DE69327654T2 - Softening compositions during washing - Google Patents

Abstract

A detergent composition comprising a crystalline layered silicate having the formula NaMSixO2x+1 yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. and a flocculating polymer selected from polymers and copolymers derived from monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethylene imine or mixtures thereof characterized in that said detergent composition comprises less than 5% of clay by weight of the detergent composition.

Description

Field of the invention

The present invention relates to detergent compositions containing a silicate as a softening system. More particularly, the present invention relates to during-the-wash softening detergent compositions comprising layered silicates and flocculant polymers.

Basis of the invention

Detergent compositions which provide fabric softening during the wash cycle are described in the art. In particular, clays are well known as agents for fabric softening during the wash. The relative ability of the softening clays to meet various performance criteria depends to a large extent on the presence and concentration of detergent adjunct ingredients. An example of such a detergent adjunct ingredient is the presence of nonionic surfactants.

When used in significant concentrations, the non-ionic surfactants mentioned prevent the clay from depositing on the fabric. It has therefore been necessary to limit the amount of non-ionic surfactants in wash-softening compositions containing clay.

It has now been found that the combination of a layered silicate and a flocculant polymer provides an efficient softening system which is fully compatible with non-ionic surfactants. This finding enables the formulation of detergent compositions which exhibit both outstanding softening and cleaning performance.

Another type of detergent additive ingredient that can be added to detergent compositions is a Dye transfer preventing polymers. The polymers mentioned are added to the detergent compositions to prevent the transfer of dyes from dyed fabrics to other fabrics washed with them. These polymers have the ability to complex or adsorb the released dyes washed out of the dyed fabrics before the dyes have a chance to bind to other items in the laundry.

Polymers have been used in detergent compositions to prevent dye transfer. Examples of such polymers are vinylpyrrolidone polymers as described in EP-A-265 257 and EP-A-508 034. Unfortunately, the vinylpyrrolidone polymers mentioned tend to interact with the clays formulated therewith. The performance of the polymers in preventing dye transfer and the softening performance of the clays are thereby negatively affected.

It has now been found that vinylpyrrolidone polymers are very compatible with the silicate-based plasticizing system, since the dye transfer inhibiting performance of the polymers is not negatively affected in the presence of the silicate-based plasticizing system. In addition, it has been found that the plasticizing performance of layered silicates formulated with the dye transfer inhibiting polymers was maintained.

This finding allows us to formulate detergent compositions that have both exceptional dye transfer prevention properties and exceptional softening performance.

According to the present invention, an alternative softening system is obtained which provides softening performance during washing without adversely affecting the overall detergency performance of the detergent formulated therewith.

Layered silicates have been described in WO-A-92/03525 and WO-A-92/08594 as builders in detergent compositions, which may contain certain polymeric compounds. The present invention therefore makes it possible to use the silicates in a dual function, e.g. as builder and as plasticizer, thereby facilitating the formulation of compact detergents.

Summary of the invention

The present invention relates to detergent compositions comprising layered silicate and flocculant polymers as in appended claim 1 and to the use of layered silicate and flocculant polymers to provide fabric softening as in appended claim 9.

Detailed description of the invention

The compositions of the present invention comprise as an essential element a crystalline sodium layered silicate of the general formula

NaMSixO2x+1yH₂O,

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline sodium layered silicates of this type are described in EP-A-0 164 514 and processes for their preparation are disclosed in DE-A-34 17 649 and DE-A-37 42 043. For the purposes of the present invention, x in the above general formula has, for example, a value of 2, 3 or 4 and is preferably 2. More preferably, M is sodium and y is 0 and preferred examples of this formula include the α-, β-, γ- and δ-forms of Na₂Si₂O₅. These materials are available from Hoechst AG, Germany, as NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6, respectively. The most preferred material is δ- Na₂Si₂O₅, NaSKS-6.

Flocculating agents

The plasticizing system of the present invention comprises a flocculant. The compositions of the present invention preferably comprise from 0.05% to 20%, based on the weight of the silicate, of a flocculant when the molecular weight is from 150,000 to 800,000, and preferably from 0.005% to 2%, based on the weight of the silicate when the molecular weight is from 800,000 to 5,000,000. Most of these materials are relatively long chain polymers and copolymers. The flocculants used in the present invention are polymers and copolymers selected from those derived from monomers selected from ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethyleneimine or mixtures thereof. Gums such as guar gum are also suitable as optional flocculants.

Ethylene oxide, acrylamide or acrylic acid polymers are preferred. For a suitable interaction with the silicate, the polymers should be relatively long-chain, i.e. they should have a weight average molecular weight of at least 100,000. For sufficient water solubility, the weight average molecular weight of the polymers should not exceed 10 million. Most preferred are polymers with a weight average molecular weight of 150,000 up to 1 million.

It should be understood that clay is present in the detergent compositions according to the present invention in amounts of less than 5%, based on the weight of the detergent composition. More preferably, the clay is present in the detergent composition in amounts of less than 1%, most preferably, the detergent composition is substantially free of clay.

Detergent additives

A wide range of surfactants can be used in the detergent compositions. A typical listing of nonionic, anionic, ampholytic and zwitterionic classes and species of these surfactants is found in U.S. Patent 3,664,961.

Non-ionic agents

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkylphenols having an alkyl group of 6 to 14 carbon atoms, preferably 8 to 14 carbon atoms, in either a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to 5 to 25 moles, more preferably 3 to 15 moles, of ethylene oxide per mole of alkylphenol. Commercially available non-ionic surfactants of this type include IgepalTM CO-630, sold by GAF Corporation, and TritonTM X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are conventionally referred to as alkylphenol alkoxylates (e.g., alkylphenol ethoxylates).

The condensation products of primary and secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention. The alkyl chain of the aliphatic alcohol can be either linear or branched, primary or secondary and generally contains 8 to 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group with 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms, with 2 to 10 moles ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of a linear C11-C15 alcohol with 9 moles of ethylene oxide), TergitolTM 24- L-6 NMW (the condensation product of a primary C12-C14 alcohol with 6 moles of ethylene oxide having a narrow molecular weight distribution), both of which are sold by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of linear C₁₄-C₁₅ alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of linear C₁₂-C₁₃ alcohol with 6.5 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of linear C₁₄-C₁₅ alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation product of linear C₁₄-C₁₅ alcohol with 4 moles of ethylene oxide), which are sold by Shell Chemical Company, and KyroTM EOB (the condensation product of C₁₃-C₁₅ alcohol with 9 Mol ethylene oxide), which is distributed by The Procter & Gamble Company.

Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkyl polysaccharides described in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, which have a hydrophobic group containing 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, and a hydrophilic polysaccharide group, e.g., a hydrophilic polyglycoside group, containing 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms may be used, e.g., 1.3 to 2.7 saccharide units. For example, glucose, galactose and galactosyl residues can be used instead of glucosyl residues (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions, thus obtaining a glucose or galactose instead of a glucoside or galactoside). The intersaccharide bonds can be present, for example, between the 1-position of the additional saccharide units and the 2-, 3-, 4- and/or 6-positions of the subsequent saccharide units.

Optionally, and less desirably, a polyalkylene oxide chain may be present connecting the hydrophobic moiety and the polysaccharide moiety. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched, having from 8 to 18, preferably 10 to 16, carbon atoms. Preferably, the alkyl group is a straight chain, saturated alkyl group. The alkyl group may have up to 3 hydroxy groups and/or the polyalkylene oxide chain may contain up to 10, preferably less than 5, alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, -di-, tri-, -tetra-, -penta- and -hexaglucosides, -galactosides, lactosides, -glucoses, -fructosides, -fructoses and/or galactoses. Suitable mixtures include coconut alkyl, -di-, tri-, -tetra- and -pentaglucosides and talc alkyl tetra-, -penta- and -hexaglucosides.

The preferred alkyl polyglycosides have the formula

R²O(CnH₂nO)t(Glycosyl)x,

wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl groups contain from 10 to 18, preferably 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first formed and this is subsequently reacted with glucose or a glucose source to form the glucoside (bond in the 1-position). The additional glycosyl units can then be bonded between their 1-position and the preceding glycosyl units in the 2-, 3-, 4- and/or 6-position, preferably predominantly in the 2-position.

Although not preferred, the condensation products of ethylene oxide and a hydrophobic base obtained by the condensation of propylene oxide with propylene glycol are also suitable for use as an additional nonionic surfactant of the nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of 1,500 to 1,800 and exhibit water insolubility. The addition of polyoxyethylene residues to this hydrophobic portion tends to increase the overall water solubility of the molecule and the liquid character of the product is maintained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available PluronicTM surfactants sold by BASF.

Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and an excess of propylene oxide and generally has a molecular weight of 2,500 to 3,000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains 40% to 80% by weight of polyoxyethylene and has a molecular weight of 5,000 to 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic™ compounds sold by BASF.

Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide, alkyl polysac charides and mixtures thereof. Most preferred are C8-C14 alkylphenol ethoxylates having 3 to 15 ethoxy groups and C8-C18 alcohol ethoxylates (preferably average C10) having 2 to 10 ethoxy groups and mixtures thereof.

Most preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants.

Also suitable as nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula

wherein R¹ is H or R¹ is C₁₋₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R² is C₅₋₃₁ hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbon chain with at least 3 hydroxyl groups directly attached to the chain, or an alkoxylated derivative thereof. Preferably R¹ is methyl, R² is straight chain C₁₁₋₁₅ alkyl or an alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, furose, maltose, lactose in a reductive amination reaction.

When present in such laundry detergent compositions, the nonionic surfactant systems of the present invention are effective in improving the greasy/oily soil removal properties of such laundry detergent compositions over a wide range of laundry conditions.

Anionic surfactants

Suitable anionic surfactants, including alkoxylated alkyl sulfate surfactants thereof, are water-soluble salts or acids of the formula RO(A)mSO3M, wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl moiety, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A represents an ethoxy or porpoxy moiety, m is greater than 0, typically from 0.5 to 6, more preferably from 0.5 to 3, and M is H or a cation which is, for example, a metal cation (e.g. B. sodium, potassium, lithium, calcium, magnesium, etc.), an ammonium or a substituted ammonium cation. Ethoxylated alkyl sulfates as well as propoxylated alkyl sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Exemplary surfactants are C₁₂-C₁₈-alkyl polyethoxylate(1,0)sulfate (C₁₂-C₁₈E(1,0)M), C₁₂-C₁₈-alkyl polyethoxylate(2,25)sulfate (C₁₂-C₁₈E(2,25)M), C₁₂-C₁₈-alkyl polyethoxylate(3,0)sulfate (C₁₂-C₁₈E(3,0)M), and C₁₂-C₁₈-alkyl polyethoxylate(4,0)sulfate (C₁₂-C₁₈E(4.0)M), wherein M is conveniently selected from sodium and potassium.

Suitable anionic surfactants to be used are alkyl ester sulfonate surfactants, including linear esters of C8-C20 carboxylic acids (i.e. fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances such as those obtained from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, particularly for laundry applications, comprises alkyl ester sulfonate surfactants having the structural formula:

wherein R³ is a C₈-C₂₀ hydrocarbyl, preferably an alkyl, or a combination thereof, R⁴ is a C₁-C₆ hydrocarbyl, preferably an alkyl, or a combination thereof, and M is a cation which forms a water-soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably R³ is a C₁₀-C₁₆ alkyl and R⁴ is methyl, ethyl or isopropyl. Particularly preferred are the methyl ester sulfonates in which R³ is C₁₀-C₁₆-alkyl.

Other suitable anionic surfactants, including the alkyl sulfate surfactants thereof, are water-soluble salts or acids of the formula ROSO₃M, wherein R is preferably a C₁₀-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀-C₂₀ alkyl moiety, more preferably a C₁₂-C₁₉ alkyl or hydroxyalkyl, and M is H or a cation, e.g. B. an alkali metal cation (e.g., sodium, potassium, lithium) or ammonium or substituted ammonium (e.g., methyl, dimethyl and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl ammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Typically, alkyl chains of C₁₂-C₁₆ are preferred for lower wash temperatures (e.g., below about 50°C) and C₁₆-C₁₈ alkyl chains are preferred for higher wash temperatures (e.g., above about 50°C).

Other anionic surfactants useful for detersive purposes may also be included in the laundry detergent compositions of the present invention. These may be salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soaps, linear C9-C20 alkylbenzene sulfonates, primary or secondary C8-C22 alkane sulfonates, C8-C24 olefin sulfonates, sulfonated polycarboxylic acids prepared by the sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g. B. as described in British Patent Specification No. 1,082,179, C6-C24 alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); Alkyl glycerol sulfonate, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C₁₂-C₁₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C₆-C₁₂ diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as the sulfates of alkyl polyglucoside (the nonionic, non-sulfated compounds being described hereinafter), branched primary alkyl sulfates, and alkyl polyethoxycarboxylates such as those of Formula RO(CH₂CH₂O)k-CH₂COO⁻M⁺, where R is C₈-C₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or obtained from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vols. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally described in U.S. Patent 3,929,678, issued December 30, 1975, Laughlin, et al. revealed in column 23, line 58 to column 29, line 23.

When included herein, the laundry detergent compositions of the present invention typically comprise 1% to 40%, preferably 3% to 20%, by weight of such anionic surfactants.

The laundry detergent compositions of the present invention may also comprise cationic, ampholytic, zwitterionic and semipolar surfactants as well as nonionic surfactants other than those already described herein.

Preferred cationic surfactant systems include nonionic and ampholytic surfactants. Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halides and those surfactants of the formula

[R²(ORt³)y][R⁴(OR³)y]₂R⁵N⁺X⁻,

wherein R² represents an alkyl or alkylbenzyl group having 8 to 18 carbon atoms in the alkyl chain, each R³ is selected from the group consisting of -CH₂CH₂-, -CH₂CH(CH₃)-, -CH₂CH(CH₂OH)-, -CH₂CH₂CH₂- and mixtures thereof; each R⁴ is selected from the group consisting of C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzyl ring structures formed by joining the two R⁴ groups, -CH₂CHOH-CHOHCOR⁴CHOHCH⁴OH, wherein R⁴ is is any hexose or hexose polymer having a molecular weight of less than 1,000, and is hydrogen when y is not 0; R5 has the same meaning as R4 or is an alkyl chain, the total number of carbon atoms of R2 plus R5 being not more than 18; each y is from 0 to 10 and the sum of the y values is from 0 to 15; and X is any compatible anion.

Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula:

R&sub1;R&sub2;R&sub3;R&sub4;N&spplus;X&supmin; (i)

wherein R₁ is C₈-C₁₆ alkyl, each of R₂, R₃ and R₄ independently represents C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzyl and -(C₂H₄₀)xH, where x has a value of 2 to 5, and X represents an anion. No more than one of R₂, R₃ or R₄ should be benzyl.

The preferred alkyl chain length for R1 is C12-C15, particularly when the alkyl group is a mixture of chain lengths obtained from coconut or palm kernel fat or by olefin buildup or OXO alcohol synthesis. Preferred groups for R2, R3 and R4 are methyl and hydroxyethyl groups and the anion X can be selected from halide, methosulfate, acetate and phosphate ions.

Examples of suitable quaternary ammonium compounds of formulae (i) for use herein are:

Coconut trimethylammonium chloride or bromide;

coconut methyl dihydroxyethyl ammonium chloride or bromide; decyltriethylammonium chloride, decyldimethylhydroxyethylammonium chloride or bromide;

C12-15 dimethylhydroxyethyl ammonium chloride or bromide;

Coconut dimethylhydroxyethylammonium chloride or bromide;

myristyl trimethyl ammonium methyl sulfate;

Lauryldimethylbenzyl ammonium chloride or bromide;

Lauryldimethyl(ethenoxy)4ammonium chloride or bromide;

Choline esters (compounds of formula (i) wherein R₁ is

and R₂, R₃, R₄ are methyl)

Dialkylimidazolines [compounds of formula (i)].

Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.

When included therein, the laundry detergent compositions of the present invention typically comprise from 0% to 25%, preferably from 3% to 15%, by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or as aliphatic derivatives of heterocyclic, secondary and tertiary amines, wherein the aliphatic moiety can be straight or branched chain. One of the aliphatic substituents contains at least 8 carbon atoms, typically 8 to 18 carbon atoms, and at least one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678, Laughlin et al., issued December 30, 1975, column 19, lines 18 to 35, for examples of ampholytic surfactants.

When included herein, the laundry detergent compositions of the present invention typically comprise 0% to 15%, preferably 1% to 10%, by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic, secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678, Laughlin et al., issued December 30, 1975, column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.

When included herein, the laundry detergent compositions of the present invention typically comprise 0% to 15%, preferably 1% to 10%, by weight of such zwitterionic surfactants.

Semipolar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides having an alkyl radical of 10 to 18 carbon atoms and 2 radicals selected from the group consisting of alkyl groups and hydroxyalkyl groups having 1 to 3 carbon atoms; water-soluble phosphine oxides having an alkyl radical of 10 to 18 carbon atoms and 2 radicals selected from the group consisting of alkyl groups and hydroxyalkyl groups having 1 to 3 carbon atoms; and water-soluble sulfoxides having an alkyl radical of 10 to 18 carbon atoms and a radical selected from the group consisting of alkyl and hydroxyalkyl radicals having 1 to 3 carbon atoms.

Semipolar nonionic detergent surfactants include the amine oxide surfactants of the formula

wherein R³ represents an alkyl, hydroxyalkyl or alkylphenyl group or a mixture thereof having 8 to 22 carbon atoms, R⁴ represents an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; x is from 0 to 3; and each R⁵ represents an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide groups. The R⁵ groups may be bonded to one another, e.g. through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants include, in particular, C₁₀-C₁₈ alkyldimethylamine oxides and C₈-C₁₂ alkoxyethyldihydroxyethylamine oxides.

When included herein, the laundry detergent compositions of the present invention typically comprise from 0% to 15%, preferably from 1% to 10%, by weight of such semi-polar nonionic surfactants.

The present invention further provides laundry detergent compositions comprising at least 1%, preferably from 3% to 65%, more preferably from 10% to 25% by weight of total surfactants.

The compositions of the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein, including aluminosilicate materials, polycarboxylates and fatty acids, materials such as ethylenediaminetetraacetate, metal ion chelating agents such as aminopolyphosphonates, particularly ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Although less preferred for obvious environmental reasons, phosphate builders may also be used herein.

Suitable builders can be formed from an inorganic ion exchange material, conventionally an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.

Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as described in Belgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxyacid)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegungsschriften 2,446,686 and 2,446,687 and in US Pat. No. 3,935,257, and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include in particular water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Dutch Application 7205873, and the oxypolycarboxylate materials such as the 2-oxa-1,1,3-propanetricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates described in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propanetetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolyzed citrates described in British Patent No. 1,082,179, whereas polycarboxylates containing phosphonic substituents are described in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran cis,cis,cis-tetracarboxylates, 2,5-tetrahydrofuran cis-dicarboxylates, 2,2,5,5-tetrahydrofuran tetracarboxylates, 1,2,3,4,5,6-hexane hexacarboxylates and the carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives described in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates with up to 3 carboxy groups per molecule, especially citrates.

Preferred builder systems for use in the present compositions comprise a mixture of a water-insoluble aluminosilicate builder, such as zeolite A or a layered silicate (SKS-6), and a water-soluble carboxylate chelating agent, such as citric acid.

A suitable chelating agent for inclusion in the detergent compositions according to the invention is ethylenediamine- N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na₂EDDS and Na₄EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg₂EDDS. The magnesium salts are most preferred for inclusion in the compositions according to the invention.

Preferred builder systems comprise a mixture of a water-insoluble aluminosilicate builder such as zeolite A and a water-soluble carboxylate chelating agent such as citric acid. Other builder materials which may form part of the builder system for use in granular compositions according to the purpose of the invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates and organic materials such as the organic phosphonates, aminopolyalkylene phosphonates and aminopolycarboxylates.

Other suitable water-soluble organic salts are the homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms.

Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates with a molecular weight of 2,000 to 5,000 and their copolymers with maleic acid anhydride, which copolymers have a molecular weight of 20,000 to 70,000, in particular about 40,000.

Detergency builder salts are typically present in amounts from 10% to 80% by weight of the composition, preferably from 20% to 70% by weight, and most typically from 30% to 60% by weight.

Detergent ingredients which may be included in the detergent compositions of the present invention include bleaching agents.

These bleach components may comprise one or more oxygen bleaches and, depending on the bleach selected, one or more bleach activators. When present, bleaching compounds will typically be present in amounts of from 1% to 10% of the detergent composition. Generally, bleaching compounds are optional components in non-liquid formulations, e.g., granular detergents. When present, the amount of bleach activators will typically be from 0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition.

The bleach component for use herein can be any of the bleaching agents useful in detergent compositions, including oxygen bleaches as well as others known in the art.

In a process aspect, the invention will further provide a process for cleaning fabrics, fibers, textiles at temperatures below about 50°C, especially below about 40°C, with a detergent composition, which composition contains polyamine N-oxide-containing polymers, optional detersive surfactants, optional detersive adjunct ingredients and a bleaching agent.

The bleaching agent suitable for the present invention may be an activated or a non-activated bleaching agent.

One category of oxygen bleaches that can be used includes percarboxylic acid bleaches and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecanedioic acid. Such bleaches are described in U.S. Patent No. 4,483,781, U.S. Patent Application No. 740,446, European Patent Application No. 0,133,354, and U.S. Patent No. 4,412,934. Highly preferred bleaches also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent No. 4,634,551.

Another category of bleaching agents that can be used include the halogen bleaching agents. Examples of hypohalite bleaching agents include, for example, trichloroisocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromoalkanesulfonamides. Such materials are normally added in amounts of from 0.5% to 10% by weight of the finished product, preferably from 1% to 5% by weight.

For example, the bleaching agents suitable for the present invention include peroxygen bleaching agents. Examples of suitable water-soluble, solid peroxygen bleaching agents include hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and peroxyhydrates. Preferred bleaching agents are percarbonates and perborates.

The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US-A-4,412,934, 3,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP-A-120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as an effective bleaching species, resulting in an improved bleaching effect. Also suitable activators are vators are acylated citrate esters (ATC) as described in WO-A-93/12067.

The hydrogen peroxide can also be present by adding an enzymatic system (that is an enzyme and a substrate therefor) capable of forming hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are described in European patent application 91202655.6, filed on October 9, 1991.

Other peroxygen bleaching agents suitable for the present invention include organic peroxyacids such as percarboxylic acids.

Bleaching agents other than oxygen bleaches are also known in the art and can be used herein. One type of bleaching agent of particular interest that is not oxygen bleach includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited on the substrate during the washing process. Upon exposure to light in the presence of oxygen, such as when hanging laundry items to dry in daylight, the sulfonated zinc phthalocyanine is activated and, as a result, the substrate is bleached. Preferred zinc phthalocyanine and a bleaching process by photoactivation are described in U.S. Patent No. 4,033,718. Typically, detergent compositions will contain from 0.025% to 1.25% by weight of sulfonated zinc phthalocyanine.

Other detergent ingredients which may be included are detersive enzymes which may be present in the detergent formulations for a wide variety of purposes including, for example, the removal of protein-based, carbohydrate-based or triglyceride-based stains and to prevent dye transfer. The enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidases and mixtures thereof. Other Types of enzymes may also be included. They can be of any suitable origin, such as plants, animals, bacteria, fungi and yeast.

Enzymes are typically incorporated in amounts sufficient to provide up to 5 mg by weight, more typically 0.05 mg to 3 mg, of active enzyme per gram of the composition.

Suitable examples of proteases are the subtilisins, which are obtained from specific strains of B. subtilis and B-lincheniformis. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the trade names Alcalase, Savinase and Esperase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (Netherlands) and FN-Base by Genencor, Optimase and Opticlean by MKC.

Of interest in the category of proteolytic enzymes, particularly for liquid detergent compositions, are enzymes referred to herein as protease A and protease B. Protease A is described in European patent application 130,756. Protease B is described in European patent application No. 87303761.8. Amylases include, for example, α-amylases obtained from a specific strain of B.lincheniformis, which are disclosed in more detail in British patent specification No. 1,296,839 (Novo). Amylolytic proteins include, for example, Rapidase, Maxamyl (International Bio-Synthetics, Inc.) and Termamyl (Novo Industries).

The cellulases applicable in the present invention include both bacterial and fungal cellulase. Preferably they will have a pH optimum between 5 and 9.5. Suitable cellulases are described in US Patent 4,435,307, Barbesgoard et al., which discloses fungal cellulase produced by Humicola insolens. Suitable Cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-A-2.247.832.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), in particular the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the variety Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella auricula solander).

Other suitable cellulases are cellulases derived from Humicola insulens, with a molecular weight of about 50 kDa, an isoelectric point of 5.5 and a content of 415 amino acids.

A particularly suitable cellulase is cellulase which provides advantages in terms of color care. An example of such cellulases is that of European patent application No. 91202879.2, filed on November 6, 1991, Carezyme (Novo).

Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as described in British Patent 1,372,034.

Suitable lipases include those which show a positive immunological cross-reaction with the antibody to the lipase produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P".

Particularly suitable lipases are lipases such as M1 Lipase (Ibis) and Lipolase (Novo).

Peroxidase enzymes are used in conjunction with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," that is, to prevent transfer of dyes or pigments removed from substrates during washing operations to other substrates in the wash solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and halogen peroxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in International Application WO 89/099813 and European Patent Application No. 91202882.6, filed November 6, 1991.

In liquid formulations, an enzyme stabilization system is preferably employed. Enzyme stabilization methods for aqueous detergent compositions are well known in the art. For example, one method for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate and calcium propionate. Calcium ions can be employed in combination with short chain carboxylic acid salts, preferably formates. See, for example, U.S. Patent No. 4,318,818. It has also been proposed to employ polyols such as glycerin and sorbitol. Alkoxy alcohols, dialkyl glycol ethers, mixtures of polyhydric alcohols with polyfunctional aliphatic amines (e.g., such as diethanolamine, triethanolamine, diisopropanolamine, etc.), and boric acid or alkyl metal borate. Enzyme stabilization methods are additionally described and illustrated in U.S. Patent No. 4,261,868, U.S. Patent No. 3,600,319, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5. Non-boric acid stabilizers and borate stabilizers are preferred. Enzyme stabilization systems are also described, for example, in U.S. Patent Nos. 4,261,868, 3,600,319, and 3,519,570.

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers as described in the co-pending European Patent Application No. 92870018.6 which was filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylenepolyamines.

Particularly preferred detergent ingredients are combinations with technologies which also provide some type of color care benefit. Examples of these technologies are polyvinylpyrrolidonopolymers as described in EP-A-0 508 034. The detergent compositions of the invention may comprise a polyvinylpyrrolidone ("PVP") having an average molecular weight of 5,000 to 400,000, preferably from 5,000 to 200,000, more preferably from 5,000 to 50,000 and most preferably from 5,000 to 20,000. Suitable polyvinylpyrrolidones are commercially available from GAF Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (average molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000) and PVP K-90 (average molecular weight 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones commercially available from BASF Corporation include Sokalan HP 165 and Sokalan HP 12.

Polyvinylpyrrolidones are known to those skilled in the detergent art; see, for example, EP-A-262,897 and EP-A-256,696. The amount of polyvinylpyrrolidone used in the present detergent compositions should be from 0.01% to 5% by weight of the detergent, preferably from 0.05% to 3%, and more preferably from 0.1% to 2% by weight. The amount of polyvinylpyrrolidone delivered in the wash solution is from 0.5 ppm to 300 ppm, preferably from 1 ppm to 60 ppm, more preferably from 1 ppm to 30 ppm, and most preferably from 1 ppm to 20 ppm.

Preferred polymers for preventing dye transfer are polyamine N-oxide-containing polymers as described in EP-A- 0579295.

The amine N-oxide polymers of the present invention typically have a ratio of amine to amine N-oxide of from 10:1 to 1:1,000,000. However, the amount of amine oxide groups present in the polyamine oxide-containing polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1,000,000. More preferably, from 1:4 to 1:1,000,000, most preferably, from 1:7 to 1:1,000,000.

Typically the average molecular weight is in the range of 500 to 1,000,000; preferably it is 1,000 to 50,000, more preferably 2,000 to 30,000, most preferably 3,000 to 20,000.

The polyamine N-oxide containing polymers of the present invention are typically present in amounts of from 0.001% to 10%, more preferably from 0.01% to 2%, most preferably from 0.05% to 1%, by weight of the detergent composition.

Other preferred polymers are N-vinylimidazole-N-vinylpyrrolidone copolymers as described in EP-A-0628624.

The N-vinylimidazole-N-vinylpyrrolidone polymers have an average molecular weight range of 5,000 to 1,000,000, preferably 20,000 to 200,000.

Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole-N-vinylpyrrolidone copolymers, said polymer having an average molecular weight range of from 5,000 to 50,000, more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.

Other examples of detergent ingredients that provide some kind of color care benefit are cellulase, peroxidase and metallocatalysts. Such metallocatalysts are described in the parallel patent application No. 92870181.2.

Another optional ingredient is a suds suppressor, exemplified by silicones and silica-silicone mixtures. Silicones may generally be represented by alkylated polysiloxane materials, whereas silica is usually employed in finely divided form, exemplified by silica gels and xerogels and hydrophobic silicas of various types. These materials may be incorporated as particulate agents wherein the suds suppressor is preferably releasably incorporated in a water-soluble or water-dispersible, substantially non-surfactant, detergent-impermeable carrier. Alternatively, the suds suppressor may be dissolved or dispersed in a liquid carrier and applied to one or more of the other components by spraying.

A preferred silicone based foam control agent is described in Bartollota et al., U.S. Patent No. 3,933,672. Other particularly useful foam suppressors are the self-emulsifying silicone based foam suppressors described in German Patent Application DT-OS 2,646,126, published April 28, 1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. A particularly preferred foam control agent is the foam suppressor system comprising a mixture of silicone oils and 2-alkylalkanols. A suitable 2-alkylalkanol is 2-butyloctanol, which is commercially available under the trade name Isofol 12R.

Such a foam suppressing system is described in the parallel European patent application No. 92870174.7, filed on 10 November 1992.

Particularly preferred silicone-based foam regulating agents are disclosed in the parallel European patent application No. 92201649.8. Said compositions may comprise a silicone-silicon dioxide mixture in combination with pyrogenic, non-porous silica, such as Aerosil®.

Other preferred foam regulating agents are described in EP-A-495 345. These foam regulating agents comprise a silicone antifoam compound, a carrier material and an organic coating material, they further contain glycerin in a weight ratio with the silicone antifoam compound of 1:2 to 3:1.

The foam suppressors described above are typically used in amounts of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.

Other components used in detergent compositions may be employed such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, anti-hazing agents, colorants, and non-encapsulated and encapsulated perfumes.

Particularly suitable materials for encapsulation are water-soluble capsules consisting of a matrix of polysaccharide and polyhydroxy compounds as described in GB-A-1,464,616.

Other suitable water-soluble encapsulating materials include dextrins obtained from non-chelated starch acid substituted dicarboxylic acid esters as described in US-A-3,455,838. These acid-ester dextrins are preferably prepared from such starches as waxy corn, waxy millet, sago, tapioca and potato. Suitable examples of said encapsulating materials include N-Lok, which is manufactured by National Starch. The N-Lok encapsulating material consists of a modified corn starch and glucose. The starch is prepared by adding monofunctional substituted groups such as octenylsuccinic anhydride.

Antiredeposition and soil suspending agents useful herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, wherein the maleic anhydride represents at least 2 mole percent of the copolymer. These materials are typically employed in amounts of from 0.5% to 10%, more preferably from 0.75% to 8%, most preferably from 1% to 6%, by weight of the composition.

Preferred optical brighteners have anionic character, Examples of which are disodium 4,4'-bis-(2-diethanolamino-4- anilino-s-triazin-6-ylamino)stilbene-2 : 2'-disulfonate, disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2 : 2'-disulfonate, disodium 4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2 : 2-disulfonate, monosodium 4',4"-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2-sulfonate, disodium 4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazine-6-ylamino)stilbene-2,2'-disulfonate, disodium 4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2'-disulfonate, (1-methyl-2-hydroxyethylamino)-s-triazine-6-ylamino)stilbene-2,2'-disulfonate and sodium 2-(stilbyl-4"-(naphto-1',2':4,5)-1,2,3-triazole-2"-sulfonate.

Other useful polymeric materials are the polyethylene glycols, particularly those having a molecular weight of from 1,000 to 10,000, more preferably from 2,000 to 8,000 and most preferably about 4,000. These are used in amounts of from 0.20 wt% to 5 wt%, more preferably from 0.25 wt% to 2.5 wt%. These polymers and the previously mentioned homo- or copolymeric polycarboxylate salts are useful for improving the maintenance of whiteness, ash deposition on the fabric and the cleaning performance against clay, protein-containing and oxidizable dirt in the presence of transition metal contaminants.

Soil release agents useful in the compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are described in commonly assigned U.S. Patent Nos. 4,116,885 and 4,711,730 and in published European Patent Application No. 0 272 033. A particularly preferred polymer according to EP-A-0 272 033 has the formula

(CH3 (PEG)43 )0.75(POH)0.25[(T-PO)2.8(T-PEG)0.4]T (PO-H)0.25((PEG )43 CH3 )0.75,

where PEG is -(OC₂H₄)O-, PO is (OC₃H₆O) and T is (pCOC₆H₄CO).

Also very useful are modified polyesters such as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol, where the end groups consist predominantly of sulfobenzoate and secondarily of monoesters of ethylene glycol and/or propanediol. The aim is to obtain a polymer capped at both ends by sulfobenzoate groups, in the present context most of the copolymers mentioned herein will be "predominantly" end-capped by sulfobenzoate groups. However, some copolymers will be less than fully capped and their end groups may therefore consist of monoesters of ethylene glycol and/or propane-1,2-diol, and thus "secondarily" consist of such species.

The polyesters selected herein contain about 46% by weight dimethylterephthalic acid, about 16% by weight propane-1,2-diol, about 10% by weight ethylene glycol, about 13% by weight dimethylsulfobenzoic acid and about 15% by weight sulfoisophthalic acid and have a molecular weight of about 3,000. The polyesters and their Manufacturing processes are described in detail in European patent application 311 342.

The detergent compositions according to the invention may be in liquid, pasty, gel, gel or granular forms. Granular compositions according to the present invention may also be in "compact form", that is, they may have a relatively higher density than conventional granular detergents, that is, from 550 to 950 g/l; in such a case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt" compared to conventional detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise no more than 10% of filler salt. The liquid compositions according to the present invention may also be in "concentrated form", in such a case the liquid detergent compositions according to the present invention will contain a lower amount of water compared to conventional liquid detergents. Typically the water content of the concentrated liquid detergent is less than 30%, more preferably less than 20%, most preferably less than 10% by weight of the detergent compositions.

The present invention also relates to a method for preventing dye transfer from one fabric to another of solubilized and suspended dyes which occur during fabric washing processes involving dyed fabrics.

The method comprises contacting fabric with a laundry solution as described hereinabove.

The process of the invention is conveniently carried out in the course of the washing process. The washing process is preferably carried out at 5°C to 75°C, especially 20°C to 60°C, but the polymers are stable up to temperatures of 95°C and more effective. The pH value of the treatment solution is preferably from 7 to 11, in particular from 7.5 to 10.5.

The process and compositions of the invention can also be used as detergent additive products.

Such additive products are intended to supplement or enhance the performance of conventional detergent compositions.

The detergent compositions according to the present invention include compositions which are applied for cleaning substrates such as fabrics, fibers, hard surfaces, skin and others, for example cleaning compositions for hard surfaces (with or without abrasives), laundry detergent compositions, dishwashing compositions for automatic or non-automatic dishwashing.

The following examples are intended to illustrate compositions of the present invention, but they are not necessarily intended to limit or otherwise define the scope of the invention, which scope is determined by the following claims.

EXAMPLE I (A/B/C/D)

The effectiveness of the combination of layered silicate and flocculating polymer as a plasticizing system was evaluated by measuring the plasticizing performance.

The softening performance was determined by a launderometer test. The test procedure was as follows: 3.5 kg laundry loads of clean fabric were washed in a Miele 423 automatic drum washing machine at 60ºC. The hardness of the water was 2 mM mol calcium and the composition concentration was 0.7% in the washing liquor.

A bundle of soiled fabrics containing fabrics soiled with particulate soil was washed with a detergent composition with and a detergent composition without the silicate as the softening system. The comparative assessment of softening was carried out by experts using a scale of 0.4 Panel Score Units (PSU). On this scale, 0 is given when there is no difference and 4 is given for the maximum difference.

A granular detergent composition according to the present invention is prepared having the following compositions:

%, based on the weight of the total detergent composition

Linear alkyl benzene sulfonate 13.70

Tallow alkyl sulfate 5.9

C₄₅-alcohol, 7-fold ethoxylated 4.00

Trisodium citrate 5.00

Zeolite 26,00

Maleic acid-acrylic acid copolymer 4.9

Diethylenetriaminepentamethylenephosphonic acid 0.6

Protease 1.5

Carboxymethylcellulose 1.5

foam suppressant (silicone) 0.3

TABLE I

Example I shows the plasticizing performance of the layered silicate in combination with the flocculant polymer versus compositions containing layered silicate without flocculant polymers. The flocculant polymer used is polyethylene oxide with an average molecular weight of 300,000. The layered silicate used is the layered silicate (SKS-6).

Test conditions:

pH value = 10.5

Washing temperature: 40ºC

A: A detergent composition according to Table I which does not contain layered silicate and flocculant polymer.

B: A detergent composition according to Table I containing 9% layered silicate and no flocculant polymer.

C: A detergent composition according to Table I containing 0.3% flocculating polymer and no layered silicate.

D: A detergent composition according to Table I containing 0.3% flocculating polymer and 9% layered silicate.

Results:

PSU values for softening performance (reference IA). Bleeding fabric composition: 100% cotton, and PSU values.

The above results demonstrate that the combination of the flocculant polymers and the silicate provides a statistically significant plasticization performance.

EXAMPLE II (A/B):

The effectiveness of the silicate-based softening system was evaluated by measuring the softening and cleaning performance.

The softening and cleaning performance was determined by a Launderometer test. The test procedure was as follows:

3.5 kg loads of clean fabric were washed in a Miele 423 automatic drum washing machine at 60ºC. The hardness of the water was 2 mM calcium and the composition concentration was 0.7% in the washing liquor.

A bundle of soiled fabrics containing fabrics soiled with particulate soil was washed with a detergent composition with and a detergent composition without the silicate as the softening system. The comparative assessment of softening and cleaning was carried out by experts using a scale of 0.4 Panel Score Units (PSU). On this scale, 0 is given when there is no difference and 4 is given for the maximum difference.

A: A detergent composition according to Table I which does not contain layered silicate and flocculant polymer.

B: A detergent composition according to Table I containing 9% layered silicate and 0.3% of a flocculant polymer.

Test conditions:

pH value = 10.5

Washing temperature: 40ºC RESULTS:

As can be seen from the above, the cleaning performance is not negatively affected by the presence of the silicate-based softening system.

EXAMPLE I (A/B/C/D/E)

A compact granular detergent composition according to the present invention is prepared having the following formulation:

%, based on the weight of the total detergent composition

(*) foam suppressant: agglomerate containing 11% by weight of the component of polydimethylsiloxane, 14% ethoxylated tallow alcohol, 5% hydrogenated C₁₂-C₂₂ fatty acids and 70% starch.

The above compositions (Example I (A/B/C/D/E)) demonstrated outstanding softening, cleaning and detergent performance with outstanding color care performance on dyed fabrics and mixed fillings of dyed and white fabrics.

Example II (A/B/C/D)

A liquid detergent composition according to the present invention is prepared having the following compositions:

%, based on the weight of the total detergent composition

EXAMPLE III (A/B/C/D/E)

A compact granular detergent composition according to the present invention is prepared having the following formulation:

%, based on the weight of the total detergent composition

EXAMPLE IV (A/B/C/D)

A liquid detergent composition according to the present invention is prepared having the following compositions:

%, based on the weight of the total detergent composition

The above compositions (Example II (A/B/C/D), III (A/B/C/D/E) and IV (A/B/C/D)) demonstrate outstanding cleaning and detergent performance with outstanding colour care performance on dyed fabrics and mixed fillings of dyed and white fabrics.

Claims (9)

1. A detergent composition comprising a crystalline layered silicate of the formula NaMSixO2x+1yH₂O, wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20; and a flocculant polymer, which polymer is selected from polymers and copolymers derived from monomers selected from ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethyleneimine or mixtures thereof, characterized in that said detergent composition comprises less than 5% clay by weight of the detergent composition, and by the proviso that the flocculant polymer is not a polyvinyl pyrrolidone polymer having an average molecular weight of up to 700,000. 2. A detergent composition according to claim 1, wherein x has a value of 2. 3. A detergent composition according to claims 1 to 2, wherein M represents sodium. 4. A detergent composition according to claims 1 to 3, wherein the silicate is α-, β-, γ- or δ-Na₂Si₂O₅. 5. A detergent composition according to claims 1 to 4, wherein the flocculant polymer is a polymer of ethylene oxide, acrylamide or acrylic acid. 6. A detergent composition according to claims 1 to 5, which is further characterized in that the clay is present in an amount of less than 1% by weight of the detergent composition, more preferably that the detergent composition is substantially free thereof. 7. Detergent composition according to claims 1 to 6, which further comprises surfactants, builders and enzymes. 8. Detergent composition according to claims 1 to 7, which is in the form of a liquid, a granule, a paste, a bar or a gel. 9. Use of a crystalline layered silicate of the formula NaMSixO2x+1yH₂O, wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20; and a flocculant polymer selected from polymers and copolymers derived from monomers selected from ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethyleneimine, or mixtures thereof, in a detergent composition for providing fabric softening.