CN1228114A - Bleach precursor compositions - Google Patents

Abstract

The present invention provides solid bleach precursor compositions comprising a bleach precursor and a surfactant system whereby the composition exhibits effective solubilization of its bleach precursor components.

Description

Bleach precursor composition

technical field of invention

The present invention relates to bleach precursor compositions and their incorporation in detergent compositions whereby the precursors exhibit effective solubilizing properties.

Background of the invention

Satisfactory removal of soils/stains from soiled/soiled substrates is a particular challenge for the formulator of detergent compositions for use in laundering processes, such as laundry or mechanical dishwashing processes.

Traditionally, such soils/stains have been removed by the use of bleaching components, such as oxygen bleaches, including hydrogen peroxide and organic peroxyacids. Organic peroxyacids are often obtained by in situ perhydrolysis reaction between hydrogen peroxide and organic peroxyacid bleach precursors, so-called "bleach precursors".

A problem encountered with the use of bleach precursors is that the rate of solubilization of the precursor decreases in cold temperature wash solutions (5°C-30°C) or under conditions of high water hardness. As the rate of perhydrolysis decreases, the wash performance decreases. This problem of low solubilization or dissolution is exacerbated when the precursor exhibits satisfactory surfactant properties. Typical examples of such precursors are amide substituted bleach precursor compounds such as (6-octanoylaminocaproyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl) as described in EP-A-0170386 ) oxybenzenesulfonate and (6-decanoylaminocaproyl)oxybenzenesulfonate. Formulators of bleach precursor compositions therefore face the challenge of formulating bleach precursor compositions that provide effective solubilization or dissolution of the precursors.

To address this low solubility problem, it has been proposed to coat and/or agglomerate the bleach precursor with a water soluble material, as described in co-pending application PCT/US95/15494.

However, despite the advances in the prior art, there remains a need for alternative compositions which provide effective dissolution of bleach precursors.

Applicants have now found that this problem is overcome by combining peroxyacid bleach precursors with surfactant systems comprising non-ethoxylated anionic surfactants and nonionic surfactants.

Summary of the invention

The present invention includes solid bleach precursor compositions comprising:

a) - bleach precursors; and

b) - surfactant systems containing non-ethoxylated anionic surfactants and nonionic surfactants;

wherein said surfactant system and said precursor are in close physical proximity.

It should be understood that close physical proximity means that the precursor and the surfactant system are not two separate separate particles in the detergent composition.

For purposes of this invention, the term "close physical proximity" means one of the following:

i) agglomerates, granules or extrudates, wherein said precursor and said surfactant system are intimate blends;

ii) bleach precursor particles coated with one or more layers, at least one layer comprising a surfactant system component and the other in intimate admixture with the bleach precursor component;

iii) Bleach precursor particles containing one surfactant system component and coated with one or more layers, at least one of which contains bleach in intimate admixture with other surfactant system components Bleach precursors;

iv) Bleach precursor particles coated with one or more layers, at least one of which contains two surfactant system components, or coated with at least two layers, at least one of which contains a surfactant system The component and at least one other layer contain other surfactant system components;

v) Bleach precursor particles comprising two surfactant system components coated in one or more layers, at least one of which contains a bleach activator.

In another embodiment of the present invention, the present invention comprises detergent compositions incorporating a solid bleach precursor composition as defined above.

Detailed description of the invention

bleach precursor

An essential component of the present invention is the bleach precursor. Bleach precursors for inclusion in the compositions of the present invention generally contain one or more N- or O-acyl groups and may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, nitriles and acylated derivatives of imidazoles and oximes, examples of useful materials of this class are disclosed in GB-A-1586789.

Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. Also suitable are the acylation products of sorbitol, glucose and all sugars with benzoylating and acetylating agents.

Specific O-acylation precursor compounds include nonanoyloxybenzenesulfonate, 3,5,5-trimethylhexanoyloxybenzenesulfonate, benzoyloxybenzenesulfonate, benzoyl Cationic derivatives of oxybenzenesulfonate, nonanoyl-6-aminocaproyloxybenzenesulfonate, monobenzoyltetraacetylglucose and pentaacetylglucose. Phthalic anhydride is a suitable anhydride-type precursor and useful N-acyl compounds are disclosed in GB-A-855735, 907356 and GB-A-1246338.

Preferred imide-type precursor compounds include N-benzoylsuccinimide, tetrabenzoylethylenediamine, N-benzoyl-substituted ureas, and N,N-N'N'tetraacetylated Alkylenediamines wherein the alkylene group contains 1 to 6 carbon atoms, especially compounds wherein the alkylene group contains 1, 2 and 6 carbon atoms. The most preferred precursor compound is N,N-N',N'tetraacetylethylenediamine (TAED).

Lactam N-acylated precursor compounds are generally disclosed in GB-A-955735. While any useful lactam may be used as the peroxyacid precursor within the broadest scope of the invention, preferred materials include caprolactam and valerolactam.

其中R¹是H或含有1-12个碳原子，优选6-12个碳原子的烷基、芳基、烷氧基芳基或烷芳基。A suitable caprolactam bleach precursor has the formula:

wherein ^R is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing 1-12 carbon atoms, preferably 6-12 carbon atoms.

其中R¹是含有H或含有1-12个碳原子，优选6-12个碳原子的烷基、芳基、烷氧基芳基或烷芳基。在高度优选的实施方案中，R¹选自苯基、庚基、辛基、壬基、2，4，4-三甲基戊基、癸烯基和它们的混合物。Suitable valerolactams have the formula:

Wherein R ¹ is an alkyl group, aryl group, alkoxyaryl group or alkaryl group containing H or 1-12 carbon atoms, preferably 6-12 carbon atoms. In a highly preferred embodiment, ^R is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.

Most preferred materials are those which are generally solid at <30°C, especially phenyl derivatives, i.e. benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogs, e.g. chloro, amino, Nitro, alkyl, alkyl, aryl and alkoxy derivatives.

Caprolactam and valerolactam precursor materials wherein the R ^moiety contains at least 6, preferably 6 to about 12 carbon atoms provide peroxyacids upon perhydrolysis of hydrophobic character which provide nucleophilicity and body soil cleansing. Precursor compounds wherein ^R1 contains 1 to 6 carbon atoms provide hydrophilic bleaching species which are especially effective in bleaching beverage stains. Mixtures of 'hydrophobic' and 'hydrophilic' caprolactams and valerolactams, typically in a weight ratio of 1:5 to 5:1, preferably 1:1, can be used herein to provide mixed stain removal.

Another preferred class of bleach precursor materials comprises cationic bleach activators derived from valerolactam and acyl caprolactam compounds of the formula: Wherein x is 0 or 1, the substituents R, R' and R" are each C1-C10 alkyl or C2-C4 hydroxyalkyl or [(C _y H _2y ) _O ]n- ^R , where y=2- 4. n=1-20 and R'' is C1-C4 alkyl or H and X are anions.

Suitable imidazoles include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl containing peroxyacid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzene Formyl pyroglutamic acid.

Another preferred class of bleach precursor compounds are amide substituted compounds of the general formula:

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 a compound containing about 1 to about 14 carbon atoms Alkyl, alkylene, aryl or alkaryl, R ² is an alkylene, arylene and alkarylene group containing about 1-14 carbon atoms, R ⁵ is H or contains 1-10 An alkyl, aryl, or alkaryl group of carbon atoms, and L can be essentially any leaving group. ^R1 preferably contains about 6-12 carbon atoms. ^R2 preferably contains about 4-8 carbon atoms. R ¹ may be straight or branched chain alkyl, substituted aryl or alkaryl containing branching, substituents or both and may be derived from synthetic or natural sources including, for example, tallow. Similar structural changes are also permissible for ^R2 . Substituents may include alkyl, aryl, halogen, nitrogen, sulfur, and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should preferably not contain together more than 18 carbon atoms. Preferred examples of bleach precursors of the above formula include those selected from (6-octanoylaminocaproyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl)oxybenzene sulfonate, (6-nonanoylaminocaproyl)oxybenzene, described in EP-A-0170386 Amide-substituted peroxyacid precursor compounds of sulfonate salts and (6-decanoylaminocaproyl)oxybenzenesulfonate salts and mixtures thereof.

包括下式类型的取代的苯并噁嗪：其中R₁是H、烷基、烷芳基、芳基、芳烷基、仲或叔胺和其中R₂、R₃、R₄和R₅可以是相同或不同的取代基，其选自H、卤素、烷基、链烯基、芳基、羟基、烷氧基、氨基、烷基氨基、COOR₆(其中R₆是H或烷基)和羰基。Also suitable are the benzoxazine precursor compounds disclosed, for example, in EP-A-332294 and EP-A-482807, especially those compounds of the formula:

Included are substituted benzoxazines of the type: wherein R ₁ is H, alkyl, alkaryl, aryl, aralkyl, secondary or tertiary amine and wherein R ₂ , R ₃ , R ₄ and R ₅ may be the same or different substituents selected from H , halogen, alkyl, alkenyl, aryl, hydroxy, alkoxy, amino, alkylamino, COOR ₆ (wherein R ₆ is H or alkyl) and carbonyl.

Especially preferred benzoxazine-type precursors are .

The bleach precursor component preferably has a particle size of 250-2000 microns.

These bleach precursors can be partially prepared by preformed peracids such as N,N-phthaloylaminoperoxyacid (PAP), nonylamide of peroxyadipate (NAPAA), 1,2-di peroxydodecanedioic acid (DPDA) and trimethylammonium acrylamido peroxymellitic acid (TAPIMA) substitution.

More preferred among the above bleach precursors are nonanoyloxybenzene sulphonates and/or amide substituted bleach precursor compounds. The most preferred bleach precursor is selected from the group consisting of (6-octanoylaminocaproyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl)oxybenzenesulfonate and (6-decanoylaminocaproyl)oxybenzenesulfonate Amide-substituted bleach precursor compounds of ) oxybenzenesulfonates and mixtures thereof.

The bleach precursors are typically added at levels of from 20% to 95% by weight of the bleach precursor component, preferably from 50% to 90%, most preferably at least 60% by weight thereof. Surfactant system

An essential feature of the present invention is a surfactant system comprising a non-ethoxylated anionic surfactant and a nonionic surfactant. The surfactant system is generally present in an amount of from 0.1% to 50% by weight of the bleach precursor composition, more preferably from 1% to 20% by weight of the bleach precursor composition. Non-Ethoxylated Anionic Surfactants

Non-ethoxylated anionic surfactants suitable for use herein include salts of anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (including, for example, sodium, potassium, ammonium and substituted ammonium salts, eg mono-, di- and triethanolamine salts).

Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl taurine, alkylsuccinates and sulfosuccinates, sulfosuccinates, Succinic acid monoesters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), sulfosuccinic acid diesters (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosine Salt. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic sulfate surfactants suitable for the present invention include linear and branched primary alkyl sulfates, fatty oleoyl glycerol sulfates, C ₅ -C ₁₇ acyl-N-(C ₁ -C ₄ alkyl) and - N-(C ₁ -C ₂ hydroxyalkyl)glucosamine sulfates and sulfates of alkyl polysaccharides, such as alkyl polyglucosides (nonionic unsulfated compounds described herein).

Alkyl sulfate surfactants are preferably selected from branched and random C10-C20 alkyl sulfates ("AS"), _CH3 ( _CH2 ) _x ( _CHOSO3 ^- M ⁺ ) _CH3 and _CH3 (CH ₂ ) C10-C18 secondary (2,3) alkyl sulfates of _y (CHOSO ₃ ⁻ M ⁺ )CH ₂ CH ₃ , wherein x and (y+1) are integers of at least 7, preferably at least about 9, and M is Water-solubilizing cations, especially sodium, unsaturated sulfates such as oleyl sulfate.

Anionic sulfonate surfactants suitable for use in the present invention include C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C _6-22 primary or secondary alkane sulfonates, C ₆ -C ₂₄ Olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and mixtures of any thereof.

Anionic carboxylate surfactants suitable for use herein include soaps ('alkyl carboxyl'), especially certain of the secondary soaps described herein.

Preferred soap surfactants are secondary soap surfactants which contain carboxyl units attached to secondary carbons. The secondary carbon may be in the ring structure, for example as in p-octylbenzoic acid, or as in the case of alkyl substituted cyclohexyl carboxylates. The secondary soap surfactant should preferably be free of ether linkages, ester linkages and hydroxyl groups. There should preferably be no nitrogen atoms in the head group (amphiphilic moiety). Secondary soap surfactants typically contain 11 to 15 total atoms, although slightly higher numbers of carbon atoms (eg, up to 16) may be tolerated, eg p-octylbenzoic acid.

Some preferred secondary soap surfactants are further illustrated by the following general structures: A. Highly preferred secondary soaps include secondary carboxyl species of formula ^R3CH ( ^R4 )COOM, where ^R3 is _CH3 ( _CH2 ) _x , R ⁴ is CH ₃ (CH ₂ ) _y , wherein y can be 0 or an integer from 1 to 4, x is an integer from 4 to 10, and the sum of (x+y) is 6 to 10, preferably 7-9, most preferably 8. B. Another preferred class of secondary soaps includes carboxyl compounds, wherein the carboxyl substituent is on the cyclohydrocarbyl unit, i.e. secondary soaps of formula ^R5 - ^R6 -COOM, wherein ^R5 is ^C7 - ^C10 , preferably ^C8 -C ⁹ alkyl or alkenyl, R ⁶ is a ring structure, such as benzene, cyclopentane and cyclohexane. (note: with respect to the carboxyl group R on the ring ⁵ can be in ortho, inter or para position). C. Yet another class of preferred secondary soaps includes secondary carboxyl compounds of the formula:

CH ₃ (CHR) _k -(CH ₂ ) _m -(CHR) _n -CH(COOM)(CHR) _o -(CH ₂ ) _p -(CHR) _q -CH ₃ where each R is C ₁ -C ₄ Alkyl, wherein k, n, o, q are integers of 0-8, provided that the total number of carbon atoms (including carboxylate) is 10-18.

In each of formulas A, B and C above, species M may be any suitable, especially water-solubilizing, counterion.

Particularly preferred secondary soap surfactants for use herein are water soluble materials selected from 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1 - Water-soluble salts of nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.

Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CON(R ¹ )CH ₂ COOM, wherein R is C ₅ -C ₁₇ linear or branched chain alkyl or alkenyl, and R ¹ is C ₁ -C ₄ alkyl, M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the sodium salt form.

Among the above-mentioned non-ethoxylated anionic surfactants, anionic sulfate surfactants, anionic sulfonate surfactants or mixtures thereof are preferred, and more preferred anionic surfactants are selected from C ₁₂ -C ₁₈ straight Alkyl sulfates, C ₅ -C ₂₀ linear alkylbenzene sulfonates and mixtures thereof, most preferably C ₅ -C ₂₀ linear alkyl benzene sulfonates.

Anionic surfactants are preferably present at from 0.1% to 49.9% by weight of the bleach precursor composition, more preferably from 1% to 19% by weight of the bleach precursor composition. nonionic surfactant

Nonionic surfactants useful in the present invention include polyhydroxy fatty acid amide surfactants, condensates of alkylphenols, ethoxylated alcohol surfactants, ethoxylated/propoxylated fatty alcohol surfactants, Condensates of ethylene oxide/propylene oxide with propylene glycol, condensation products of ethylene oxide with propylene oxide/ethylenediamine adducts, alkyl polysaccharide surfactants, fatty acid amide surfactants and mixtures thereof. Exemplary, non-limiting classes of useful nonionic surfactants are listed below.

The polyhydroxy fatty acid amide suitable for the present invention is the compound of structural formula R ² CONR ¹ Z, wherein R ¹ is hydrogen, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or their mixture, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (i.e. methyl); R ² is C ₅ -C ₃₁ hydrocarbon, preferably straight chain C ₅ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₇ alkyl or alkenyl or a mixture thereof; Z is a type having at least three directly connected lines Polyhydroxyhydrocarbyl moieties or alkoxylated derivatives thereof (preferably ethoxylated or propoxylated) of hydroxyl groups in the hydrocarbyl chain. Z is preferably derived from a reducing sugar in a reductive amination reaction, more preferably Z is a glycosyl moiety.

Polyoxyethylene, polyoxypropylene, polyoxybutylene condensates of alkylphenols are suitable for use in the present invention. Polyoxyethylene condensates are generally preferred. These compounds include the condensation products of alkylphenols with ethylene oxide having an alkyl group having from about 6 to about 18 carbon atoms in a linear or branched configuration.

Alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use in this invention. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains 6-22 carbon atoms. Especially preferred are the condensation products of alcohols having alkyl groups containing 8 to 20 carbon atoms and from about 2 to about 10 moles of ethylene oxide per mole of alcohol.

As ethoxylated/propoxylated fatty alcohol surfactants, ethoxylated _C6 - _C18 fatty alcohols and _C6 - _C18 mixed ethoxylated/propoxylated fatty alcohols are useful in the present invention Suitable surfactants, especially if water soluble. Preferred ethoxylated fatty alcohols are C ₁₀ -C ₁₈ ethoxylated fatty alcohols with a degree of ethoxylation of 3-50, most preferably C ₁₂ -C ₁₈ ethoxylated alcohols with a degree of ethoxylation of 3-40 Alcohols. Preferred mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of 10-18 carbon atoms, a degree of ethoxylation of 3-30 and a degree of propoxylation of 1-10.

Condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol are suitable for use in the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Examples of compounds of this type include certain commercially available Pluronic ^™ surfactants sold by BASF.

The condensation products of ethylene oxide with the product obtained by the reaction of propylene oxide and ethylenediamine are suitable for use in the present invention. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of from about 2500 to about 3000. Examples of nonionic surfactants of this type include certain of the commercially available Tetronic ^™ compounds sold by BASF.

Suitable alkylpolysaccharides for use in the present invention are disclosed in US 4,565,647, Llenado, issued January 22, 1986, containing hydrophobic groups of about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms and containing A polysaccharide such as a polyglycoside with about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7 saccharide units has a hydrophilic group. Any reducing sugar containing 5 or 6 carbon atoms can be used, for example glucose, galactose and galactosyl moieties can be used in place of glucosyl moieties. (The hydrophobic group is optionally attached at the 2-, 3-, 4-, etc. position, resulting in glucose or galactose relative to glucoside or galactoside.) The intersugar linkage can be at, for example, one position of the added sugar unit and Between the 2-, 3-, 4- and/or 6-positions of the preceding sugar unit.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains 10-18 , preferably 12-14 carbon atoms; n is 2 or 3; t is 0-10, preferably 0, x is 1.3-8, preferably 1.3-3, most preferably 1.3-2.7. The glycosyl is preferably derived from glucose.

Fatty acid amide surfactants suitable for use in the present invention are compounds of the formula R ⁶ CON(R ⁷ ) ₂ , wherein R ⁶ is an alkyl group containing 7-21, preferably 9-17 carbon atoms, and each R ⁷ is selected from Hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and -(C ₂ H ₄ O) _x H, wherein x is 1-3.

Among the nonionic surfactants mentioned above, ethoxylated surfactants are preferred, preferably selected from the group consisting of ethoxylated alcohol surfactants, ethoxylated/propoxylated fatty alcohol surfactants, ethylene oxide/cyclo Condensates of propylene oxide with propylene glycol, condensation products of ethylene oxide with propylene oxide/ethylenediamine adducts, more preferably ethoxylated alcohol surfactants.

The most preferred ethoxylated alcohol surfactants are condensation products of alcohols containing alkyl groups of 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol, especially with an average of 3 moles of ethylene oxide Alkanes condensed linear primary alcohols (C12/C14).

The nonionic surfactant is preferably present in an amount of from 0.01% to 20% by weight of the bleach precursor composition, more preferably from 0.1% to 5% by weight of the bleach precursor composition. optional components

Optional components may be present in the bleach precursor composition. Suitable optional components for use in the present invention include hydrotrope components, acids, binders, additional surfactants, such as cationic surfactants, and mixtures thereof.

Hydrotropes are especially useful as optional components of bleach precursor compositions because they unexpectedly aid in the solubilization of bleach precursor compositions. When used, hydrotropes are generally present in amounts of from 0.1% to 20%, preferably from 0.5% to 10% by weight of the bleach precursor composition.

Optional hydrotropes suitable for use in the present invention are selected from lower alkyl aryl sulfonates, C ₆ -C ₁₂ alkanols, C ₁ -C ₆ carboxy sulfates or sulfonates, urea, C ₁ -C ₄ Hydrocarboxylates, C ₁ -C ₄ carboxylates and C ₂ -C ₄ diacids and mixtures thereof.

Suitable lower alkyl aryl sulfonates are preferably C ₇ -C ₉ alkyl aryl sulfonates including sodium, potassium, calcium and ammonium xylene sulfonates, sodium, potassium, calcium and ammonium toluene sulfonates, cumene Sodium, potassium, calcium and ammonium olefin sulfonates, sodium, potassium, calcium and ammonium naphthalene sulfonates and mixtures thereof.

Suitable C ₁ -C ₈ carboxysulfate or sulfonate salts are any water-soluble salts of organic compounds containing 1 to 8 carbon atoms (excluding substituents) which are substituted by sulfate or sulfonate groups and have at least one carboxyl. Substituted organic compounds can be cyclic, acyclic or aromatic, ie benzene derivatives. Preferred alkyl compounds contain 1-4 carbon atoms substituted by sulfate or sulfonate and have 1-2 carboxyl groups. Examples of suitable hydrotropes include sulfosuccinates, sulfophthalates, sulfoacetates, m-sulfobenzoates and sulfosuccinate diesters, preferably as disclosed in US3915903 sodium or potassium salts.

Suitable C ₁ -C ₄ hydrocarbon carboxylates, C ₁ -C ₄ carboxylates for use in the present invention include acetates and propionates and citrates. Suitable _C2 - _C4 diacids for use in the present invention include succinic acid, glutaric acid and adipic acid.

Other compounds suitable for use as hydrotropes in the present invention that provide a hydrotropic effect include C ₆ -C ₁₂ alkanols and urea.

Preferred hydrotropes for use in the present invention are selected from the group consisting of cumene sulfonates, xylene sulfonates, toluene sulfonates and mixtures thereof. Salts suitable for use in the present invention are sodium, potassium, calcium and ammonium. Sodium tosylate is most preferred.

Acids may also be used in the compositions of the invention, especially as stabilizers. Such acids are typically present at levels of from 0.1% to 40%, preferably from 1% to 20%, by weight of the bleach precursor composition. Suitable acids are preferably water-soluble, such as fatty acids, glycolic acid, glutaric acid, citric acid and polymeric carboxylic acids.

Binders may optionally be used in the compositions of the present invention. Typical levels of such binders are from 0.01% to 20%, preferably from 0.5% to 10% by weight of the bleach precursor composition. Suitable binders include starch, cellulose and cellulose derivatives (such as sodium carboxymethylcellulose), sugars and film-forming polymers, such as polymeric carboxylic acids, including copolymers, polyvinylpyrrolidone, polyvinyl acetate ester. Cellulose and cellulose derivatives such as sodium carboxymethylcellulose are especially preferred. Form of the bleach precursor composition

The surfactant system and the bleach precursor of the solid bleach precursor composition are in close physical proximity.

It should be understood that close physical proximity means that the precursor and the surfactant system are not two separate separate particles in the detergent composition.

For purposes of this invention, the term "close physical proximity" means one of the following:

i) agglomerates, granules or extrudates, wherein said precursor and said surfactant system are intimate blends;

ii) coating the bleach precursor with one or more layers, at least one layer comprising a surfactant system component and the others in intimate admixture with the bleach precursor component;

iii) Bleach precursor particles containing one surfactant system component and coated with one or more layers, at least one of which contains bleach in intimate admixture with other surfactant system components Bleach precursors;

iv) Bleach precursor particles coated with one or more layers, at least one of which contains two surfactant system components, or coated with at least two layers, at least one of which contains a surfactant system The component and at least one other layer contain other surfactant system components;

v) Bleach precursor particles comprising two surfactant system components coated in one or more layers, at least one of which contains a bleach activator.

The bleach precursor composition may preferably be in any known particulate form suitable for incorporation into detergent compositions, such as agglomerates, granules, extrudates or spherical extrudates. The bleach precursor composition is preferably in the form of a pellet extrudate.

A preferred method of preparing the bleach precursor pellets comprises the following steps:

(i) preparing a mixture of solid and optionally liquid containing a bleach activator;

(ii) extruding the mixture under pressure through a die to form an extrudate;

(iii) crushing the extrudate to form spherical extrudates; and

(iv) Optionally coating the particles to improve friability and flow.

The mixing step (i) is performed using any conventional powder/liquid mixer, for example a Loedige KM mixer. Extrusion step (ii) can be achieved using any conventional extruder, which can be axial, radial or more preferably domed, such as the Fuji Paudal Model DGL-1, most preferably a die with openings less than 0.1mm, Squeeze at a pressure of about 20 bar. Step (iii) is preferably carried out using a rotating disc pelletizer, such as a Fuji Paudal QJ-1000, wherein the extrudate is broken into short lengths to form substantially spherical particles.

Alternatively, the extrudate may then be dried in a vibrating fluid bed dryer, such as Niro, to obtain crisp, free-flowing granules with a particle size of 0.25mm-20mm and a Heubach dust measurement of less than 100 mg/g.

The optional coating step (iv) may comprise substances such as film forming polymers or preferably liquid fixatives such as nonionic surfactants and inert powders such as zeolite A.

Effective solubilization rate means that using a composition comprising a bleach precursor and a surfactant system as described above provides better bleach precursor solubilization compared to using the same composition without a surfactant system . Peroxyacid bleach precursor particles may suitably be incorporated into detergent compositions. Detergent compositions incorporating peroxyacid bleach precursor particles will generally contain from 1% to 20% by weight of the composition of precursor particles, more usually from 1% to 10%, most preferably from 1% to 7%.

The detergent composition will, of course, contain the necessary source of alkaline hydrogen peroxide to form the peroxyacid bleaching species in the wash solution, and preferably also other conventional ingredients of detergent compositions.

Detergent compositions incorporating the particulate peroxyacid precursors of the present invention will include hydrogen peroxide or a source thereof. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, usually in the form of the sodium salt as the source of alkaline hydrogen peroxide in the wash liquor. The perhydrate is typically incorporated at a level of from 3% to 40% by weight of the composition, more preferably from 5% to 35% by weight of the composition, most preferably from 8% to 30% by weight of the composition.

The perhydrate can be any alkali metal inorganic salt such as perborate monohydrate or tetrahydrate, percarbonate, perphosphate and persilicate, but is usually an alkali metal perborate or percarbonate salt.

The preferred perhydrate-sodium percarbonate is an adduct of formula _{2Na2CO3.3H2O2} , _commercially available _{as a} crystalline solid. The most commercially available materials include low levels of heavy metal chelating agents, such as EDTA, 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP), or aminophosphonates, which are incorporated during manufacture. For the detergent composition aspects of the present invention, the percarbonate salts can be incorporated into detergent compositions without additional protection, although preferred embodiments of the compositions use the material in coated form. Various coatings can be used, including borates, boric acid and citrates or sodium silicate with a _SiO2 : _Na2O ratio of 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to obtain pressed Silicate solids content of 2% to 10% (typically 3% to 5%) by weight of carbonate. However, the most preferred coating is a mixture of sodium carbonate and sodium sulfate or sodium chloride.

The particle size of the crystalline percarbonate ranges from 350 microns to 1500 microns, with an average of about 500-1000 microns.

Besides the bleach precursor particles and hydrogen peroxide or source thereof, the detergent composition may contain additional components. The exact nature of these additional ingredients and the levels at which they are incorporated will depend upon the physical form of the composition and the nature of the laundering operation for which it is employed. For example, the compositions of the present invention may be formulated as hand and machine laundry detergent compositions, including laundry additive compositions and compositions suitable for pretreatment of soiled fabrics and machine dishwashing compositions. When incorporated into compositions suitable for use in machine laundering processes, such as machine laundry and machine dishwashing processes, the compositions of the present invention preferably contain one or more additional detersive ingredients.

Accordingly, preferred detergent compositions will incorporate one or more of surfactants, builders, chelating agents, enzymes, soil-suspending and anti-redeposition agents, suds suppressors, optical brighteners, photoactivated bleaching agents, agents, fragrances and colorants. Surfactant

A variety of surfactants can be used in detergent compositions. Typical anionic, nonionic, amphoteric and zwitterionic classes and such surfactant materials are listed in US Patent 3,929,678, Laughlin and Heuring, issued December 30,1975. Suitable cationic surfactants are given in US Patent 4,259,217, Murphy, issued March 31,1981.

Non-limiting examples of surfactants useful in the present invention at levels typically ranging from 1% to 55% by weight include conventional C ₁₁ -C ₁₈ alkylbenzene sulfonates ("LAS") and primary, branched, and or random C ₁₀ -C ₂₀ alkyl sulfonates ("AS"), formulas CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ )CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^- M ⁺ ) C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates of CH ₂ CH ₃ , wherein x and (y+1) are integers of at least 7, preferably at least 9, and M is water-soluble Cations, especially sodium, unsaturated sulfates such as oleyl sulfate, C ₁₀ -C ₁₈ alkyl alkoxy sulfates (“AE _x S”; especially EO 1-7 ethoxy sulfates), C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially EO 1-5 ethoxy carboxylates), C ₁₀ -C ₁₈ glyceryl ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulphates Polyglycosides, and C ₁₂ -C ₁₈ α-sulfonated fatty acid esters. If desired, conventional nonionic and amphoteric surfactants such as C ₁₂ -C ₁₈ alkyl ethoxylates ("AE"), including so-called narrow peak alkyl ethoxylates, may also be included in the overall composition. and C ₆ -C ₁₂ alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxylates), C ₁₂ -C ₁₈ betaines and sultaines ("sultaines ”), C ₁₀ -C ₁₈ amine oxides, etc. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include C ₁₂ -C ₁₈ N-methyl glucamides. See WO9206154. 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 glucamides can be used for low sudsing applications. Conventional _C10 - _C20 soaps may also be used. If high lather is desired, branched _C10 - _C16 soaps can be used. Other suitable surfactants for use in the present invention are anionic alkali metal sarcosinates of the formula:

R-CON(R ¹ )CH ₂ COOM wherein R is a C ₉ -C ₁₇ linear or branched chain alkyl or alkenyl group, R ¹ is a C ₁ -C ₄ alkyl group, and N is an alkali metal ion. Preferred examples are lauroyl, cocoyl (C ₁₂ -C ₁₄ ), myristyl and oleoyl methyl sarcosinates in the form of their sodium salts. Cationic surfactants may also be used in the compositions of the present invention. Suitable cationic surfactants include quaternary ammonium surfactants selected from mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are replaced by methyl, hydroxyethyl or hydroxypropyl substitution. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. builder

Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic and organic builders can be used. Builders are generally used in fabric washing compositions to aid in the removal of soil particles. The builder level can vary widely depending on the end use of the composition and its desired physical form. When present, the compositions will generally contain at least 1% of builder. Granular formulations generally contain from 10% to 80%, more typically from 15% to 50%, by weight of detergent builder. However, this does not mean that lower or higher builder levels are excluded.

Inorganic or phosphate-containing detergency builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (eg, tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates).

Non-phosphate builders can also be used. They may include, but are not limited to, phytic acids, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulfates, aluminosilicates and monomeric polycarboxylates , homo- or co-polymeric polycarboxylic acids or their salts, wherein the polycarboxylic acids contain at least two carboxyl groups separated from each other by not more than two carbon atoms, organic phosphonates and aminoalkylene poly(alkylene phosphonates) ). The compositions of the present invention can be used even in the presence of so-called "weak" builders (compared to phosphates) such as citrates, or in so-called "underbuilt" environments created by the use of zeolite or layered silicate builders. also works well.

Examples of silicate builders are the so-called 'amorphous' alkali metal silicates, especially those having a _SiO2 : _Na2O ratio in the range of 1.6:1 to 3.2:1, and crystalline layered Silicates such as layered sodium silicates as described in US4664839. NaSKS-6 is a trademark for a crystalline layered silicate sold by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 is a phyllosilicate with _a δ- _Na2Si2O5 morphological configuration _. It can be prepared by methods as described in DE-A-3417649 and DE-A-3742043. SKS-6 is a very preferred phyllosilicate for use herein, but other phyllosilicates may be used, such as those having the general formula _{NaMSixO2x + 1.yH2O} , where M is sodium or hydrogen, Phylosilicates where x is a value from 1.9 to 4, preferably 2, and y is a value from 0 to 20, preferably 0. Various other layered silicates are commercially available from Hoechst, including NaSKS-5, NaSKS-7, and NaSKS-11, in the alpha, beta, and gamma forms. As noted above, δ- _Na2Si2O5 (NaSKS-6 form) is most preferably used _{herein .} Other silicates are also useful, such as magnesium silicate, as a crisping agent in granular formulations, a stabilizer for oxygen bleaches and a component of foam control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates in German Patent Application 2321001, published November 15,1973.

Aluminosilicate builders are of paramount importance in the most popular commercially available heavy duty granular detergent compositions and can also be an important builder ingredient in liquid detergent formulations. Aluminosilicate builders include builders having the following empirical formula:

Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ]·xH ₂ O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to 0.5, and x is an integer of 15-264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be of crystalline or amorphous structure and can be naturally occurring aluminosilicates or synthetically derived. A method of preparing aluminosilicate ion exchange materials is disclosed in US3985669. Preferred synthetic crystalline aluminosilicate ion exchange materials for use in the present invention are commercially available under the designations Zeolite A, Zeolite P(B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ].xH ₂ O where x is 20 to 30, especially 27. This material is called Zeolite A. Dehydrated zeolites (x=0-10) can also be used in the present invention. The aluminosilicate preferably has a particle size of 0.1-10 microns in diameter.

Organic detergent builders suitable herein include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" means a compound having a plurality of carboxylate groups, preferably at least 3 carboxylate groups. Polycarboxylate builders can generally be incorporated into the compositions in acid form, but can also be added in neutralized salt form. When used in salt form, alkali metal such as sodium, potassium and lithium salts, or alkanolammonium salts are preferred. Polycarboxylate builders include a wide variety of useful materials. An important class of polycarboxylate builders include ether polycarboxylates, including oxydisuccinic acids, as described in US3128287 and US3635830. See also "TMS/TDS" builders in US4633071. Suitable ether polycarboxylates may also include cyclic compounds, especially cycloaliphatic compounds, such as those described in US Pat. Other useful detergency builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether or acrylic acid, 1,3,5-trihydroxybenzene-2,4,6-trisulfonate various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates such as mellitic acid, succinic acid, oxygen Disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxydisuccinic acid, and their water-soluble salts.

Citrate builders, such as citric acid and its soluble salts (especially the sodium salt), are ideal for heavy duty liquid detergent formulations due to their availability and biodegradability from renewable resources. Polycarboxylate builders of particular interest. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

The 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in US4566984 are also suitable for use in the compositions of the present invention. Useful succinic acid builders include _C5 - _C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: lauryl succinate, myristyl succinate, cetyl succinate, 2-dodecenyl succinate (preferred), 2-decenyl succinate Pentacenyl succinate, etc. Lauryl succinate is one of the preferred builders and is described in EP0200263. Other suitable polycarboxylates are disclosed in US4144226 and US3308067. See also US3723322.

Fatty acids, such as _C12 - _C18 monocarboxylic acids, may also be incorporated into the composition alone, or in combination with the aforementioned builders, especially citrate and/or succinate builders, to produce additional builders active. This use of fatty acids often results in reduced foam, which should be taken into account by the formulator.

Where phosphorus-based builders can be used, and especially in the formulation of bars for handwashing operations, the various alkali metal phosphates such as the known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used . Phosphonate builders can also be used, such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, eg, US Pat. Chelating agent

The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, as defined below. While not wishing to be bound by theory, it is believed that the benefits of these materials are due in part to their superior ability to remove iron and manganese ions from wash solutions through the formation of soluble chelates.

Amino carboxylates that may be used as optional chelating agents include EDTA, N-HydroxyethylEDTA, Nitrilotriacetate, EDTA , triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts, and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediamine tetrakis (methylene phosphonates), such as DEQUEST and hydroxyethane 1,1-diphosphonic acid (HEDP). These amino phosphonates preferably do not contain alkyl or alkenyl groups of more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also suitable for use in the compositions of the present invention. See US3812044, Connor et al., issued May 21,1974. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), particularly the [S,S] isomer and/or hydroxy-ethane 1,1 diphosphonic acid ( HEDP).

The compositions of the present invention may also contain water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a chelating agent or co-builder with, for example, insoluble builders such as zeolites, layered silicates, etc. .

If utilized, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. Even more preferably, if used, such chelating agents comprise from about 0.1% to about 3% by weight of the composition. enzyme

A variety of enzymes may be included in the compositions of the present invention for a variety of purposes including the removal of protein-based, carbohydrate-based or triglyceride-based stains from stain carriers, in order to prevent the transfer of fugitive dyes during fabric laundering , and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof, from any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Their preference is influenced by factors such as pH-activity and/or stability optimum, thermostability and stability to active detergents, builders and the like. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

As used herein, "detersive enzyme" refers to any enzyme having a cleaning, stain removal or other benefit in laundry, hard surface cleaning and personal care detergent compositions. Preferred detergent enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred for use in automatic dishwashing are amylases and/or proteases, both currently available and improved, but for improved species, although increasingly compatible with bleach through continual improvement, It still has a residual degree of bleach inactivation sensitivity.

Enzymes are typically incorporated into detergent compositions at levels sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removing, soil removing, whitening, deodorizing or freshness improving effect on a soil carrier such as fabrics, containers and the like. Indeed, typical amounts of active enzyme are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, per gram of detergent composition for today's commercial formulations. In other words, the compositions of the invention generally comprise from 0.001% to 5%, preferably from 0.01% to 1%, by weight of a commercial enzyme preparation. The level of protease in such commercial enzyme preparations should generally be sufficient to provide 0.005-0.1 Anson Units (AU) of activity per gram of composition.

Suitable examples of proteases are subtilisins obtained from special strains of Bacillus subtilis and Bacillus licheniformis. A suitable protease is obtained from a Bacillus strain having maximum activity in the pH range of 8-12, developed by Novo Industries A/S of Denmark, hereinafter "Novo", and sold as ESPERASE(R). The preparation of this and similar enzymes is described in GB 1243784 to Novo. Other suitable proteases include ALCALASE(R) and SAVINASE(R) from Novo and MAXATASE(R) from International Bio-Synthetics, Inc, The Netherlands; and Protease A disclosed in EP130756, and Protease B disclosed in EP303761 and EP130756. See also the high pH protease from Bacillus NCIMB 40338 described in WO9318140A to Novo. Enzyme detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO9203529A to Novo. Other preferred proteases include the enzymes in WO9510591A to Procter & Gamble. Proteases with reduced absorbency and increased hydrolysis are available, if desired, as described in WO9507791 to Procter & Gamble. A trypsin-like recombinant protease suitable for use in the detergents of the present invention is described in WO9425583 to Novo. In more detail, a particularly preferred protease known as "Protease D" is described in US Series No. 08/322676 by A. Baeck et al. as "Protease-Containing Cleaning Compositions" and in US Series No. 08/322676 by C. Ghosh et al. 08/322677 entitled "Bleaching Compositions Comprising Proteases".

Amylases suitable for use in the present invention include, for example, the alpha-amylases described in GB 1296839 to Novo; RAPIDASE® from International Bio-Synthetics, Inc and TERMAMYL® from Novo. FUNGAMYL(R) from Novo is particularly useful. Enzyme engineering for improved stability, such as oxidative stability, is known. See, eg, J. Biological Chem, Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain preferred embodiments of the compositions of the present invention may employ amylases having improved stability in detergents such as automatic dishwashing type detergents, especially as determined relative to the TERMAMYL® reference point used commercially in 1993 improved oxidation stability. These preferred amylases of the invention are characterized as "increased stability" amylases, as measured against the aforementioned reference point amylases, characterized by at least a measurable improvement in one or more of the following: e.g. at pH 9-10 Oxidative stability to hydrogen peroxide/tetraacetylethylenediamine in a buffer solution; thermal stability such as at a typical washing temperature such as about 60° C.; or alkali stability such as at a pH of about 8 to about 11. Stability can be measured using any of the assays disclosed in the art. See, eg, what is disclosed in WO9402597. Stability-enhanced amylases are available from Novo or from Genencor International. A highly preferred class of amylases of the present invention have in common that they are derived by site-directed mutagenesis from one or more Bacillus amylases, especially from Bacillus α-amylases, regardless of whether one, two or Are multiple amylase strains intermediate precursors. Preference is given to using amylases with increased oxidative stability relative to the reference enzymes mentioned above, especially for use in bleaching detergent compositions according to the invention, more preferably in detergent compositions according to the invention for oxygen bleaching as opposed to chlorine bleaching. Such preferred amylases include (a) amylases according to above incorporated WO9402597, Novo, 3 February 1994, which can be further described by a mutant wherein alanine or threonine is used, preferably Substitution of threonine for the methionine residue at position 197 of a Bacillus licheniformis alpha-amylase called TERMAMYL®, or variants at homologous positions similar to the parent amylase such as Bacillus amyloliquefaciens, Bacillus subtilis or Bacillus stearothermophilus (b) Genencor International described the stable Amylases with Increased Resistance, where it mentions that bleach in automatic dishwashing detergents inactivates alpha-amylases, but Genencor made amylases with improved oxidative stability from Bacillus licheniformis NCIB8061. Methionine (Met) proved to be the most easily modified residue. Met was substituted one at a time at positions 8, 15, 197, 256, 304, 366 and 438 to obtain specific mutants, particularly important M197L and M197T, with the M197T variant being the most stably expressed variant. Stability is measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases for use in the present invention include amylase variants with additional modifications in intermediate precursors as described in WO9510603A and available from assignee Novo as DURAMYL® was obtained. Other particularly preferred amylases with increased oxidative stability include those described in WO9418314 to Genencor International and WO9402597 to Novo. Any other amylase with increased oxidative stability may be used, for example derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications can be made. See WO9509909A to Novo.

Other amylases include those described in WO95/26397 and co-pending application PCT/DK96/00056 at Novo Nordisk. Particular amylases suitable for use in the detergent compositions of the present invention include alpha-amylases characterized by having a specific activity at least 25 higher than Termamyl® at a temperature range of 25°C to 55°C and at a pH of 8-10 % specific activity of alpha-amylase as determined by the Phadebas(R) alpha-amylase activity test. (The Phadebas(R) alpha-amylase activity assay is described on pages 9-10 of WO/95/26397). The present invention also includes alpha-amylases that are at least 80% identical to the amino acid sequences shown in the SEQ ID listings in the references. These enzymes are preferably incorporated into laundry detergent compositions at a level of from 0.00018% to 0.060% by weight of the total composition, more preferably from 0.00024% to 0.048% by weight of the total composition, pure enzyme.

The cellulases used in the present invention include bacterial and fungal types, preferably having an optimum pH value of 5-9.5. Barbesgoard et al. disclosed in US4435307 March 6, 1984 a suitable fungal cellulase from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and Cellulase extracted from the hepatopancreas of the raw mollusk Dolabella Auricula Solander. GB-A-2075028, GB-A-2095275 and DE-OS-2247832 also disclose suitable cellulases. CAREZYME(R) and CELLUZYME(R) (Novo) are particularly useful. See also WO9117243 to Nevo.

Lipases suitable for use in detergents include microorganisms of the genus Pseudomonas, such as the lipase produced by Pseudomonas stutzeri ATCC 19.154 as disclosed in GB1372034. See also lipases in Japanese Patent Application No. 53,20487, published February 24,1978. This lipase is available from Amano Pharmaceutical Co. Ltd. of Nagoya, Japan under the tradename Lipase P "Amano" or "Amano-P". Other suitable commercial lipases include Amano-CES from Chromobacter viscosum, such as Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; lipase; and lipase from Pseudomonas gladioli. The LIPOLASE(R) enzyme from Humicola lanuginosa and commercially available from Novo, see also EP341947, is a preferred lipase for use in the present invention. Peroxidase-stable lipase and amylase variants are described in WO9414951A to Novo. See also WO9205249 and RD94359044. Despite numerous publications on lipases, so far only lipases obtained from Humicola lanuginosa and produced in Aspergillus oryzae as a host are widely used as additives for fabric washing products. It is available under the trade name Lipolase ^(TM) from Novo Nordisk as described above. To optimize the stain removal performance of Lipolase, Novo Nordisk has prepared various variants. As described in WO92/05249, the D96L variant of the native Humicola lanuginosa lipase was 4-fold more efficient at removing lard stains than the wild-type lipase (enzymes compared in amounts ranging from 0.075-2.5 mg protein per liter). Research Disclosure No. 35944 (Novo Nordisk), published March 10, 1994, discloses that a lipase variant (D96L) may be added in an amount corresponding to 0.001-100 mg per liter of wash liquor (5-500000 LU/l). Cutinases suitable for use in the present invention are described in WO 8809367A to Genencor.

Peroxidase enzymes can be used in combination with oxygen sources such as percarbonate, perborate, hydrogen peroxide, etc. for "solution bleaching", or to prevent removal of dyes or pigments from the substrate during washing Transfer to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, haloperoxidase such as chloro- or bromoperoxidase. Peroxidase-containing detergent compositions are disclosed in WO89099813A, Novo, October 19, 1989 and WO8909813A, Novo.

WO9307263A and WO9307260A to Genencor International, WO8908694A to Novo and US3553139 to McCarty et al., Jan. 5, 1971 also disclose a range of enzyme materials and their incorporation into synthetic detergent compositions. Enzymes are further disclosed in US4101457, Place et al., Jul. 18, 1978 and US4507219, Hughes, Mar. 26, 1985. US Patent 4,261,868, Hora et al., April 14, 1981, discloses enzyme materials for use in liquid laundry formulations, and methods for their incorporation into such formulations. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in US3600319, Gedge et al., August 17, 1971, and EP 199405 and EP200586, Venegas, October 29, 1986. Enzyme stabilization systems are also described eg in US3519570. WO9401532A to Novo describes useful protease, xylanase and cellulase-giving Bacillus sp. AC13. polymer dispersant

Polymeric dispersants may be used at levels from 0.5% to 8% by weight in the compositions of the invention, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates are selected from the group consisting of acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, uraconic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates of the present invention of monomeric moieties not containing carboxylate groups such as vinyl methyl ether, styrene, ethylene etc. is suitable provided that the moiety does not constitute more than 40% by weight . The polymeric polycarboxylate materials may also optionally include other monomeric units, such as nonionic spacer units. For example, suitable nonionic ionic spacer units may include vinyl alcohol or vinyl acetate.

Especially preferred polymeric polycarboxylates are copolymers derived from acrylic acid and maleic acid monomers. The average molecular weight of the polymer in acid form is in the range of 2000-10000, more preferably 4000-7000, and most preferably 4000-5000. Water-soluble salts of such acrylic acid/maleic acid polymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble polymers are known substances. The use of such polyacrylates in detergent compositions is disclosed, for example, in US Patent 3,308,067, Diehl, issued March 7,1967. The ratio of acrylate to maleate moieties in the copolymer is generally in the range of 30:1 to 1:1, more preferably in the range of 10:1 to 2:1. Such soluble acrylate/maleate copolymers are known substances and are described in EP66915 as well as in EP193360, which also describes such polymers comprising hydroxypropyl acrylate. Among the acrylic acid/maleic acid based copolymers, water-soluble salts of copolymers of acrylic acid and maleic acid are preferred.

Another polymeric polycarboxylate suitable for use in the present invention is a homopolymeric polycarboxylate derived from acrylic acid. The average molecular weight of the acid homopolymer is preferably in the range of 2,000-100,000, more preferably 3,000-75,000, most preferably 4,000-65,000.

Other examples of polymeric polycarboxylates useful herein include maleic/acrylic acid/vinyl alcohol terpolymers. Such materials are disclosed in EP193360 and include, for example, a 45/45/10 terpolymer of acrylic acid/maleic acid/vinyl alcohol.

Another example of polymeric polycarboxylate compounds useful in the present invention includes biodegradable polyaspartic acid and polyglutamic acid. Foam inhibitor

A wide variety of substances can be used as suds suppressors, and suds suppressors are known to those skilled in the art. See, eg, Kirk Othmer, Encyclopedia of Chemical Technology, Third Edition, Vol. 7, pp. 430-447 (John Wiley & Sons, Inc., 1979). One class of suds suppressors of particular interest includes monocarboxylic fatty acids and soluble salts thereof. See US2954347. The monocarboxylic fatty acids and salts thereof useful as suds suppressors generally have hydrocarbon chains of 10-24 carbon atoms, preferably 12-18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium, and ammonium and alkanolammonium salts.

The detergent compositions herein can also contain non-surfactant suds suppressors. These include, for example, high molecular weight hydrocarbons such as paraffins, fatty acid esters such as fatty acid triglycerides, fatty acid esters of monovalent alcohols, aliphatic _C18 - _C40 ketones such as stearyl ketone, and the like. Other suds suppressors include N-alkylated aminotriazines such as tri- to hexa-alkyl melamines, or as reaction products of cyanuric chloride with two or three moles of primary or secondary amines containing 1 to 24 carbon atoms Formed di- to tetra-alkyldiamine chlorotriazines, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate and monostearyl di-alkali metals (such as K, Na and Li ) phosphates and phosphate esters. Hydrocarbons such as paraffins and chlorinated paraffins may be used in liquid form. It is also known to use waxy hydrocarbons having a melting point preferably below 100°C. Hydrocarbons constitute a preferred class of suds suppressors for use in detergent compositions. Hydrocarbon suds suppressors are described, for example, in US4265779. Thus, the hydrocarbons include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having 12-70 carbon atoms. The term "paraffin" as used in the discussion of the suds suppressor is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors includes silicone suds suppressors. This class includes the use of polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxanes with silica particles, wherein The polyorganosiloxane is chemisorbed or fused into the silica. Silicone suds suppressors are known in the art, for example disclosed in US4265779 and EP354016.

Other silicone suds suppressors are disclosed in US 3,455,839 which relates to compositions and methods for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.

Mixtures of polysiloxanes and silanized silicas are described, for example, in German patent application DOS2124526. US3933672 and US4652392 disclose silicone antifoams and suds control agents in granular detergent compositions.

An exemplary silicone-based suds suppressor for use herein is a suds suppressing amount consisting essentially of:

(i) polydimethylsiloxane fluid with a viscosity of 20cs.-1500cs. at 25°C;

(ii) Based on 100 parts by weight of (i), 5-50 parts of a silicone resin composed of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, wherein (CH ₃ ) ₃ SiO _1/2 The ratio of units to _SiO2 units is 0.6:1-1.2:1; and

(iii) 1-20 parts of solid silica gel per 100 parts by weight of (i).

In preferred silicone suds suppressors for use herein, the solvent for the continuous phase is a polyethylene glycol or polyethylene glycol-polypropylene glycol copolymer or a mixture thereof (preferred), or Composed of polypropylene glycol. The main polysiloxane suds suppressors are branched/crosslinked and preferably non-linear.

The silicone suds suppressors of the present invention preferably comprise polyethylene glycol and polyethylene/polypropylene glycol copolymers, all having an average molecular weight of less than 1000, preferably 100-800. The water solubility of polyethylene glycol and polyethylene glycol/polypropylene glycol copolymers at room temperature is greater than 2% by weight, preferably greater than 5% by weight.

The preferred solvent of the present invention is an average molecular weight less than 1000, more preferably 100-800, most preferably polyethylene glycol of 200-400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. The weight ratio of polyethylene glycol:polyethylene glycol-polypropylene glycol copolymer is preferably from 1:1 to 1:10, most preferably from 1:3 to 1:6.

Preferred silicone suds suppressors for use herein do not contain polypropylene glycol, especially polypropylene glycol having a molecular weight of 4,000. They are also preferably free of block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other suds suppressors useful herein include secondary alcohols such as 2-alkyl alkanols and mixtures of such alcohols with silicone oils such as those disclosed in US4798679, US4075118 and EP150872. Secondary alcohols include _C6 - _C16 alkanols having a _C1 - _C16 chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the tradename ISOFOL 12. Mixtures of secondary alcohols are available from Enichem under the tradename ISALCHEM 123. Mixed suds suppressors generally comprise a mixture of alcohol and silicone in a weight ratio of 1:5 to 5:1.

For any detergent composition to be used in an automatic washing machine, the suds formed should not overflow the washing machine. If used, suds suppressors are preferably used in "suds suppressing amounts". "Suds suppressing amount" means that the formulator of the composition can select the amount of such suds suppressing agent to sufficiently control suds to obtain a low sudsing laundry detergent for use in automatic washing machines.

The present compositions generally contain 0% to 5% suds suppressor. When used as suds suppressors, the monocarboxylic fatty acids and their salts can be present in detergent compositions in amounts up to 5% by weight. Preferably 0.5% to 3% of fatty monocarboxylate suds suppressors are used. Silicone suds suppressors can be used in detergent compositions in amounts up to 2.0% by weight, although higher amounts can also be used. This upper limit is in fact a matter of practice, primarily to minimize cost and effectively control foam at lower amounts. Preferably 0.01% to 1% silicone suds suppressor is used, more preferably 0.25% to 0.5%. These weight percentages as used herein include any silica that may be used in combination with the polyorganosiloxane, as well as any auxiliary materials that may be used. Typical levels of monostearyl phosphate suds suppressors range from 0.1% to 2% by weight of the composition. Typical levels of hydrocarbon suds suppressors range from 0.01% to 5.0%, although higher levels may also be used. Alcohol suds suppressors are typically used in amounts of 0.2% to 3% by weight of the final composition. polymeric detergent

Polymeric soil release agents are characterized by having both a hydrophilic portion which makes the surface of hydrophobic fabrics such as polyester and nylon hydrophilic; and a hydrophobic portion which deposits on the hydrophobic fibers and remains there until the wash and cleaning cycle is complete. adheres thereto and thus serves as an anchor point for the hydrophilic part. This ensures that, in the subsequent washing process, the dirt generated after the treatment with the detergent can be easily washed away.

Polymeric soil release agents suitable for use in the present invention include, among other things, soil release agents comprising: (a) one or more nonionic hydrophilic components consisting essentially of (i) a degree of polymerization of at least 2 or (ii) propylene oxide or polyoxypropylene moieties having a degree of polymerization of 2-10, wherein said hydrophilic moiety does not include any oxypropylene units unless it is bonded at each end via an ether bond to On the adjacent part, or (iii) mixed units of oxyalkylene units comprising ethylene oxide and 1 to 30 oxypropylene units, wherein the mixed units comprise sufficient oxyethylene units so that the hydrophilic component has a sufficiently large In order to increase the hydrophilicity of the surface of conventional polyester synthetic fibers to the detergent deposited on the surface, the hydrophilic part preferably comprises at least 25% of ethylene oxide units and more preferably, especially for For the component having 20-30 propylene oxide units, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) _C3 oxyalkylene terephthalate base ester moiety, wherein, if the hydrophobic component further comprises oxyethylene terephthalate, the ratio of oxyethylene terephthalate: _C3 oxyalkylene terephthalate units is 2:1 or less, (ii) C ₄ -C ₆ alkylene or C ₄ -C ₆ oxyalkylene moieties or mixtures thereof, (iii) poly(vinyl esters) having a degree of polymerization of at least 2 ) moieties, preferably poly(vinyl acetate), or (iv) C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituents, or mixtures thereof, wherein said substituents are C ₁ -C ₄ Alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives, and mixtures thereof, and such cellulose derivatives are amphiphilic so that they have a sufficient content of C ₁ -C ₄ alkyl ether and/or or C ₄ hydroxyalkyl ether unit to be deposited on the conventional polyester synthetic fiber surface, and keep sufficient content to adhere to the hydroxyl group on this conventional synthetic fiber surface, to improve the hydrophilicity of the fiber surface, or (a) and ( b) combination.

The polyethylene oxide moiety of (a)(i) generally has a degree of polymerization of 200, preferably 3-150, more preferably 6-100, although higher degrees of polymerization may be used. Suitable oxy C ₄ -C ₆ alkylene hydrophobic moieties include, but are not limited to, polymeric soil release capping units such as MO ₃ S(CH ₂ ) _n OCH ₂ CH ₂ O— as described in US4721580, wherein M is sodium and n is an integer of 4-6.

Polymeric soil release agents useful in the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, ethylene terephthalate or trimethylene terephthalate and polyethylene oxide terephthalate Alkane or polypropylene oxide ester copolymer block, etc. Such soil release agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow) and carboxyalkyl celluloses such as Metolose (Shin Etsu). Cellulosic soil release agents useful in the present invention also include those selected from _C1 - _C4 alkyl celluloses and _C4 hydroxyalkyl celluloses, see US4000093.

Soil release agents characterized by poly(vinyl ester) hydrophobic moieties include graft copolymers of poly(vinyl ester), such as C ₁ -C ₆ vinyl ester, preferably grafted onto a polyalkylene oxide backbone, such as a polyethylene oxide backbone poly(vinyl acetate) (see EP0219048). Commercially available such detergents include the SOKALAN class of materials such as SOKALAN HP-22 from BASF (West Germany).

A preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate (PEO). The molecular weight of such polymeric soil release agents is in the range of 25,000-55,000. See US3959230 and US3893929.

Another preferred soil release agent is a polyester whose repeating units are ethylene terephthalate units, comprising 10-15% by weight of ethylene terephthalate units, and 90-80% by weight % of polyoxyethylene terephthalate units derived from polyoxyethylene diols with an average molecular weight of 300-5000. Examples of such polymers include the commercially available materials ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also US4702857.

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprising an oligoester backbone of terephthaloyl and oxyalkyleneoxy repeating units, and co- The terminal part that is valently bonded to the backbone. These detergents have been described in US4968451. Other suitable polymeric soil release agents include terephthalate polyesters in US4711730, anionically terminated oligoesters in US4721580, and block polyester oligomers in US4702857.

Another preferred polymeric soil release agent is an oligomer whose repeating units are terephthaloyl units, sulfoisophthaloyl units, oxyethyleneoxy units and oxy-1,2-propylene units . The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate capping units. A particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, five terephthaloyl units, oxyethyleneoxy units and oxy-1,2-propylene in a ratio of 1.7-1.8 baseoxy unit, and two 2-(2-hydroxyethoxy)-ethanesulfonate sodium capping units. The soil release agent also includes from 0.5 to 20% by weight of the oligomer of a crystallization reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures thereof.

Preferred polymeric soil release agents also include the soil release agents of US4877896 which discloses anionic, especially sulfoaroyl terminated terephthalates.

If used, soil release agents will generally comprise from 0.01 to 10.0%, usually from 0.1 to 5.0%, preferably from 0.2 to 3.0%, by weight of the compositions herein. Clay soil removal/anti-redeposition agent

Granular detergent compositions containing these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylated amines and liquid detergent compositions typically contain from 0.01% to 5%.

The most preferred soil release/anti-redeposition agent is ethoxylated tetraethylenepentamine. US4597898 further describes exemplary ethoxylated amines. Another preferred class of clay soil removal/anti-redeposition agents are cationic compounds, which are disclosed in EP111965. Other clay soil removal/anti-redeposition agents that may be used include the ethoxylated amine polymers disclosed in EP111984, the zwitterionic polymers disclosed in EP112592, the amine oxides disclosed in US4548774 and carboxymethylcellulose (CMC) substances. These substances are known in the art. dye transfer inhibitor

Such dye transfer inhibiting agents typically include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases, and mixtures thereof . If used, these agents will generally range from 0.01% to 10%, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%, by weight of the composition. brightener

The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide dye transfer inhibition. If used, the compositions of the present invention preferably comprise from 0.01% to 1.2% by weight of such optical brighteners.

The hydrophilic optical brighteners used in the present invention are those compounds having the following structural formula: Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methyl ylamino, morpholino, chlorine and amino; M is a salt-forming cation such as sodium or potassium.

When in the above formula, R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl and M is a cation, such as sodium, the brightener is 4,4'-bis[(4-anilino- 6-(N-2-Bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid disodium salt. A particular brightener material is commercially sold under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation.

When in the above formula, R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation, such as sodium, the brightener is 4,4'-bis[ (4-Anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid disodium salt. A particular brightener material is sold commercially by Ciba-Geigy under the trade name Tinopal 5BM-GX.

When in the above formula, _R1 is anilino, _R2 is morpholino and M is a cation, such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morpholino- s-triazin-2-yl)amino]2,2'-stilbene disulfonic acid sodium salt. A particular brightener material is sold commercially by Ciba-Geigy under the trade name Tinopal AMS-GX.

Conventional optical brighteners or other brightening or whitening agents known in the prior art can generally be incorporated into the present invention at a level of 0.005%-5%, preferably 0.01%-1.2%, and most preferably 0.05%-1.2% by weight. In the detergent composition of the invention. Available commercial optical brighteners can be classified into subclasses which include, but are not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanine, dibenzothiophene-5,5-dioxide compounds, pyrroles, derivatives of 5- and 6-membered ring heterocycles and other heterochromants. Examples of such brighteners are in "Preparation and Use of Optical Brighteners", M. Zahradnik, published by John Wiley & Sons, New York (1982). Other optical brighteners that may also be used include naphthalimides, benzoxazoles, benzofurans, benzimidazoles, and mixtures thereof. fabric softener

Various in-wash fabric softeners, especially the fine-grained smectite clays of US4062647 and other softener clays known in the prior art may optionally be present at 0.5% to 10% by weight, preferably 0.5% to 2% Amounts of <RTI ID=0.0>A</RTI> are used in the compositions of the present invention to provide fabric softener benefits while fabrics are laundered. Clay softeners may be used in combination with amine and cationic softeners as disclosed in US4375416 and US4291071. other components

A variety of ingredients for other functions in detergent compositions may be included in the compositions of the present invention, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations , A solid filler for block compositions. The detergent compositions of the present invention are preferably formulated so that, when used in an aqueous washing operation, the wash water will have a pH of 6.5-11, preferably 7.5-10.5. Techniques for controlling pH within the recommended range include the use of buffers, bases, acids, etc., and are known to those skilled in the art. other optional components

Other optional ingredients suitable for use in the compositions of the present invention include colorants and filler salts, with sodium sulfate being the preferred filler salt. form of composition

The detergent compositions of the present invention can be formulated in any desired form, such as powders, granules, pastes, liquids and gels. The detergent compositions of the present invention are preferably in granular form. gel composition

The detergent compositions of the present invention may also be in gel form. The composition is usually formulated with a polyalkenyl polyether having a molecular weight of 750,000-4,000,000. solid composition

The detergent compositions of the present invention can also be in solid form, such as powders and granules.

The average particle size of the components of the granular composition is preferably such that no more than 5% of the particles are larger than 1.4mm in diameter and no more than 5% of the particles are smaller than 0.15mm in diameter.

The term "average particle size" is defined herein by sieving a sample of the composition over a set of Tyler sieves into fractions (usually 5 fractions). The weight fraction thus obtained is plotted against the aperture diameter of the sieve. The average particle size is the size of the pores through which 50% by weight of the sample passes.

The bulk density of the granular detergent compositions of the present invention is especially useful in concentrated granular detergent compositions, characterized by a relatively high density compared to conventional laundry detergent compositions. The high density composition typically has a bulk density of at least 400 g/l, more preferably from 650 g/l to 1200 g/l, most preferably from 800 g/l to 1000 g/l. Method of preparation - granular composition

The granular detergent compositions of the present invention can generally be prepared by a variety of methods including dry blending, spray drying, agglomeration and granulation.

The invention is illustrated by the following non-limiting examples in which all percentages are by weight unless otherwise indicated.

In the detergent composition of the present invention, the abbreviated component symbols have the following meanings: XYAS: C _1X - _{C 1Y} alkyl sodium sulfate XYEZ: C _1X -C _1Y condensed with the average z moles of ethylene oxide is mainly linear chain uncle

Alcohol XYEZS: _C1X - _C1Y alkylsulfuric acid condensed with average z moles of ethylene oxide per mole

Sodium TFAA: C ₁₆ -C ₁₈ alkyl N-methylglucamide CEQ: R ₁ COOCH ₂ CH ₂ N ⁺ (CH ₃ ) ₃ , R ₁ =C ₁₁ -C ₁₃ QAS: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₁₂ -C ₁₄ LAS : linear C ₁₂ sodium alkylbenzene sulfonate TAS : sodium tallow alcohol sulfate Soap: linear sodium alkyl carboxylate, derived from tallow and an 80/20 blend of coconut oil

Get STPP: anhydrous sodium tripolyphosphate zeolite A: hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O, primary particles

0.1-10 _microns in size NaSKS-6: crystalline layered silicate of formula δ- _Na2Si2O5 Carbonate: anhydrous sodium carbonate with _particle size 200-900 microns Silicate: amorphous silicic acid Sodium (SiO ₂ : Na ₂ O ratio = 2.0) sulfate: anhydrous sodium sulfate citrate: trisodium citrate dihydrate, 86.4% active, particle size distribution

425-850 microns MA/AA : 1:4 maleic acid/acrylic acid copolymer, average molecular weight about 70000CMC : sodium carboxymethylcellulose Savinase : proteolytic enzyme with an activity of 4KNPU/g Carezyme : an activity of 1000CEVU/g Cellulolytic enzyme Termamyl : amylolytic enzyme with an activity of 60KNU/g Lipolase : a lipase with an activity of 100KLU/g

Unless otherwise _stated , are sold by _{Novo Industries A/S and active above PB4: sodium perborate tetrahydrate of nominal formula NaBO2.3H2OH2O2 PB1 : of nominal} formula _NaBO2.H2O2 Anhydrous sodium perborate bleach Percarbonate: Sodium percarbonate of nominal formula 2Na2CO ₃ 3H ₂ O ₂ TAED: Tetraacetylethylenediamine NACA-NOBS: (6-nonanoylaminocaproyl)oxybenzene Sulfonate NOBS: Nonanoyloxybenzenesulfonate, sodium salt form DTPMP: Diethylenetriaminepenta(methylene phosphonate), commercially available from Monsanto

Dequest 2060 sells photoactivated bleaches: sulfonated zinc phthalocyanine brighteners encapsulated with dextrin-soluble polymers 1 : 4,4'-bis(2-sulfostyryl)biphenyl disodium White agent 2: 4,4'-5 bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)ammonia

Base) stilbene-2: 2'-disodium disulfonate HEDP : 1,1-hydroxyethanediphosphonic acid STS : sodium toluenesulfonate SRP : sulfobenzoyl end-capped with oxyethyleneoxy and para benzene

Defoaming of ester polysiloxane with diformyl skeleton: polydimethylsiloxane foam control agent and silicone agent as dispersant - oxyalkylene copolymer, the foam control agent and the dispersant

The ratio is 10:1-100:1

Example 1

Prepare bleach precursor granules as follows: Example 1 2 3 4 5 6 7 8 NACA-OBS 65 65 - - 65 38 74.5 65 NOBS - - 65 - - - - - TAED - - - 65 - 27 - - LAS 9.8 - - 9.8 9.8 9.8 10 10 28AS - 9.8 9.8 - - - - - 24E3 0.3 0.3 0.3 0.3 0.3 0.5 0.5 0.5 STS 0.96 0.96 0.96 0.96 - 0.9 1.0 1.0 citric acid 11.3 11.3 11.3 11.3 - 11.3 10 10 CMC 6.2 6.2 6.2 6.2 - 6.2 2.0 10 Water balance to 100%

In each of Examples 1-6, the bleach precursor (i.e. NACA-OBS and/or TAED or NOBS) was pre-mixed with CMC before adding water, with (Examples 2-7) or without (Example 1) Nonionic surfactant. Add remaining ingredients and mix in Loedige FM mixer. The premix was then fed into a dome extruder (Fuji Paudal Model DGL-1 ) with a die opening of 0.8 mm and extruded at a pressure of about 20 bar. The resulting extrudate was then fed into a rotating disc pelletizer (Fuji Paudal QJ-400) where it was broken into short lengths to form substantially spherical particles. The granules were then dried in a Niro vibrating fluid bed dryer to yield crisp, free-flowing, dust-free granules with a particle size of 0.25 mm to 2.00 mm and a Heubach dust measurement of less than 100 mg/g.

The granules of Example 1 were removed, coated with 24E3 surfactant in a drum mixer, and further dusted with 1 part zeolite in a second drum mixer. The resulting granules remained crisp and free flowing, showing improved resistance to dust generation as illustrated by a drop in the Heubach dust value from 35 mg/g (uncoated) to 12 mg/g.

The granules of Example 7 were removed, coated with 0.4 parts of 24E3 surfactant in a drum mixer, and further dusted with 1 part of zeolite in a second drum mixer. The resulting granules remained crisp and free flowing, showing improved resistance to dust generation as illustrated by a drop in the Heubach dust value from 35 mg/g (uncoated) to 12 mg/g.

The bleach granules of Example 8 were prepared by premixing the bleach precursor and CMC and adding 20 parts water. The mixture was mixed for 5 minutes in a Loedige FM mixer. The remaining ingredients were added and mixing continued for an additional 5 minutes. The resulting wet agglomerates are then passed through a fluid bed dryer to remove moisture, resulting in crisp free-flowing granules.

Example 2

A detergent formulation of the present invention was prepared wherein Formulation A is a phosphorus-containing detergent composition, Formulation B is a zeolite-containing detergent composition and Formulation C is a compact detergent composition. A B C blown powder STPP 24.0 - 24.0 Zeolite A - 24.0 - Sulfate 9.0 6.0 13.0 MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 - - Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 spray C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Polysiloxane defoamer 0.3 0.3 0.3 spices 0.3 0.3 0.3 dry additive carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10 PB1 4.0 4.0 - Bleach Precursor Granules (*) 3.0 3.0 1.0 photoactivated bleach 0.02% 0.02% 0.02% Savinase 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Termamyl 0.25 0.30 0.15 Sulfate 3.0 3.0 5.0 Balance (moisture and trace components) to 100 Density (g/l) 630 670 670 (*) Bleach precursor particles prepared in any one of Examples 1-8. Example 3 Preparation of the following detergent formulation DE according to the invention: D. E. LAS 20.0 14.0 QAS 0.7 1.0 TFAA - 1.0 C25E5/C45E7 - 2.0 C45E3S - 2.5 STPP 30.0 18.0 Silicate 9.0 5.0 carbonate 13.0 7.5 Bicarbonates - 7.5 DTPMP 0.7 1.0 SRP1 0.3 0.2 MA/AA 2.0 1.5 CMC 0.8 0.4 Savinase 0.8 1.0 Termamyl 0.8 0.4 Lipase 0.2 0.1 Carezyme (5T) 0.15 0.05 photoactivated bleach 70ppm 45ppm Brightener 1 0.2 0.2 PB1 6.0 2.0 Bleach Precursor Granules (*) 2.0 1.0 Balance (moisture and trace components) to 100 (*) Bleach precursor particles prepared in any of Examples 1-8.

Example 4 Preparation of the following detergent formulation FH according to the invention: f G h blown powder Zeolite A 30.0 22.0 6.0 Sulfate 19.0 10.0 7.0 MA/AA 3.0 3.0 6.0 LAS 14.0 12.0 22.0 C45AS 8.0 7.0 7.0 Silicate - 1.0 5.0 soap - - 2.0 Brightener 1 0.2 0.2 0.2 carbonate 8.0 16.0 20.0 DTPMP - 0.4 0.4 spray C45E7 1.0 1.0 1.0 dry additive PVPVI/PVNO 0.5 0.5 0.5 Savinase 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Termamyl 0.1 0.1 0.1 carezyme 0.1 0.1 0.1 Bleach Precursor Granules (*) - 6.1 4.5 PB1 1.0 5.0 6.0 Sulfate - 6.0 - Balance (moisture and trace components) to 100 (*) Bleach precursor particles prepared in any of Examples 1-8. Example 5 A high density and bleach-containing detergent formulation IK according to the invention was prepared as follows: I J K blown powder Zeolite A 15.0 15.0 15.0 Sulfate - 5.0 - LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 2.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 carbonate 8.0 8.0 4.0 spray spices 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - - dry additive Citrate 5.0 - 2.0 Bicarbonates - 3.0 - carbonate 8.0 15.0 10.0 Bleach Precursor Granules (*) 6.0 2.0 5.0 PB1 14.0 7.0 10.0 Polyethylene oxide, MW5000000 - - 0.2 Bentonite - - 10.0 Savinase 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Termamyl 0.6 0.6 0.6 carezyme 0.6 0.6 0.6

Polysiloxane defoaming particles 5.0 5.0 5.0 dry additive Sulfate - 3.0 - Balance (moisture and trace components) to 100.0 Density (g/l) 850 850 850 (*) Bleach precursor particles prepared in any of Examples 1-8. Example 6 High density detergent formulations L and M according to the invention were prepared as follows: L m Agglomerates C45AS 11.0 14.0 Zeolite A 15.0 6.0 carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 spray C25E5 5.0 5.0 spices 0.5 0.5 dry additive HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 Bleach Precursor Granules (*) 5.0 7.0 PC 20.0 20.0 SRP1 0.3 0.3 Savinase 1.4 1.4 Lipase 0.4 0.4 carezyme 0.6 0.6 Termamyl 0.6 0.6 Polysiloxane defoaming particles 5.0 5.0

Brightener 1 0.2 0.2 Brightener 2 0.2 - Balance (moisture and trace components) to 100 Density (g/l) 850 850 (*) Bleach precursor particles prepared in any of Examples 1-8. Example 7 Preparation of the following laundry detergent composition NO of the present invention: N o LAS 8.0 8.0 C25E3 3.4 3.4 CEQ 0.8 - QAS - 0.8 Zeolite A 18.1 18.1 carbonate 13.0 13.0 Silicate 1.4 1.4 Sulfate 26.1 26.1 PB4 9.0 9.0 Bleach Precursor Granules (*) 1.5 1.5 DETPMP 0.25 0.25 HEDP 0.3 0.3 protease 0.26 0.26 Amylase 0.1 0.1 MA/AA 0.3 0.3 CMC 0.2 0.2 Photoactivated Bleach (ppm) 15ppm 15ppm Brightener 1 0.09 0.09 spices 0.3 0.3 Polysiloxane defoamer 0.5 0.5 Microcomponents / Minor components to 100% Density (g/L) 850 850 (*) Bleach precursor particles prepared in any of Examples 1-8.

Claims (13)

1. solid bleaching precursor composition, it contains:

A)-bleach precursor; With

B)-contain the surfactant system of non-ethoxylated anion surfactant and nonionogenic tenside;

Wherein said surfactant system and described precursor are that intimate physical is approaching.

2. according to the composition of claim 1, wherein said surfactant system exists in the amount by bleach precursor compositions weight 0.1%-50%.

3. according to the composition of one of claim 1 or 2, wherein said bleach precursor exists in the amount by bleach precursor compositions weight 10%-99%.

4. according to one of any composition among the claim 1-3, wherein said anion surfactant is selected from sulfate surfactant, sulfosalt surfactant, carboxylate surface active agent, sarcosinate surfactant and their mixture.

5. according to the composition of claim 4, wherein said anion surfactant is C ₅-C ₂₀Linear alkylbenzene sulfonate.

6. according to one of any composition among the claim 1-5, wherein said nonionogenic tenside is selected from the condensation product of condenses, oxyethane and propylene oxide/quadrol affixture of ethoxylated alcohol surfactant, ethoxylated/propoxylated fatty alcohol surfactant, ethylene oxide/propylene oxide and propylene glycol and their mixture.

7. according to the composition of claim 6, wherein said nonionogenic tenside is to contain the alcohol of alkyl of 8-20 carbon atom and the condensation product of every mol of alcohol 2-10 moles of ethylene oxide, preferably with the straight chain primary alcohol (C12/C14) of average 3 moles of ethylene oxide condensations.

8. according to one of any composition among the claim 1-7, wherein said bleach precursor is selected from nonanoly acyloxy benzene sulfonate, (the amino caproyl of 6-decoyl) oxygen base benzene sulfonate, (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate, (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate and their mixture.

9. according to one of any composition among the claim 1-8, wherein said composition also contains the hydrotropic agent that is preferably selected from cumene sulfonate, xylenesulfonate, tosylate and their mixture.

10. according to one of any composition among the claim 1-9, wherein said composition also contains water-soluble organic acid, optimization citric acid.

11. according to one of any composition among the claim 1-10, wherein said composition also contains membrane polymer.

12. according to one of any composition among the claim 1-11, wherein said composition is the form of agglomerate or spherical extrudate.

13. mix granular detergent composition as one of any defined solid bleaching precursor composition among the claim 1-12.