inhibitors include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone with N-vinylimidazole, manganese phthalocyanine, peroxidase and mixtures thereof. Included. When such inhibitors are used, they typically comprise from about 0.01% to about 10%, preferably from about 0.01% to about 5%, more preferably from about 0.05% to about 2% by weight of the composition.

More specifically, preferred polyamine N-oxide polymers for use in the present invention are RA _A -P, wherein P is a polymerizable unit to which an NO group may be bonded, an NO group which may form part of a polymerizable unit, or NO is a group that can be bonded to both units, A is one of -NC (0)-,-(CO) OS-, -O-, -N =, x is 0 or 1, and R is NO Groups of which the nitrogen of the group may be bonded or the NO group is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or cycloaliphatic group or combination thereof). Preferred polyamine N-oxides are heterocyclic groups wherein R is pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

N-O Group

Wherein R ₁ , R ₂ or R ₃ is an aliphatic, aromatic, heterocyclic or cycloaliphatic group or combination thereof, x, y and z are 0 or 1 and the nitrogen of the NO group is bonded to the above group Or form part thereof). The amine oxide unit of the polyamine N-oxide is pKa10, preferably pKa7, more preferably pKa6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has dye transfer inhibition properties. Examples of suitable polymeric backbones are polyvinyl, polyalkylene, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. Such polymers include random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The ratio of amine to amine N-oxide of the amine N-oxide polymer is typically from 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer may vary depending on suitable copolymerization or suitable N-oxidation degrees. Polyamine oxides can also obtain almost any degree of polymerization. Typically, the average molecular weight ranges from 500 to 1,000,000, more preferably 1,000 to 500,000, most preferably 5,000 to 100,000. This preferred class of materials can be referred to as PVNO.

The most preferred polyamine N-oxides useful in this detergent composition are poly (4-vinylpyridine-N-oxides) having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4.

Copolymers of N-vinylpyrrolidone with N-vinylimidazole polymers (referred to as PVPVI) are also preferred for use in the present invention. Preferably, PVPVI has an average molecular weight range of 5,000 to 1,000,000, more preferably 5,000 to 200,000, most preferably 10,000 to 20,000 (average molecular weight ranges are described in Barth, et al. , Chemical Analysis, Vol 113. Modern Methods of Polymer Characterization]. PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone in the range of 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1. Such copolymers may be straight or branched.

The compositions of the present invention may also use polyvinylpyrrolidone (PVP) having an average molecular weight of about 5,000 to about 400,000, preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000. PVP is known to those skilled in the detergent field and see European Patent Publications 262,897 and 256,696, which are incorporated herein by reference. Compositions containing PVP may also contain polyethylene glycol (PEG) having an average molecular weight of about 500 to about 100,000, preferably about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP in the wash liquor is from about 2: 1 to about 50: 1, more preferably from about 3: 1 to about 10: 1, based on ppm.

The detergent composition may also contain about 0.005 to 5% by weight of certain types of hydrophilic optical brighteners, which optionally provide dye transfer inhibitory activity. When used, the composition preferably comprises about 0.01 to 1% by weight of an optical brightener.

Hydrophilic optical brighteners useful in the present invention are compounds of formula (2).

[Formula 2]

In Formula 2, R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, and R ₂ is N-2-bis-hydroxyethyl, N-2-hydroxy Hydroxyethyl-N-methylamino, morpholino, chloro and amino, M is a salt forming cation such as sodium or potassium.

In Formula 2, when R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M is a cation such as sodium, the brightening agent is 4,4'-bis [(4-anilino-6- ( N-2-bis-hydroxyethyl) -S-triazin-2-yl) amino] -2,2'-stilbenesulfonic acid and disodium salt. This particular varnish species is commercially available from Ciba-Geigy Corporation under the tradename Tinopal-UNPA-GX. Tinopal UNPA-GX is a preferred hydrophilic optical brightener useful in detergent compositions.

In Formula 2, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino, and M is a cation such as sodium, the brightening agent is 4,4'-bis [(4-anyl Lan-6- (N-2-hydroxyethyl-N-ethylamino) -S-triazin-2-yl) amino] -2,2-stilbendisulfonic acid and disodium salt. This particular varnish species is commercially available from Ciba-Geigy Corporation under the tradename Tinopal 5BM-GX.

In Formula 2, when R ₁ anilino, R ₂ is morpholino, and M is a cation such as sodium, the brightening agent is 4,4'-bis [(4-anilino-6-morpholino-s-triazine -2-yl) amino] -2,2'-stilbendisulfonic acid and disodium salt. This particular varnish species is commercially available from Ciba-Geigy Coporation under the tradename Tinopal AMS-GX.

Certain optical varnish species selected for use in the present invention provide effective dye transfer inhibition performance advantages, particularly when used in combination with the selected polymeric dye transfer inhibitors. The combination of the selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) with the selected polymeric material (e.g. PVNO and / or PVPVI) is a combination of the two detergent composition components, respectively. The inhibition of dye transfer in aqueous wash liquor is significantly better than when used alone. Without being limited by theory, the brightener works as above because it has a high affinity for the fabric in the wash liquor and deposits on the fabric relatively quickly. The degree to which the brightener is deposited on the fabric in the wash liquor can be defined as a parameter called the adsorption coefficient. The adsorption coefficient is generally the ratio of the polish material (a) deposited on the fabric to the initial polish concentration (b) in the wash liquor. Brighteners having a relatively high adsorption coefficient are most suitable for inhibiting dye transfer in the present invention.

Of course, other conventional optical brightener type compounds may optionally be used in the compositions to obtain the whitening advantage of conventional fabrics rather than the dye transfer inhibitory effect. Such use is common and well known in detergent formulations.

Other Ingredients-A variety of other ingredients useful in detergent compositions may be included in the composition, including other active ingredients, carriers, combustible triggers, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for solid soap compositions, and the like. This includes. If a high degree of lathering is desired, suds accelerators such as C ₁₀ -C ₁₆ alkanolamides can be introduced into the composition at levels typically of 1 to 10%. C ₁₀ -C ₁₄ monoethanol and diethanol amides are typical classes of such suds accelerators. It is also advantageous to use such suds accelerators with high sudsification co-surfactants such as amine oxides, betaines and sultaines described above. If desired, soluble magnesium salts such as MgCI ₂ , MgSO _4, and the like may be added at levels typically of 0.1 to 0.2% for further lathering and also to enhance oil removal performance.

The various washing components used in the composition may optionally be absorbed into the porous hydrophobic substrate and then further stabilized by coating the substrate with a hydrophobic coating. Preferably, the cleaning component is mixed with the surfactant prior to absorption into the porous substrate. If a cleaning component is used, it is released from the substrate into the aqueous wash liquor to achieve the intended cleaning performance.

To describe the technique in more detail, porous hydrophobic silica (SIPERNAT D10 from Degussa) containing 3 to 5% C ₁₃ -C ₁₅ ethoxylated alcohol (EO 7) nonionic surfactant Mix with protease solution. Typically, the enzyme / surfactant solution is 2.5 × silica in weight. The resulting powder is dispersed with stirring in silicone oil (various silicone oils with a viscosity range of 500 to 12,500 can be used). The resulting silicone oil dispersion is emulsified or added to the final detergent matrix. As such, components such as enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescent materials, fabric softeners and hydrolyzable surfactants may be protected for use in detergents including liquid laundry detergent compositions.

Liquid detergent compositions may contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable. Although monohydric alcohols are preferred for the stabilization of surfactants, polyols containing 2 to about 6 carbon atoms and containing 2 to about 6 hydroxyl groups, such as 1,3-propanediol, ethylene glycol, glycerin and 1,2- Propanediol) may also be used. The composition may contain 5 to 90%, typically 10 to 50%, of such carriers.

The detergent composition is preferably formulated such that the pH of the wash liquor is about 6.5 to about 12, preferably about 7.5 to 11, during use in aqueous laundry operations. Techniques for adjusting pH to suggested levels of use include the use of buffers, alkalis, acids, and the like, which are well known to those skilled in the art.

Example 1

[Ethoxylation of Poly (ethyleneimine) with an Average Molecular Weight of 1,200]

Klee Now head, the thermostat thermometer connected to (Therm-O-Watch ^TM, I ² R), switch the purge tube and the mounting 250ml mechanical stirrer were, three-necked molecular weight in the round bottom flask, 1200 poly (ethylene imine) poly Cyan Cis Incorporated (Polysciences, Inc.), 65.6 g, 0.055 mole] is added. Ethylene oxide gas (Liquid Carbonics) is added through a spurge tube with very rapid stirring until an increase in weight of 16.8 g (corresponding to 0.25 ethoxy units) is obtained at about 140 ° C. under argon. Store 25 g of yellow gel-like material. Ethylene oxide is added to the remaining material as above until a weight gain of 11.7 g (corresponding to a total of 0.50 ethoxy units) is obtained. Store 25 g of yellow gel-like material. Ethylene oxide is added to the remaining material as above until a weight gain of 8.3 g (corresponding to a total of 0.78 ethoxy units) is obtained. Store 25 g of yellow gel-like material. Ethylene oxide is added to the remaining material as above until a weight increase of 3.4 g (corresponding to a total of 1 ethoxy unit) is obtained to give 27.4 g of an orange gel-like material.

Example 2

[Ethoxylation of Poly (ethyleneimine) with an Average Molecular Weight of 1,800]

Klee now red, thermostat poly (Therm-O-Watch ^TM, I ² R) connected to a thermometer, to switch the purge tube and the mounting 250ml mechanical stirrer, a three-necked molecular weight in the round bottom flask 18 (ethyleneimine) (Poly Scientific Cis incorporated, 50.0 g, 0.028 mole) is added. Ethylene oxide gas (Liquid Carbonics) is added through a spurge tube with very rapid stirring until an weight gain of 52 g (corresponding to 1.2 ethoxy units) is obtained at about 140 ° C. under argon. Store 50 g of yellow gel-like material. Potassium hydroxide pellets (Baker, 0.30 g, 0.0053 mole) are added to the remaining material. After dissolving potassium hydroxide, ethylene oxide is added as above until a weight gain of 60 g (corresponding to 4.2 total ethoxy units) is obtained. Store 53 g of a yellow viscous liquid. Ethylene oxide was added to the remaining material as above until a weight gain of 35.9 g (corresponding to a total of 7.1 ethoxy units) was obtained, yielding 94.9 g of a dark brown liquid. Potassium hydroxide in the last two samples is neutralized by adding theoretical amounts of methanesulfonic acid.

Example 3

[Benzylation and Subsequent Ethoxylation of 10mole% Nitrogen in Poly (ethyleneimine) with Molecular Weight 18000]

A 100 mI, three-neck round bottom flask is equipped with a magnetic stir bar, condenser, thermometer, thermostat (Therm-O-Watch ^™ , I ² R) and an addition funnel. To the reaction flask, poly (ethyleneimine) having a molecular weight of 1,800 (polysciences incorporated, 20.0 g, 0.011 mole) was added. To the addition funnel is added benzyl chloride (Aldrich, 5.9 g, 0.047 mole) sufficient to react with 10 mole% of useful nitrogen in poly (ethyleneimine). The reaction flask is heated to 110 ° C. under argon, at which temperature benzyl chloride is added dropwise at a rate of about 1 drop every 3 seconds. Note the exotherm of about 10 ° C. during the addition process. After adding benzyl chloride, the heat of reaction is maintained at 100 ° C. under argon for 5 hours. After cooling for a short time, the orange product is dissolved in methanol to form a 20% by weight solution. To the solution is added a theoretical amount of 25% solution of sodium methoxide in methanol (Aldrich, 10.1 g, 0.047 mole) to neutralize the HCl formed during the reaction. The precipitated salt is filtered off using an intake vacuum to remove from the yellow solution. The solution is then stripped with methanol on a rotary evaporator (Buchi) at 50 ° C. and intake vacuum to yield benzylated PEI-1800.

Ethoxylation of benzylated PEI-1800 - 250ml to a 3-neck round bottom gas inlet tube with a glass tip assembly to the flask, a thermometer, a temperature controller ^{(Therm-O-Watch TM,} I 2 R) and glass shaft and Teflon blade The automated stirrer. Benzylated poly (ethyleneimine) (10.2 g, 0.005 mole) prepared as described above is placed in the reaction flask. The reaction is brought to 150 ° C. under vigorous stirring under argon. At this point ethylene oxide (liquid carbonics) was introduced into the reaction vessel until a weight increase of 3.7 g in the product was obtained (corresponding to an increase in weight corresponding to an ethoxylation degree of E of 0.5 for the useful nitrogen position of the polymer). Foam. A portion (4.1 g) of this product is taken out to the reaction vessel and the reaction temperature is maintained at 150 ° C. Ethylene oxide is introduced into the reaction until a weight increase of 2.7 g of product (degree of ethoxylation E = 1) is achieved. A portion (5.4 g) of brown product oil is removed from the reaction and 1 mole% potassium hydroxide is added as catalyst. Ethylene oxide is continuously introduced until an increase in weight of 13.4 g of product (degree of ethoxylation E = 5.6) is achieved. Again a portion of the product (9.5 g) is removed and additional potassium hydroxide catalyst (0.112 g) is added followed by continued ethoxylation with the stomach. The product increases in weight by 12.8 g (E = 14) during this step of the ethoxylation process. In the last two ethoxylations the base catalyst is neutralized with methanesulfonic acid (Aldrich). The polymer samples are each tested for water solubility in deionized water in small screw cap vials. Samples with E = 5.6 and samples with E = 14 are dissolved in a 10% by weight solution and samples with E = 1 are dissolved in a 1% by weight solution. Samples with E = 0.5 are only partially dissolved in 1% by weight solution. In this case a slightly opaque suspension is formed.

Example 4

[Synthesis of poly (ethyleneimine) with molecular weight of 18000, propoxylation to P = 1 and ethoxylation to E = 6.5 and E = 10.1]

A 250 ml three-neck round bottom flask is equipped with a magnetic stir bar, dry ice condenser, addition funnel, thermometer and thermostat (Therm-O-Watch ^™ , I ² R). To the reaction flask, poly (ethyleneimine) having a molecular weight of 1,800 (polysciences incorporated, 20.2 g, 0.011 mole) was added and an equivalent amount of distilled water was added. Propylene oxide (Aldhiri, 11.8 g, 0.203 mole) is added to the addition funnel. The reaction flask is heated to 80 ° C. under argon and at this temperature propylene oxide is added dropwise to the reaction in small increments over 1 hour. The addition of propylene oxide leads to a fume reaction. Therefore, the addition rate is controlled so that the reaction temperature does not exceed about 90 ° C. After all of the propylene oxide has been added, the reaction mixture is heated for an additional hour until no further reflux of propylene oxide is observed. The product solution is transferred to a 250 ml round bottom flask and stripped with water on a rotary evaporator (Buy) at 60 ° C. and an intake vacuum. To a portion of the viscous clear yellow product (35.1 g, 0.008 mole) is added 3.8 g of 25% solution of sodium methoxide (Aldrich) in methanol. The flask is then placed in Kugelrohr (Aldrich) until all the methoxide salt is dissolved and methanol and all residual water are distilled off at 160 ° C. and 2 mmHg for 5 hours.

The above product (17.0 g, 0.004 mole) is fitted with a gas inlet tube with assembled glass tip, thermometer, thermostat (Therm-O-Watch ^TM , I ² R) and an automated stirrer with glass shaft and Teflon blade 250 ml of the flasks are transferred to a three-neck round bottom flask. The reaction is brought to 150 ° C. under vigorous stirring under argon. At this point, the reaction vessel is thoroughly flushed with a heavy stream of argon for about 15 minutes. The ethylene oxide gas (liquid carbonics) is then bubbled through the reaction until a weight gain of 45.0 g of product (the corresponding weight increase corresponds to an ethoxylation degree E of 6.5 for the useful nitrogen position of the polymer) is obtained. . A portion of the gold product (30.2 g) is removed from the reaction vessel and the reaction temperature is maintained at 150 ° C. At this point, the reaction system is purged again with a lot of argon for about 15 minutes. After purging ethylene oxide is introduced until the product records a weight increase of 12.5 g (degree of ethoxylation E = 10.1). The product color at this time is essentially the same as the previous E level. The base catalyst in each ethoxylation product is neutralized with methanesulfonic acid (Aldrich). The polymer samples are each dissolved in a 10% solution in deionized water.

Example 5

[Benzoylation (25mol%) and Subsequent Ethoxylation of Poly (ethyleneimine) with Molecular Weight 600]

A 250 ml three-neck round bottom flask is equipped with a magnetic stir bar, thermometer, thermostat (Therm-O-Watch ^™ , I ² R), a modified Klyzen head and a condenser for distillation. To the reaction flask, poly (ethyleneimine) having a molecular weight of 600 (polysciences incorporated, 61.9 g, 0.103 mole) and methyl benzoate (Aldrich, 48.7 g, 0.358 mole) were added. The reaction is heated at 150 ° C. while distilling methanol under argon. The product is a viscous pale yellow oil (stores 10 g of this). Approximately 82.7 g of product is a 3-necked 500 ml, equipped with gas inlet tube with assembled glass tip, thermometer, thermostat (Therm-O-Watch ^TM , I ² R) and an automated stirrer with glass shaft and Teflon blade Add to round bottom flask. The reaction is brought to 150 ° C. or lower under argon with constant stirring. At this point, ethylene oxide (liquid carbonics) was added to 36.0 g of the product until a weight increase was achieved (corresponding to that weight increase corresponding to an ethoxylation degree E of about 1.0 for the remaining amino nitrogen NH position of the polymer). Foam into the reaction vessel. A portion (19.6 g) of dark red product is taken out of the reaction vessel and the reaction temperature is maintained at 150 ° C. Potassium hydroxide catalyst (Baker, 0.48 g, 1 mole%) is added to the reaction and dissolved. Ethylene oxide is introduced into the reaction until a weight gain of 37.1 g (degree of ethoxylation E = 2.2) is achieved. Again a portion of the brown product oil (49.2 g) is removed and the ethoxylation continues until an additional weight increase (E = 5.7) of 66.4 g of product is achieved. Stop ethoxylation and store the final dark brown product oil. The base catalyst in the last two ethoxylation products is neutralized with methanesulfonic acid (Aldrich). 25 mol% benzoylated PEI-600 forms an opaque white solution of 1% in deionized water that exhibits very limited solubility. The first two ethoxylated products dissolve completely in a 10% solution in deionized water, while the maximum E value does not dissolve completely at this concentration.

Example 6

[Synthesis of molecular weight 2018.5, reaction with poly (ethyleneimine) of 1,8000 molecular weight and subsequent ethoxylation]

A 100 ml three-neck round bottom flask is equipped with a magnetic rod, condenser, addition funnel, thermometer and thermostat (Therm-O-Watch ^™ , I ² R). Poly (ethylene glycol) and methyl ether (Aldrich, 60.0 g, 0.030 mole) having a molecular weight of 2,000 are added to the reaction flask. The reaction vessel is made below 65 ° C. to melt poly (ethylene glycol), methyl ether, then the reaction is cooled to 55 ° C. and maintained at this temperature. Thionyl chloride (Aldrich, 11.7 g, 0.100 mole) is added to the addition funnel and added dropwise to the reaction flask over 20 minutes. The reaction is heated at 55 ° C. under argon overnight. The bright orange waxy product is dissolved in an amount of methylene chloride (baker) sufficient to form a 30% by weight solution and then stripped on a rotary evaporator at 45 ° C. and intake vacuum. At this point the product pH measured by the pH strip is 2 or less. The product is again dissolved in 30% solution in methylene chloride (baker) and placed in a separating funnel. The product solution is washed once with saturated potassium carbonate (baker) solution in water. The methylene chloride layer is discharged and stripped again on a rotary evaporator under the above conditions. α- (2-chloroethyl) -ω-methoxy-poly (oxy-1,2-ethanediyl) is obtained as an orange waxy material.

α- (2-chloroethyl) -ω-methoxy-poly (oxy-1,2-ethanediyl) (13.1 g, 0.0065 mole), poly (ethyleneimine) (polysciences) having a molecular weight of 1,800, 11.7 g, 0.0065 mole) and a sufficient amount of deionized water to prepare a 35% by weight solution was filled with 100 ml with a stir bar, condenser, thermometer and thermostat (Therm-O-Watch ^TM , I ² R), 3 Add to old round bottom flask. The clear reaction solution is heated at 80 ° C. under argon overnight. After the reaction is complete, theoretical amounts of 50% sodium hydroxide solution (baker) are added to neutralize the acid formed. The solution is then placed in a 250 ml round bottom flask and streamed on a rotary evaporator at 60 ° C. and intake vacuum. Trace amounts of water are removed in a Kugelor apparatus (Aldrich) for 3 hours under conditions of 2 mmHg or less and 120 ° C. A portion of the waxy yellow product (14.2 g, 0.004 mole) was assembled with a gas inlet tube with an assembled glass tip, a thermometer, a thermostat (Therm-O-Watch ^TM , I ² R) and an automation with glass shaft and Teflon blades. 100 ml with a stirrer are weighed in a three neck round bottom flask. The reaction is brought to 150 ° C. or less with vigorous stirring under argon. At this point, ethylene oxide (liquid carbonics) was introduced into the reaction vessel until a weight increase of 3.4 g of the product was obtained (corresponding to the weight increase corresponding to ethoxylation degree E of 0.7 for the useful nitrogen position of the polymer). Foam. A portion of this dark yellow wax is removed and ethylene oxide continues to flow at 150 ° C. until a weight increase of 2.7 g (ethoxylation degree E = 1.1) is achieved. Again a portion of this orange product is stored and 1 mole% potassium hydroxide (baker) is added as catalyst. Ethoxylation is continued at 150 ° C. until a final weight increase (E = 2.0) of 3.1 g of product is achieved. The base catalyst in the red polymer is neutralized with methanesulfonic acid (Aldrich). All polymer samples show good solubility with a 10% solution of deionized water.

An example of the structure of ethoxylation degree 1 except for MPEG is

to be.

Example 7

A granular detergent composition comprising the following ingredients is prepared.

Component weight%

C ₁₃ straight chain alkyl benzene sulfonates 22

Phosphate (as Sodium Tripolyphosphate) 30

Sodium Carbonate 14

Sodium Silicate 3

Zeolite A (0.1 to 10 μ) 8.2

Nonanoyloxybenzenesulfonate 3.2

Sodium percarbonate ^* 4.5

Chelating Agent (Diethylenetriaminepentaacetic Acid) 0.4

Sodium Sulfate 5.5

Dispersant (Example 3) 0.4

Add minor ingredients, filler ^** and water to 100%.

Average particle size: 400 to 600μ

** can be selected from conventional materials such as CaCOS ₃ , talc, clay, silicate and the like.

The following test methods are used to test the dispersion performance of the dispersant:

White fabrics comprising cotton knit, heavy cotton knit, polycotton, terrycle rod, 60/40 polycotton, 50/50 polycotton and 100% polyester are used for the test. The fabric is removed with a commercially available granular detergent (DASH) using a Sears KENMORE washing machine. Washing is carried out for 12 minutes at a temperature of 120 ° F. (48.8 ° C.) with 0 grains (0 gpg water) per gallon of water and washing with 120 g (48.8 ° C.) with 0 gpg water. After performing this removal step twice, the washing process is carried out twice more using only water. The degreased fabric is made into specimen pieces (5 in ² ).

The test is carried out in a five-port automatic washing machine (AMW), similar to hand washing operations using standard conditions. After filling the AMW pots with 7.6 liters (2 gallons) of water each, a detergent composition (above) and a dispersant are added to each pot. The washed test specimen pieces are then added with an amount of unwashed contaminated consumer ballast to bring the desired level from about 0.5: 1 to about 15: 1 (L: Kg) of water / cloth ratio. The ballast is equally divided in half between the formulation containing the dispersant and the pot containing the same control formulation without the dispersant. Wash cycles are performed in 8 gpg water at a temperature of 77 ° F. (25 ° C.). The wash cycle consists of 30 minutes of soaking and 10 minutes of shaking. After the wash cycle, two 2-minute wash cycles and two 2-minute wash cycles using 8 gpg water at a temperature of 77 ° (25 ° C.) are performed. For the multiple cycle test, the test specimen piece is dried and the above steps are repeated using the same test piece piece and a new contaminated laundry package.

At the end of the final wash cycle, the test specimen pieces are dried in a dryer. Then three stimulation meters are read (L, a, b) for each test specimen piece. The brightening performance is then calculated from the Hunter brightening value (W) according to the following equation:

W = (7L ² -40Lb) / 700

The larger the w value, the better the brightening performance. All fabrics show increased whitening compared to fabrics that are not exposed to the dispersants of the invention after washing.

Example 8

Laundry solid soaps suitable for hand washing of contaminated fabrics are prepared by standard extrusion processes, which include the following.

Component weight%

C ₁₃ straight chain alkyl benzene sulfonate 30

Phosphates (as Sodium Tripolyphosphate) 7

Sodium Carbonate 25

Sodium Pyrophosphate 7

Coconut Monoethanolamide 2

Zeolite A (0.1-10 μ) 5

Carboxymethylcellulose 0.2

Polyacrylate (molecular weight 1400) 0.2

Dispersant (Example 1) 0.5

Polishes, Flavors 0.2

Protease 0.3

CaSO ₄ 1

MgSO ₄ 1

Water 4

Filler ^{* Add up to} 100%.

* Choose from convenient materials such as CaCO ₃ , talc, clay, silicate, etc.

The test recipe used in Example 7 is followed to test the soil dispersion performance of the dispersant. All fabrics show increased whitening compared to fabrics that have not been exposed to the soil dispersant of the invention after washing.

Example 9

A concentrated liquid detergent composition comprising the following ingredients is prepared.

Component weight%

C _14-15 Alkyl Polyethoxylate (2.25) sulfonic acid 10.6

C _12-13 straight chain alkylbenzene sulfonic acid 12.5

C _12-13 alkyl polyethoxylates (6.5) 2.4

Sodium Cumene Sulfonate 6

Ethanol 1.5

1,2-propanediol 4

Monoethanolamine 1

C _12-14 Fatty Acid 2

Dispersant (Example 2) 1.5

Sodium hydroxide pH 9 or higher.

Add up to 100% of trace ingredients, filler ^* and water

* Choose from convenient materials such as CaCO ₃ , talc, clay, silicate, etc. The test recipe used in Example 7 is followed to test the soil dispersion performance of the dispersant. All fabrics show increased whitening compared to fabrics that are not exposed to the soil dispersant of the invention after washing.

Although the compositions and processes of the present invention are particularly useful for hand washing fabric washing operations, they are also useful for laundry systems with a low water to fabric ratio. One such system is described in Spendel, U.S. Patent No. 4,489,455 (December 25, 1984), where a washing machine has a lower water to fabric ratio than conventional methods of immersing fabric in an aqueous bath. The fabric is brought into contact with the wash water containing the detergent ingredients. Typically, the ratio of water; fabric ranges from about 0.5: 1 to about 6: 1 (liters of water: kg of fabric).

Example 10

Using the washing machine and washing operation described in US Pat. No. 4,489,455, above, 25 g of the composition according to Example 9 is used for fabric washing. If desired, lathering of the composition can be minimized by introducing 0.2 to 2% by weight of fatty acid, secondary alcohol or silicone lather control components.

[Dishwashing composition]

Another aspect of the invention relates to dishwashing compositions, in particular automatic and manual dishwashing compositions, in particular manual liquid dishwashing compositions.

The liquid dishwashing composition according to the invention preferably contains at least about 0.1% of dispersant, more preferably from about 0.5 to about 30%, most preferably from about 1 to about 15% and from about 1 to about 99.9% of detergent surfactant. Include.

The liquid dishwashing composition according to the present invention may comprise any of the above components. In addition, the dishwashing composition may include fungicides, chelating agents, suds enhancers, milk whitening agents and other ingredients such as calcium and magnesium ions.

Example 11

The liquid composition of the present invention is prepared by mixing the following ingredients in the amounts shown.

Tartrate Monosuccinate / Tartrate Disuccinate 80:20 Mixture

Example 12

The automatic dishwashing composition is as follows.

¹ BRITTESIL, PQ Corporation

² Suds inhibitor of polyethylene oxide / polypropylene oxide

³ ACCUSOL, Rohm and Haas

In the above compositions, the surfactant can be replaced with an equivalent amount of all low foaming nonionic surfactants. Examples thereof include low- or non-foaming ethoxylated straight chain alcohols, such as the Flurafac ^TM RA series from Euran Co., Lutensol ^TM LF series from BASF Company, Rom and Haas Company's Triton ^™ DF series and ICC Company's Synperonic ^™ LF series.

The automatic dishwashing composition may be in granular, tablet form, solid soap or wash aid form. Processes for preparing granular, tablet, solid soaps or cleaning aids are known in the art. See, for example, US Patent Application Nos. 08 / 106,022, 08 / 147,222, 18 / 147,224, 08 / 147,219, 08 / 052,860, and 07 / 867,941.

All of the above-described particulate compositions may be provided as spray dried granules or as high density (600 g / l or more) granules or aggregates. Such granules (which should not contain oxidizable components) may include, for example, water-soluble silicates, carbonates and the like.

Although the above examples illustrate the use of this technique in wash / dirt dispersion compositions designed for use in laundry and dishwashing, those skilled in the art will recognize that the system can be used in environments where improved dirt dispersion is required. will be. Thus, the technique of the present invention can be used, for example, in cleaning prosthetic devices such as dentures with a dentifrice composition and in other environments where dirt dispersal is beneficial to the user.

Claims (16)

Charged with a nitrogen-containing backbone having an average molecular weight of 600 to 10,000, an ethoxylation and propoxylation degree of 0.5 to 10 per nitrogen, and no more than two positive charges for every 40 nitrogen atoms present in the uncharged backbone or backbone A soil dispersing composition comprising an alkoxylated polyalkyleneamine polymer of formula (I) comprising at least 0.1 weight percent of the composition comprising a backbone. Wherein R ¹ is each independently C ₂ -C ₁₂ alkylene, alkenylene, arylene or alkylarylene, and R ² is each independently H, straight, branched or cyclic C ₁ -C ₈ alkyl residue, phenyl , Benzyl, C ₁ -C ₈ aroyl or alkaroyl residues, or residues -LX, wherein X is a nonionic group or an anionic group and L is a polyoxyachelene residue [(R ⁵ O) _m (CH ₂ CH ₂ O) _n- (R ⁵ O) _m (CH ₂ CH ₂ O) _n ], where R ⁵ are each independently H, C ₃ -C ₄ alkylene or hydroxyalkylene, m '+ m '' Is m, n '+ n''is n, m is 0-4, n is 0-16 and m + n is 1-16), provided that R ² residues 0.5 or more of-is -LX, w is 1 or 0, x + y + z is 14 or more, and B shows the continuation of the said structure by branching. The composition of claim 1, wherein the alkoxylated polyalkyleneamine polymer comprises up to 4 propoxylates per available nitrogen position. The composition of claim 11 comprising 1 to 55% detergent detergent. A dirt dispersion composition according to claim 1; Detergent surfactants selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof; And one or more components selected from enhancers, enzymes, enzyme stabilizers, bleaches, bleach activators, polymeric antifouling agents, dispersants, fabric softeners, dye transfer inhibitors, carders, combustibles, dyes, pigments, carriers, and mixtures thereof Laundry detergent composition comprising a. An automatic dishwashing composition comprising a low foaming nonionic surfactant and a dirt dispersion composition according to claim 11. A liquid detergent composition comprising the dirt dispersion composition according to claim 1. A detergent bar composition comprising the soil dispersion composition according to claim 11. A charged chain having a nitrogen-containing backbone having an average molecular weight of 600 to 10,000, having an ethoxylation and propoxylation degree of 0.5 to 10 per nitrogen, and having up to 2 positive charges for every 40 nitrogen atoms present in the uncharged backbone or backbone A method for improving the soil dispersion performance of a laundry, dish or light surface detergent composition, comprising adding an alcoholylated polyalkyleneamine polymer of Formula 1 comprising a backbone in an amount dispersed in a wash medium in an amount ranging from 0.1 ppm to 700 ppm. Wherein R ¹ is each independently C ₂ -C ₁₂ alkylene, alkenylene, arylene or alkylarylene, and R ² is each independently H, straight, branched or cyclic C ₁ -C ₈ alkyl residue, phenyl , Benzyl, C ₁ -C ₈ aroyl or alkanoyl residues, or residues -LX, wherein X is a nonionic group or an anionic group and L is a polyoxyalkylene residue [(R ⁵ O) _m (CH ₂ CH ₂ O) _n- (R ⁵ O) _m (CH ₂ CH ₂ O) _n ] where R ⁵ are each independently H, C ₃ -C ₄ alkylene or hydroxyalkylene, m '+ m''Is m, n' + n '' is n, m is 0-4, n is 0-16 and m + n is 1-16), provided that the R ² residue 0.5 or more are -LX, w is 1 or 0, x + y + z is 14 or more, and B shows the continuation of the said structure by side chaining. Fabric, comprising contacting a fabric, light surface, or tableware with an aqueous medium comprising the soil dispersion composition according to claim 11 in an amount such that the alkoxylated polyalkyleneamine polymer is dispersed from 0.1 ppm to 700 ppm in the wash medium, How to brighten and / or wash hard surfaces or dishes. 10. The method of claim 9, wherein the pH of the aqueous medium is at least 9. Charged with a nitrogen-containing backbone having an average molecular weight of 600 to 10,000, an ethoxylation and propoxylation degree of 0.5 to 10 per nitrogen, and no more than two positive charges for every 40 nitrogen atoms present in the uncharged backbone or backbone Adding an alkoxylated polyalkyleneamine polymer of formula (I) comprising a backbone of the main chain to at least 0.1% by weight of the dispersant composition to effectively disperse the nonpolar dirt into an aqueous medium containing the nonpolar dirt. , A method of dispersing nonpolar dirt. Wherein R ¹ is each independently C ₂ -C ₁₂ alkylene, alkenylene, arylene or alkylarylene, and R ² is each independently H, straight, branched or cyclic C ₁ -C ₈ alkyl residue, phenyl , Benzyl, C ₁ -C ₈ aroyl or alkanoyl residues, or residues -LX, wherein X is a nonionic group or an anionic group and L is a polyoxyalkylene residue [(R ⁵ O) _m (CH ₂ CH ₂ O) _{n '} -(R ⁵ O) _m (CH ₂ CH ₂ O) _n ], where R ⁵ are each independently H, C ₃ -C ₄ alkylene or hydroxyalkylene, m' + m '' Is m, n '+ n''is n, m is 0-4, n is 0-16 and m + n is 1-16), provided that R ² residues 0.5 or more of-is -LX, w is 1 or 0, x + y + z is 14 or more, and B shows the continuation of the said structure by branching. (a) at least 1% by weight detergent detergent, (b) at least 1% by weight of an enhancer and (c) up to 2 positive charges per 40 nitrogen atoms present in the uncharged backbone or backbone, comprising a backbone containing nitrogen containing an average molecular weight of 600 to 10,000, and having an ethoxylation and propoxylation degree of 0.5 to 10 per nitrogen; A laundry detergent composition comprising at least 0.1% by weight of a soil dispersible alkoxylated polyalkyleneamine polymer of formula (I) comprising a charged backbone having: Wherein R ¹ is each independently C ₂ -C ₁₂ alkylene, alkenylene, arylene or alkylarylene, and R ² is each independently H, straight, branched or cyclic C ₁ -C ₈ alkyl residue, phenyl , Benzyl, C ₁ -C ₈ aroyl or alkanoyl residues, or residues -LX, wherein X is a nonionic group or an anionic group and L is a polyoxyalkylene residue [(R ⁵ O) _{m '} (CH ₂ CH ₂ O) _{n '} -(R ⁵ O) _m (CH ₂ CH ₂ O) _n ], where R ⁵ are each independently H, C ₃ -C ₄ alkylene or hydroxyalkylene, m' + m '' is m, n '+ n''is n, m is 0-4, n is 0-16, m + n is 1-16), provided that R ² At least 0.5 of the residues are -LX, w is 1 or 0, x + y + z is at least 14, and B represents the continuation of the structure by branching. The composition of claim 12 comprising a detergent surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. A C ₁₁ -C ₁₈ alkyl benzene sulfonate, C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfate, C ₁₀ -C ₂₀ alkyl sulfate, C ₁₀ -C ₁₈ alkyl alkoxy sulfate, C ₁₂ A composition comprising a detergent surfactant selected from the group consisting of -C ₁₈ alkyl ethoxylates, C ₁₀ -C ₁₈ amine oxides, C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides and mixtures thereof. 13. The composition of claim 12 wherein the enhancer is selected from the group consisting of alkali metal silicates, aluminosilicates, carbonates, polycarboxylates, citrates, and mixtures thereof. The composition of claim 15 wherein the enhancer is a zeolite enhancer.