EP1124929A1 - Bleach-containing detergent composition - Google Patents

Abstract

A detergent composition comprising a bleach-sensitive component and a hydrogen peroxide source, wherein the hydrogen peroxide source is present in a particulate component having an average particle size, by weight, of from 700 microns to 1100 microns, preferably from 750 microns to 1000 microns, whereby at least 80% by weight of the particulate component comprising the hydrogen peroxide source has a particle size of between 70% to 130% of the of the average particle size. The compositions preferably comprise a bleach activator of a specified average particle size.

Description

Bleach-Containing Detergent Composition

Field of the Invention

The invention relates to detergent compositions comprising bleach sensitive ingredients and a hydrogen peroxide source of a specific particle size.

Background to the Invention

Bleach-containing detergent compositions generally contain an oxygen-based bleach, typically a perborate or percarbonate salts which releases hydrogen peroxide in the wash water, and often a bleach activator or precursor. In solid detergent compositions, these compounds are typically admixed as separate granules to the base composition.

Detergents also contain certain ingredients which are bleach-sensitive and which can react with the bleaching agent during manufacturing or storage or in use. Thus, these bleach-sensitive ingredients may loose some of their performance when present in bleach-containing compositions. For example perfumes, enzymes, dyes and brighteners can react with bleaching agent, in particular percarbonate and perborate bleach and in particular when they are present as spray-on component or as admixed component. Various techniques are known to protect the bleach-sensitive ingredients, for example coating of these ingredients. However, there is still a need to further improve the stability of bleach-sensitive ingredients.

The inventors have now found that this problem can be reduced when particulate hydrogen peroxide sources of a specific, larger particle size and having a narrow particle size distribution are incorporated in the solid detergent compositions. It is believed that this is due to the fact that the larger particle size hydrogen peroxide sources have a smaller surface area per weight unit and thus per active oxygen or available oxygen. There is thus a smaller total surface area per amount of active oxygen bleach in the composition, which may be in contact with the bleach-sensitive ingredients. Thus, there is a reduced possibility that the bleach-sensitive ingredients and the percarbonate or perborate are in contact and react together.

In particular in compositions whereby bleach-sensitive ingredients are present as admixed granules, or even more in compositions whereby the bleach-sensitive ingredients are sprayed onto the detergent particles, including the percarbonate, it has been found beneficial for the stability ofthe bleach-sensitive ingredients, that the hydrogen peroxide source has the larger particle size ofthe invention.

It is known that in general the larger the particle size of a particle, the slower the particle dissolves in water. Thus, this would also be expected for particulate hydrogen peroxide sources dissolve slower in water. However, the inventors have surprisingly found that the larger particle size hydrogen peroxide sources ofthe invention, in particular percarbonate salts, have a water-solubility which is comparable to the water-solubility of smaller sources, such as for example percarbonate salts having an average particle size of around 600 or even 500 microns.

Also, the inventors have surprisingly found that the bleaching performance of detergent compositions incorporating a hydrogen peroxide source and a bleach activator is not always satisfactory after storage, even when the bleach is stable. Also they have found that the bleaching performance may differ from one batch of product to another.

They have now found that this can be due to the segregation ofthe hydrogen peroxide source component in, particularly, the granular product, during manufacturing or during storage, resulting in an uneven distribution ofthe hydrogen peroxide source component and/or bleach activator component. The inventors have found that it can be advantageous that the a bleach activator component, or part thereof, also has an large average particle size, preferably similar to the particle size ofthe hydrogen peroxide source component, to reduce the segregation of theses components in the product. Preferably, the base granules ofthe composition also have an average particle size similar to the particle size ofthe hydrogen peroxide source component and preferably the bleach activator component.

Summary of the Invention

The invention provides a solid composition comprising a bleach-sensitive component and a hydrogen peroxide source wherein the hydrogen peroxide source is present in a particulate component having an average particle size, by weight, of from 700 microns to 1100 microns, preferably from 700 microns to 1000 microns, whereby at least 80% by weight ofthe particulate component comprising the hydrogen peroxide source has a particle size of between 60% to 140% ofthe ofthe average particle size.

Preferably, the composition comprises one or more bleach activators.

Detailed Description ofthe Invention

Hydrogen Peroxide Source.

The hydrogen peroxide source herein is present in a particulate component ofthe composition, preferably being admixed to the other detergent components, preferably in the form of a separate granular component ofthe composition. The particulate component containing the hydrogen peroxide source preferably has an average particle size of from 700 microns to 1000 microns, more preferably from 750 or even 800 microns to 950 microns or even from 820 to 920 microns. Hereby at least 80%, preferably at least 90% or even at least 95% or even substantially 100% by weight ofthe particulate component comprising the hydrogen peroxide source has a particle size which is 60% to 140% ofthe ofthe weight average particle size, preferably between 70% and 130% ofthe weight average particle size, or even more preferably from 80% to 120% ofthe weight average particle size.

It may be preferred that at least 70% or even at least 80% and more preferably at least 90%o or even at least 95% ofthe component comprising the hydroxy peroxide source has a particle size of from 600 or even 710 microns to about 1180 microns, preferably from 710 microns to 1000 microns.

Hereby it may be preferred that less than 10 % by weight or even less than 6% or even less than 4% by weight has a particle size of less than 425 microns or even 600 microns. Hereby it may also be preferred that less than 10 % by weight or even less than 6% or even less than 4% by weight has a particle size of more than 1400 microns or even 1180 microns

Preferably the weight distribution ofthe particle sizes ofthe component comprising the hydrogen peroxide source is very narrowly distributed around one mean or average or median.

For example preferred may be that the weight average particle size is 800 microns, whereby (by weight) 5% or less has a particle size of less than 600 microns and less than 2% has a particle size of more than 1180 microns. Also preferred may be that the weight average particle size is 800 microns whereby (by weight) 3% or less has a particle size of less than 425 microns and less than 5% has a particle size of more than 1400 microns The average particle size when used herein is a weight average particle size, obtained by analysing the particle size of a sample ofthe product by any conventional way, known in the art, for example by sieving the material through a series of sieves of given mesh sizes and measuring the weight fractions ofthe material which remain on the sieve and/ or pass through the sieve. Minimum and maximum particle sizes are also measurable by sieving the material with sieves of a given mesh size, by ways known in the art.

Preferred hydrogen peroxide sources are perhydrate bleaches, such as metal peroxymonopersulfate, more preferably metal perborates and most preferably metal percarbonates, particularly the potassium or more preferably the sodium salts thereof.

In particular the percarbonate salts are used herein may be coated. Suitable coating agent are known in the art, for example hydrophobing agents such as wax, inorganic salts such as magnesium salts, sulphate salts and carbonates salts and silicates or mixtures thereof.

It may be preferred that the hydrogen peroxide source, and preferably the component containing it, has a solubility in water of 10°C such that 75% ofthe theoretical maximum available oxygen (AvO) of said component is delivered in less than 10 minutes, preferably less than 8 minutes or even less than 6 minutes. It may be preferred hereby that at least 50% ofthe maximum theoretical available oxygen is delivered in less than 5 minutes, preferably in less than 4 minutes.

The solubility can be measured by: adding 5.0 gram ofthe hydrogen peroxide source or the component comprising it, in a plastic beaker of a Tergotometer ERWEKA, model DT6R, containing 1 litre of de-ionised water at 10C containing 50ml acetic acid, mixing the water-hydrogen peroxide source-mixture with paddles with a speed of 150rpm, taking 15 ml samples at the required times, and measuring the available oxygen in the sample by titration, for example with thiosulphate 0.1N with an automatic Mettler DL 25 titrator. Bleach-Sensitive Ingredients

When used herein, the bleach-sensitive ingredients can be any ingredients known in the art which can be incorporated in detergent compositions and which may react with the hydrogen peroxide source or hydrogen peroxide during manufacturing ofthe composition, storage or in use, during the washing or cleaning operation with the composition.

For the purpose ofthe invention, the bleach-sensitive components or part thereof may in particular be present in the form of a spray-on component, which is sprayed onto the granules ofthe solid detergent composition ofthe invention. However, the bleach- sensitive components or part thereof may also be present in other forms, for example as admixed granules, or the bleach-sensitive component or part thereof may be comprised in the base granules.

Preferred bleach-sensitive components herein comprise perfumes, enzymes, brighteners, dyes, photo-bleaching agents, dispersants, soil release agent, in particular any of these ingredients comprising a functional group which can be oxidised, for example an alkenyl group, an aldehyde group or amine group. Suitable bleach-sensitive ingredients for use in the compositions ofthe present invention are described hereinafter.

The Detergent Composition

The detergent compositions ofthe invention are preferably solid laundry, dish washing or hard-surface cleaning compositions, most preferably laundry or dish washing compositions. The compositions are preferably in the form of granules, although also envisaged herein are tablets, bars and flakes, preferably made from particulate components. The composition preferably comprises granules whereof at least 60%), more preferably at least 80%oby weight have an average particle size, by weight, of from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns or even 750 to 1000 microns. It may be preferred that the compositions comprises less than 20% or even less than 10%) or even less than 5% by weight of particulate components of a particle size of less than 300 microns, or even less than 425 microns or even less than 600 microns; it may also be preferred the composition comprise less than 20%> or even less thanl0% or even less than 5% by weight ofthe composition, of particulate components of a particle size of more than 1700 microns, or even more than 1400 microns or even more than 1180 microns.

The composition can be made by any method known in the art, including by agglomeration and/ or spray-drying, whereby certain ingredients may be admixed or sprayed-on as described herein. It may be preferred that the composition is made by mixing all or part ofthe granules, including those made by agglomeration or spray- drying, and subsequently adding a binder and mixing or agglomerating the granules and binder to form the, preferably agglomerated detergent granules. These may be ofthe required particle size or they may be sieved to obtain particles ofthe required size. Hereby, it may be preferred that the admixed hydrogen peroxide source-containing component is not mixed agglomerated together with the other granules and the binder.

The compositions are preferably solid detergents which preferably have a density of at least 350g/litre, more preferably at least 500 g/ litre or even at least 580 g/ litre.

The compositions in accord with the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incoφoration thereof will depend on the physical form ofthe composition or component, and the precise nature ofthe washing operation for which it is to be used. Highly preferred is that as additional ingredient one or more bleach activators are present, as described hereinafter.

In one embodiment ofthe invention, it may be preferred that the detergent composition herein comprise one or more anionic surfactants and an aluminosilicate builder, whereby it is preferred that only small amounts ofthe aluminosilicate builder and the anionic surfactant are in an intimate mixture, i.e. less than 50% or even less than 30% ofthe total amount ofthe anionic surfactant and less than 50% or even less than 30% ofthe total amount of alumnisilicate; it may even be preferred that substantially no anionic surfactant and aluminosilicate builder are in an intimate mixture. Thus, it may be preferred that the composition comprises at least two separate particles which comprise either anionic surfactant or aluminosilicate. 'Intimate mixture' means for the puφose ofthe invention that the two or more ingredients the component are substantially homogeneously divided in the component or particle. Namely, it has been found that the solubility and/ or dispensing ofthe composition is thereby improved.

In another embodiment ofthe invention, it maybe preferred that the composition only comprises low levels of aluminosilicate builder, for example less than 10% or even less than 5% by weight ofthe composition, whereby it is preferred that the composition comprises highly soluble builders, for example sodium citrate or citric acid, carbonate, and/ or crystalline layered silicate.

It may also be preferred that the composition comprises as builder system or as part ofthe builder system, an agglomerate comprising from 0.5% to 80% by weight a crystalline layered silicate, preferably, NaSKS-6, and from 10% to 70% by weight of a surfactant, preferably an anionic surfactant, whereby it may be preferred that less than 10% by weight ofthe agglomerate of free moisture, more preferably 30% to 60% by weight a crystalline layered silicate and 20% to 50% by weight of an anionic surfactant. Effervescence Component

It may be highly preferred that the detergent composition comprises an effervescence component, preferably comprising an acid source and an alkali source capable of reacting together to form a gas upon contact with water, in particular a carbon dioxide gas, formed by reaction of an organic carboxylic acid and a carbonate source. For the puφose ofthe invention, the ingredients ofthe effervescence components may be present in an intimate mixture with one another, preferably in the form of a granule or the may be present in separate particles.

It may be preferred that the effervescence component is a particulate component having an average particle size, by weight, of from 700 microns to 1400 microns, preferably from 750 microns to 1100 microns, preferably comprising an acid source and an alkali source.

It may be preferred that the effervescence component is substantially free of water, preferably such that no water has been intimately mixed with the effervescence component or part thereof, or that no water is present other than the moisture of the raw materials themselves. Typically, the level of water in intimate mixture with the effervescence component is below 5% by weight of the total granule, preferably below 3%> and more preferably below 1.5%, preferably obtainable by dry-powder compaction or pressure agglomeration.

These preferred dry effervescent particles result in a very fast carbon dioxide production and therefore in accelerated dispersibility and dissolution rate of the granular composition. The granular compositions of the present invention, as described herein, comprising the dry effervescent granules allow dispensing and dissolution in water of the granular compositions in a shorter period of time and at lower total level of effervescent particles/materials and ensure a faster and more effective delivery of detergent ingredients to the wash. Suitable acids to be used herein include solid organic, mineral or inorganic acids, salts or derivatives thereof or a mixture thereof. It may be preferred that the acids are mono-, bi- or tri-protonic acids. Such acids include mono- or polycarboxylic acids preferably citric acid, adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid, malonic acid. Such acids are preferably used in their acidic forms, and it may be preferred that their anhydrous forms are used, or mixtures thereof. Derivatives also include ester ofthe acids.

The effervescence component or source preferably comprises a carbonate source, including carbonate, bicarbonate and percarbonate salts, in particular bicarbonate and/or carbonate. Suitable carbonates to be used herein include carbonate and hydrogen carbonate of potassium, lithium, sodium, and the like amongst which sodium and potassium carbonate are preferred. Suitable bicarbonates to be used herein include any alkali metal salt of bicarbonate like lithium, sodium, potassium and the like, amongst which sodium and potassium bicarbonate are preferred. Bicarbonate may be preferred to carbonate, because it is more-weigh effective, i.e., at parity weigh bicarbonate is a larger CO2 "reservoir" than carbonate. However, the choice of carbonate or bicarbonate or mixtures thereof in the dry effervescent granules may be made depending on the pH desired in the aqueous medium wherein the dry effervescent granules are dissolved. For example where a relative high pH is desired in the aqueous medium (e.g., above pH 9.5) it may be preferred to use carbonate alone or to use a combination of carbonate and bicarbonate wherein the level of carbonate is higher than the level of bicarbonate, typically in a weight ratio of carbonate to bicarbonate from 0J to 10, more preferably from 1 to 5 and most preferably from 1 to 2.

Such an effervescence granule may also comprise a binder, including surfactants, such as anionic and nonionic surfactants.. The effervescence component is preferably present in the composition according to the present invention at a level of from 0.5% to 60% by weight, preferably from 2% to 50%, more preferably from 5% to 45 % and preferably such that the acid component is present at a level of from 0J%> to 40%, more preferably from 1.0% to 35%, or even 2% to 25% or even to 15% by weight ofthe composition.

Bleach Activator

The composition preferably comprises a bleach activator, preferably comprising an organic peroxyacid bleach precursor. It may be preferred that the composition comprises at least two peroxy acid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxy acid bleach precursor, as defined herein. The production ofthe organic peroxyacid occurs then by an in situ reaction ofthe precursor with a source of hydrogen peroxide.

The bleach activator may alternatively, or in addition comprise a preformed peroxy acid bleach.

It is preferred that the bleach activator is present in a particulate component in the compositions herein. It may be preferred that the is present as a separate, admixed particle. Alternatively, the bleach activator or part thereof can be present in the base detergent particle.

Preferably, at least one ofthe bleach activators, preferably a peroxy acid bleach precursor, is present in a particulate component having an average particle size, by weight, of from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns. More preferably, all ofthe activator are present in one or more particulate components having the specified weight average particle size. Hereby, it may be preferred that at least 80%, preferably at least 90% or even at least 95 % or even substantially 100% ofthe component or components comprising the bleach activator have a particle size of from 300 microns to 1700 microns, preferably from 425 microns to 1400 microns.

The hydrophobic peroxy acid bleach precursor preferably comprises a compound having a oxy-benzene sulphonate group, preferably NOBS, DOBS, LOBS and/ or NACA-OBS, as described herein.

The hydrophilic peroxy acid bleach precursor preferably comprises TAED, as described herein.

Peroxyacid Bleach Precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as

O

X-C-L

where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure ofthe peroxyacid produced is

O

Ii

X-C -OOH For the puφose ofthe invention, hydrophobic peroxyacid bleach precursors produce a peroxy acid ofthe formula above wherein X is a group comprising at least 6 carbon atoms and a hydrophilic peroxyacid bleach precursor produces a peroxyacid bleach ofthe formula above wherein X is a group comprising 1 to 5 carbon atoms.

Peroxyacid bleach precursor compounds are preferably incoφorated at a level of from 0.5%) to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight ofthe detergent compositions. The ratio of hydrophilic to hydrophobic bleach precursors, when present, is preferably from 10: 1 to 1 : 10, more preferably from 5;1 to 1 :5 or even from 3:1 to 1 :3.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Leaving Groups

The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition. Preferred L groups are selected from the group consisting of:

O O

-N— C— R¹ -N Λ N -N— C » -CH— R⁴ I

R³ R³ Y

I

Y

R³ Y I I -0-CH=C— CH=CH₂ -O-CH=C-CH=CH₂

R³ O Y

I ii I

0-C=CHR⁴ , and -N— S— CH— R⁴ I , II R³ O

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to

14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 i •s H or R 3 , and Y is H or a solubilizing group. Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.

The preferred solubilizing groups are -SO₃ ^"M⁺, -CO₂ ^~M⁺, -SO₄ ^"M⁺, -N⁺(R³)₄X^" and

O<-N(R 3 )~ and most preferably -SO, - M + and -CO- - M + wherein R 3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkyl Percarboxylic Acid Bleach Precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds ofthe imide type include the N-

,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred as hydrophilic peroxy acid bleach precursor.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose. Amide Substituted Plkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those ofthe following general formulae:

R¹ C N R^{2 ■}C L R N R^{z 1} K "

O R O or R⁵ O O

wherein R^Ϊ is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R^ is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R-5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R* preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. Rl may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. R2 can include alkyl, aryl, wherein said R^ may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R-5 is preferably H or methyl. Rl and

R-5 should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. It can be preferred that

RI and R-5 forms together with the nitrogen and carbon atom a ring structure.

Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate, (6- decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6- nonanamidocaproyl)oxy benzene sulfonate, and mixtures thereof as described in EP-A- 0170386.

Perbenzoic Acid Precursor

Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those ofthe imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic Peroxyacid Precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any ofthe ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors ofthe N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

Benzoxazin Organic Peroxyacid Precursors

Also suitable are precursor compounds ofthe benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

wherein R, is H, alkyl, alkaryl, aryl, or arylalkyl.

Preformed Organic Peroxyacid

The detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15% by weight, more preferably from 1% to 10%o by weight ofthe composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds ofthe following general formulae:

R¹ — C — N — R² — C — OOH R¹ — N — C — R² — C — OOH

O R⁵ O or R⁵ O O

wherein RI is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R-5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein. Dye

A preferred ingredients ofthe compositions ofthe invention are dyes and dyed particles or speckles, which can be bleach-sensitive. The dye as used herein can be a dye stuff or an aqueous or nonaqueous solution of a dye stuff. It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing ofthe detergent particles or speckles, preferably such that levels of dye solution are obtained up to 2% by weight ofthe dyed particle, or more preferably up to 0.5% by weight, as described above. The dye may also be mixed with a non-aqueous carrier material, such as non-aquous liquid materials including nonionic surfactants.

Optionally, the dye also comprising other ingredients such as organic binder materials, which may also be a non-aqueous liquid.

The dyestuff can be any suitable dyestuff. Specific examples of suitable dyestuffs include El 04 - food yellow 13 (quinoline yellow), El 10 - food yellow 3 (sunset yellow FCF), E131 - food blue 5 (patent blue V), Ultra Marine blue (trade name), E133 - food blue 2 (brilliant blue FCF), E140 - natural green 3 (chlorophyll and chloφhyllins), E141 and Pigment green 7 (chlorinated Cu phthalocyanine). Preferred dyestuffs may be Monastral Blue BV paste (trade name) and/ or Pigmasol Green (trade name).

The dyed detergent particles preferably comprise such a up to 10% or more preferably up to 2% or even up to 1% by weight ofthe dyed particle.

Perfumes Another preferred ingredient ofthe compositions ofthe invention is a perfume or perfume composition. Any perfume composition can be used herein. The perfumes may also be encapsulated.

Preferred perfumes containing at least one component with a low molecular weight volatile component , e.g. having a molecular weight of from 150 to 450 or preferably 350.

Preferably, the perfume component comprises an oxygen-containing functional group. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

Suitable aliphatic ketones are e.g.:

- 2J,8,-trimethyl-l-acetyl-cyclododeca-2,5J-triene

- 7-acetyl-lJ,6,7,-tetramethyl-lJJ,4,5,6J,8,-octahydronaphthalene

- isolongifolanone

- gamma-irone

- alpha-vetivone

Suitable aromatic ketones are e.g.:

- 4-(p-hydroxyphenyl)-butan-2-one

- 1 ,1 ,2,4,4,7-hexamethl-6-acetyl-tetralin

- benzophenone

- methyl naphthyl ketone

Suitable aliphatic aldehydes are e.g.: - 2-methylhendecanal

- undecanal

- 4(4'-methyl-4'-hydroxypentyl)-cyclohex-3-ene carbaldehyde

- 7-(formyl-5-isopropyl-2-methyl-bicyclo[2JJ]oct-2-ene - 4-(tricyclo[5JJ.0{2,6}]decylidene-8)-butanal

- 4-(4'-metylpent-3-enyl)-cyclohex-3-ene carbaldehyde

Suitable aromatic aldehydes are e.g.:

- alpha-hexylcinnamic aldehyde

- anisic aldehyde

- helliotropin

- 2-phenylpropanal

- dihydrocinnamic aldehyde

- 3-(p-tert.butylphenyl)-2-methylpropanal

Suitable condensaton products of aldehydes and amines are e.g.

- methyl N-(2,4-dimethyl-3-cyclohexenyl)methylidene-anthranilate

- methyl N-(3,7-dimethyl-7-hydroxy-octylidene)-anthranilate

- methyl N-(4-(4'-methyl-4'-hydroxypentyl)cyclohex-3-enyl]methylideneanthranilate

Suitable macrocyclic lactone musks are e.g.:

- ethylene dodecanedioate

- 11-oxahexadecanolide

- cyclopentadecanolide Preferred perfumes herein can be modified starch encapsulated High Impact Accord ("HIA") perfume oil particles. Preferred HIA perfume oils include

4-(2J,6-Trimethylcyclohex- 1 -enyl)-2-en-4-one

2,4 - Decadienoic acid, ethyl ester (E,Z) -

6-(and -8) isopropylquinoline

Acetaldehyde phenylethyl propyl acetal

Acetic acid, (2-methylbutoxy)-, 2-propenyl ester

Acetic acid, (3-methylbutoxy)-, 2-propenyl ester

2,6,10-Trimethyl-9-undecenal

Glycolic acid, 2-pentyloxy-, allyl ester

Hexanoic acid, 2-propenyl ester l-Octen-3-ol trans-Anethole iso buthyl (z)-2-methyl-2-butenoate

Anisaldehyde diethyl acetal

Benzenepropanal, 4-(l ,1 -dimethylethyl)-

2,6 - Nonadien-1-ol

3-methyl-5-propyl-cyclohexen-l-onre

Butanoic acid, 2-methyl-, 3-hexenyl ester, (Z)-

Acetaldehyde, [(3,7-dimethyl-6-octenyl)oxy]-

Lauronitrile

2,4-dimethyl-3-cyclohexene- 1 -carbaldehyde 2-Buten- 1 -one, 1 -(2,6,6-trimethyl- 1 J -cyclohexadien- 1 -yl)-

2-Buten-l-one, l-(2,6,6-trimethyl-2-cyclohexen-l-yl)-, (E)- gamma-Decalactone trans-4-decenal decanal

2 -P entylcyclopentanone

1 -(2,6,6 Trimethyl 3 Cyclohexen-l-yl)-2 Buten-1-one)

2,6-dimethylheptan-2-ol

Benzene, lJ'-oxybis-

4-Penten- 1 -one, 1 -(5 ,5-dimethyl- 1 -cyclohexen- 1 -yl)-

Butanoic acid, 2-methyl-, ethyl ester

Ethyl anthranilate

2-Oxabicyclo [2 JJ] octane, 1,3,3-trimethyl-

Eugenol

3-(3-isopropylphenyl)butanal methyl 2-octynoate

4-(2,6,6-trimethyl- 1 -cyclohexen- 1 -yl_-3-buten-2-one

Pyrazine, 2-methoxy-3-(2-methylpropyl)-

Quiniline, 6-secondary buty

Isoeugenol

2H-Pyran-2-one, tetrahydro-6-(3-pentenyl)-

Cis-3-Hexenyl Methyl Carbonate

Linalool

1,6,10-Dodecatriene, 7,H-dimethyl-3-methylene-, (E)- 2,6-dimethyl-5-heptenal

4,1 Methanoindan 1-carboxaldehyde, hexahydro

2-methylundecanal methyl 2-nonynonate

1 , 1 -dimethoxy-2J,5-trimethyl-4-hexene

Benzoic acid, 2-hydroxy-, methyl ester

4-Penten- 1 -one, 1 -( , 5 -dimethyl- 1 -cyclohexen- 1 -yl)

2H-Pyran, 3,6-dihydro-4 methyl-2-(2-methyl-l-propenyl)-

2,6-Octadienenitrile, 3,7-dimethyl-, (Z)-

2,6-nonadienal

6-Nonenal, (Z)- nonanal octanal

2-Nonenenitrile

Acetic acid, 4-methylphenyl ester

Gamma Undecalactone

2-noφinene-2-propionaldehyde 6,6 dimethyl

4-nonanolide

9-decen-l-ol

2H-Pyran, tetrahydro-4-methyl-2-(2 -methyl- 1 -propenyl)-

5-methyl-3-heptanone oxime

Octanal, 3,7-dimethyl-

4-methyl-3-decen-5-ol

10-Undecen-l-al Pyridine, 2-(l-ethylpropyl)- Spiro[furan-2(3H),5'-[4,7]methano[5H]indene], decahydro-

Additionally, the perfume can also contain a perfume precursor.

Perfume precursors are capable of forming a perfume component, with the characteristics described above, once exposed to wash conditions. Preferably, the perfume precursor forms a perfume component by hydrolysis under aqueous conditions.

Preferred perfume precursors herein are nonionic or anionic esters of an allylic alcohol perfume having the formula:

O

R— [C— O— CR'₂-CR"=CR'"₂]n

wherein n is an integer of 1 or greater; and R is selected from the group consisting of C\ -

C30, preferably C\ - C20 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, or aryl group, and represents the group attached to the carboxylate function of the carboxylic acid used to make the perfume ester. Each R', R", and each R" selected from the group consisting of hydrogen, or a C^ - C20 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, or aryl group. R, R', R" and R'" are selected in such a manner that the molecular weight ofthe allylic alcohol is from 150 to 350.

In the most preferred embodiment, R' and R" are hydrogen, one R'" is hydrogen, methyl, or ethyl, and the other R'" is a straight, branched or cyclic C\ - C^Q alkyl or alkenyl group. Also cis/trans (also referred to as Z/E) isomers at the double bond in the structure shown above and stereoisomers ofthe above structure are possible. Preferred perfume components may be selected from the group comprising the esters of geraniol and/or nerol. Geraniol and nerol are trans/cis structural isomers (at the 2,3 position double bond) ofthe molecules having the formula HO-CH2-CH=C(CH3)-CH2-

CH₂-CH=C(CH₃)₂.

Heavy Metal Ion Sequestrant

The compositions ofthe invention preferably contain as an optional component a heavy metal ion sequestrant or chelant or chelating agent. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight ofthe compositions or component

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.

Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid. Other suitable heavy metal ion sequestrant for use herein include mtrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3 -sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509J82 are also suitable.

EP-A-476J57 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane- 1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'- disuccinic acid (HPDDS) are also suitable.

Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N,N'- disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.

In particular the chelating agents comprising a amino or amine group can be bleach- sensitive and are suitable in the compositions ofthe invention. Enzyme

Another highly preferred ingredient useful in the compositions herein is one or more additional enzymes.

Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incoφorated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incoφorated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight ofthe composition.

Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1 ,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873.

Amylase enzyme may be incoφorated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight ofthe composition. Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight ofthe compositions.

The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain ofHumicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Optical Brightener

The compositions herein also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, as mentioned above.

Hydrophilic optical brighteners useful herein include those having the structural formula:

wherein R] is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, moφhilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, Ri is anilino, R2 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-triazine- 2-yl)amino]-2J'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Coφoration. Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, R is anilino, R2 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-triazine-2-yl)amino]2J'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Coφoration.

When in the above formula, R\ is anilino, R2 is moφhilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-moφhilino-s-triazine-2-yl)amino]2J'- stilbenedisulfonic acid, sodium salt. This particular brightener species are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Coφoration. Photo-Bleaching Agent

Photo-bleaching agents are preferred ingredients ofthe compositions herein. Preferred photo-bleaching agent herein comprise a compounds having a poφhin or poφhyrin structure.

Poφhin and poφhyrin, in the literature, are used as synonyms, but conventionally poφhin stands for the simplest poφhyrin without any substituents; wherein poφhyrin is a sub-class of poφhin. The references to poφhin in this application will include poφhyrin.

The poφhin structures preferably comprise a metal element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al , most preferably Zn.

It can be preferred that the photo-bleaching compound or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.

The photo-bleaching compound or component can have solubilizing groups as substituents. Alternatively, or in addition hereto the photo-bleaching agent can comprise a polymeric component capable of solubilizing the photo-bleaching compound, for example PVP, PVNP, PVI or co-polymers thereof or mixtures thereof.

Highly preferred photo-bleaching compounds are compounds having a phthalocyanine structure, which preferably have the metal elements or cations described above. Metal phthalocyanines and their derivatives have the structure indicated in Figure 1 and/or Figure 2, wherein the atom positions ofthe phthalocyanine structure are numbered conventionally.

The phthalocyanines can be substituted for example the phthalocyanine structures which are substituted at one or more of the 1-4, 6, 8-11, 13, 15-18, 20, 22-25, 27 atom positions.

Surfactant

The compositions in accord with the invention preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Muφhy on March 31, 1981.

Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.

Anionic Surfactant

The compositions in accord with the present invention preferably comprise an additional anionic surfactant. Essentially any anionic surfactants useful for detersive puφoses can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono- , di- and tri ethanolamine salts) ofthe anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.

Highly preferred are surfactants systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxylsulfates, as described herein, preferably combined with a cationic surfactants as described herein.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C₁ ~-C, „ monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C^-C, , diesters), N-acyl sarcosinates. 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 Surfactant

Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cι-C4 alkyl) and -N-(C^* -

C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary ClO'Cl 8 ^alkyl sulfates, more preferably the Ci 1-C15 branched chain alkyl sulfates and the Ci 2-C|4 linear chain alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting ofthe ClO'Cl 8 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C_j 1 - C\g, most preferably Cn-C], 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect ofthe invention employs mixtures ofthe preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic Sulfonate Surfactant Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C5-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic Carboxylate Surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)_x

CH2C00^"M⁺ wherein R is a Cg to C\g alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRι-CHR2-O)-R3 wherein R is a Cg to Ci g alkyl group, x is from 1 to 25, R\ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting ofthe water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors. Alkali Metal Sarcosinate Surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (Ri) QJ2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R^ is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Alkoxylated Nonionic Surfactant

Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes ofthe nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.

Nonionic Alkoxylated Alcohol Surfactant

The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain ofthe aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R²CONR¹Z wherein : RI is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably C alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C^ \-C\- alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those having the formula: R"CON(R ')2 wherein R^ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R^ is selected from the group consisting of hydrogen, C -C4 alkyl, C\- C4 hydroxyalkyl, and -(C2H4θ)_xH, where x is in the range of from 1 to 3.

Nonionic Alkylpolysaccharide Surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula:

R2O(C_nH_2nO)t(glycosyl)₎ wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1J to 8. The glycosyl is preferably derived from glucose.

Amphoteric Surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R3(OR4)_χNθ(R5)2 wherein R^ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R^ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R$ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are Ci Q-C^g alkyl dimethylamine oxide, and Cιo-18 acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant

Zwitterionic surfactants can also be incoφorated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R')2N⁺R2C00^" wherein R is a Cg-Ci g hydrocarbyl group, each Ri is typically Ci -C3 alkyl, and R² is a C1-C5 hydrocarbyl group. Preferred betaines are C 12.18 dimethyl-ammonio hexanoate and the ClO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic Surfactants

Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono Cg-

C\ , preferably Cg-Ci Q N-alkyl or alkenyl ammonium surfactants wherein the remaining

N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.

Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.

Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example -CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic Mono- Alkoxylated Amine Surfactants

Highly preferred herein are cationic mono-alkoxylated amine surfactant preferably ofthe general formula I:

wherein R is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R² and R- are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R² and R3 are methyl groups; R4 is selected from hydrogen (preferred), methyl and ethyl; X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.

Preferably the ApR^ group in formula I has p=l and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the ^■ — OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR^ groups are — CH₂CH₂OH, — CH₂CH₂CH₂OH, — CH₂CH(CH₃)OH and —

CH(CH3)CH2OH, with — CH2CH2OH being particularly preferred. Preferred R¹ groups are linear alkyl groups. Linear R groups having from 8 to 14 carbon atoms are preferred.

Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are ofthe formula

wherein R is C^Q-CI S hydrocarbyl and mixtures thereof, especially C\Q-C\4 alkyl, preferably Ci Q and Cj2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.

As noted, compounds ofthe foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2θ] and

[CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and or Pr and/or i-Pr units.

The levels ofthe cationic mono-alkoxylated amine surfactants used in detergent compositions ofthe invention is preferably from 0.1% to 20%, more preferably from 0.2%) to 1%, most preferably from 0.3% to 3.0% by weight ofthe composition.

Cationic Bis- Alkoxylated Amine Surfactant

The cationic bis-alkoxylated amine surfactant preferably has the general formula II:

wherein Rl is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about

14 carbon atoms; R² is an alkyl group containing from one to three carbon atoms, preferably methyl; R- and R^ can vary independently and are selected from hydrogen

(preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i.e., -

CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use herein are ofthe formula

wherein R is CJQ-CI S hydrocarbyl and mixtures thereof, preferably Cιo_> Ci2_> Ci4 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound Rl is derived from (coconut) Ci 2- C14 alkyl fraction fatty acids, R² is methyl and ApR-3 and A'qR^ are each monoethoxy. Other cationic bis-alkoxylated amine surfactants useful herein include compounds ofthe formula:

wherein R^ is CJ Q-C I S hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R² is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.

Other compounds ofthe foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2θ] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

Bleach Catalyst

The composition can contain a transition metal containing bleach catalyst.

One suitable type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243. Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Others are described in European patent application publication no. 549,272. The bleach catalysts useful herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl- l,4,7-triazacyclononane)(OCH3)3_(PF6).

Still another type of bleach catalyst, as disclosed in U.S. Pat. 5J 14,606, is a water- soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso- erythritol, meso-inositol, lactose, and mixtures thereof.

U.S. Pat. 5, 114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are ofthe formula:

R² R³

R¹ -N=C-B-C=N-R⁴

wherein Rl, R R3, and R^ can each be selected from H, substituted alkyl and aryl groups such that each R1 -N=C-R2 and R^-C-^N-R^ form a five or six-membered ring.

Said ring can further be substituted. B is a bridging group selected from O, S. CR5R6,

NR and C=O, wherein R-5, R6, and R-*⁷ can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2J'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2J'-bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(π) perchlorate, Co(2J-bispyridylamine)2θ2θθ4, Bis-(2J'- bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.

Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4Mn^πι(u-O)2MnrVN4)⁺and [Bipy2Mn^III(u-O)2Mn^Ivbipy2]- (ClO₄)₃.

Other bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-poφhyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,H9,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).

The bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein. By "catalytically effective amount" is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal ofthe stain or stains of interest from the target substrate. The test conditions will vary, depending on the type of washing appliance used and the habits ofthe user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance ofthe bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully- formulated detergent and bleach compositions can be appropriately adjusted. As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million ofthe active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 1 ppm to about 200 ppm ofthe catalyst species in the wash liquor. To illustrate this point further, on the order of 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3-5 fold may be required under U.S. conditions to achieve the same results.

Water-Soluble Builder Compound

The compositions in accord with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15%> to 40% by weight ofthe composition.

The detergent compositions ofthe invention preferably comprise phosphate-containing builder material. Preferably present at a level of from 0.5% to 60%), more preferably from 5% to 50%, more preferably from 8% to 40.

The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any ofthe foregoing.

The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-lJJ-propane tricarboxylates described in British Patent No. 1,387,447. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5%> to 8% by weight ofthe composition.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids ofthe monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Partially Soluble or Insoluble Builder Compound

The compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight ofthe composition.

Examples of largely water insoluble builders include the sodium aluminosilicates. As mentioned above, it may be preferred in one mbodiment ofthe inevntion, that only small amounts of alumino silicate builder are present. Suitable aluminosilicate zeolites have the unit cell formula Na_z[(AlO2)_z(SiO2)y]- XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:

Na i2 [AlO₂) i2 (SiO₂)i2]. H2θ

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na 6 [(AlO₂)86(SiO₂)l06]- 276 H₂O.

Another preferred aluminosilicate zeolite is zeolite MAP builder.

The zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40%) by weight ofthe compositions.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate ofthe zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2. Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1J5 and, more particularly, not greater than 1.07.

In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a d5_Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.

The d5_Q value indicates that 50% by weight ofthe particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in

EP 384070 A.

Organic Polymeric Compound

Organic polymeric compounds are preferred additional components ofthe compositions herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any ofthe high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quaternised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent in accord with the invention.

Organic polymeric compound is typically incoφorated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0J%o to 15%, most preferably from 0.5%) to 10% by weight ofthe compositions. Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers ofthe latter type are disclosed in GB-A-1, 596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.

The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Teφolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incoφoration in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.

Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al, and in particular according to US application no.60/051517. Another organic compound, which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines ofthe formula:

wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42.

Other dispersants/ anti-redeposition agents for use herein are described in EP-B-011965 and US 4,659,802 and US 4,664,848.

Suds Suppressing System

The detergent compositions ofthe invention, when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight ofthe composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Cl8"C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises:

(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%>, preferably 75% to 95%) by weight ofthe silicone antifoam compound; and

(ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by weight ofthe silicone/silica antifoam compound;

wherein said silica silicone antifoam compound is incoφorated at a level of from 5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1 :1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;

(c) an inert carrier fluid compound, most preferably comprising a C \ g-C \ ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point

Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid.

Polymeric Dye Transfer Inhibiting Agents

The compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5%) by weight of polymeric dye transfer inhibiting agents. The polymeric dye transfer inhibiting agents are preferably selected from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.

Polymeric Soil Release Agent

Polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, ofthe compositions.

Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.

Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incoφorated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end-capped 1 J-propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m- sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1 -C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093,

December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional classes of SRA's include: (I) nonionic tejephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals ofthe polymer through an ester ofthe isolated carboxylic acid of trimellitic anhydride rather than by opening ofthe anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.. Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;

Other Optional Ingredients

Other optional ingredients suitable for inclusion in the compositions ofthe invention include colours and filler salts, with sodium sulfate being a preferred filler salt.

Highly preferred compositions contain from about 2% to about 10%> by weight of an organic acid, preferably citric acid. Also, preferably combined with a carbonate salt, minor amounts (e.g., less than about 20%) by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incoφorated by reference), can be present. Form ofthe Compositions

The composition ofthe invention can be made via a variety of methods, including dry- mixing, agglomerating, compaction, or spray-drying ofthe various compounds comprised in the detergent component, or mixtures of these techniques.

The compositions herein can take a variety of physical forms including liquid, but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular forms.

The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.

Chlorine-Based Bleach

The detergent compositions can include as an additional component a chlorine-based bleach. However, since the detergent compositions ofthe invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable.

Alternatively, the detergent compositions can be formulated such that they are chlorine- based bleach-compatible, thus ensuring that a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process.

The chlorine-based bleachis such that a hypochlorite species is formed in aqueous solution. The hypochlorite ion is chemically represented by the formula OCT. Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and chlorimides. Specific examples of compounds of this type include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, l,3-dichloro-5,5- dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine B and Dichloramine B. A preferred bleaching agent for use in the compositions ofthe instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof. A preferred chlorine-based bleach can be Triclosan (trade name).

Most ofthe above-described hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation ofthe compositions ofthe instant invention. Some ofthe above materials are available as aqueous solutions.

Laundry Washing Method

Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount ofthe detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Preferred washing machines may be the so- called low-fill machines. In a preferred use aspect the composition is formulated such that it is suitable for hard- surface cleaning or hand washing. In another preferred aspect the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.

Abbreviations used in the Granular Detergent Composition Examples

In the detergent compositions, the abbreviated component identifications have the following meanings:

LAS Sodium linear Cl 1-13 alkyl benzene sulfonate

TAS Sodium tallow alkyl sulfate

CxyAS Sodium Clx - Cly alkyl sulfate

C46SAS Sodium C14 - C16 secondary (2,3) alkyl sulfate

CxyEzS Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide

CxyEz : C 1 x-C 1 y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide

QAS : R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14

QAS 1 : R2.N+(CH3)2(C2H4OH) with R2 = C8 - C 11

APA : C8 - CIO amido propyl dimethyl amine

Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids

STS : Sodium toluene sulphonate

CF AA : C 12-C 14 (coco) alkyl N-methyl glucamide

TFAA : C 16-C 18 alkyl N-methyl glucamide

TPKFA : C12-C14 topped whole cut fatty acids

STPP : Anhydrous sodium tripolyphosphate

TSPP : Tetrasodium pyrophosphate

Zeolite A : Hydrated sodium aluminosilicate of formula

Nal2(AlO2SiO2)12J7H2O having a primary particle size in the range from 0J to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 Crystalline layered silicate of formula d- Na2Si2O5 Citric acid Anhydrous citric acid Borate Sodium borate

Carbonate : Anydrous sodium carbonate with a particle size between 200μm and 900μm

Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm

Silicate : Amoφhous sodium silicate (SiO2:Na2O = 2.0:1)

Sulfate : Anhydrous sodium sulfate

Mg sulfate : Anhydrous magnesium sulfate

Citrate : Tri-sodium citrate dihydrate of activity 86.4%> with a particle size distribution between 425μm and 850μm

MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000

MA/AA (1) Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000

AA : Sodium polyacrylate polymer of average molecular weight 4,500

CMC : Sodium carboxymethyl cellulose

Cellulose ether : Methyl cellulose ether with a degree of polymerization of

650 available from Shin Etsu Chemicals

Protease : Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries A S under the tradename Savinase

Protease I : Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.

Alcalase : Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S Cellulase : Cellulytic enzyme, having 0J3%> by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme

Amylase : Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T

Lipase : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase

Lipase (1) : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A S under the tradename Lipolase Ultra

Endolase : Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S

PB4 : Particle containing sodium perborate tetrahydrate of nominal formula NaBO2JH2 O, the particles having a weight average particle size of 950 microns, 85% particles having a particle size of from 850 microns to 950 microns

PB1 : Particle containing anhydrous sodium perborate bleach of nominal formula NaBO2.H 202, the particles having a weight average particle size of 800 microns, 85% particles having a particle size of from 750 microns to 950 microns

Percarbonate : Particle containing sodium percarbonate of nominal formula

2Na2CO3JH2O2, the particles having a weight average particle size of 850 microns, 5% or less having a particle size of less than 600 microns and 2% or less having a particle size of more than 1180 microns

NOBS : Particle comprising nonanoyloxybenzene sulfonate in the form of the sodium salt, the particles having a weight average particle size of 750 microns to 900 microns

NAC-OBS : Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate, the particles having a weight average particle size of from 825 microns to 875 microns

TAED I : Particle containing tetraacetylethylenediamine, the particles having a weight average particle size of from 700 microns to 1000 microns TAED II Tetraacetylethylenediamine of a particle size from 150 microns to 600 microns

DTPA : Diethylene triamine pentaacetic acid

DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by

Monsanto under the Tradename Dequest 2060

Photoactivated: Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer

Photoactivated : Sulfonated alumino phthlocyanine encapsulated in bleach

(2) dextrin soluble polymer

Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl

Brightener 2 : Disodium 4,4'-bis(4-anilino-6-moφholino-1.3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate

EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.

HEDP : 1,1 -hydroxyethane diphosphonic acid

PEGx : Polyethylene glycol, with a molecular weight of x (typically 4,000)

PEO : Polyethylene oxide, with an average molecular weight of 50,000

TEPAE : Tetraethylenepentaamine ethoxylate

PVI : Polyvinyl imidosole, with an average molecular weight of 20,000

PVP Polyvinylpyrolidone polymer, with an average molecular weight of

60,000

PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000

PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000 QEA : bis((C2H5O)(C2H4O)n)(CH3) -N+-C6H12-N+-(CH3) bis((C2H5O)-(C2H4 O))n, wherein n = from 20 to 30

SRP 1 : Anionically end capped poly esters

SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate) short block polymer

PEI : Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen

Silicone antifoam : Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1

Opacifier : Water based monostyrene latex mixture, sold by BASF

Aktiengesellschaft under the tradename Lytron 621

Wax : Paraffin wax

In the following examples all levels are quoted as % by weight ofthe composition:

TABLE I

The following compositions are in accordance with the invention.

TABLE II

The following compositions are in accordance with the invention.

Table HI

The following are high density and bleach-containing detergent formulations according to the present invention:

Claims

Claims

1. A solid detergent composition comprising a bleach-sensitive component and a hydrogen peroxide source, wherein the hydrogen peroxide source is present in a particulate component having an average particle size, by weight, of from 700 microns to 1100 microns, preferably from 700 microns to 1000 microns, whereby at least 80% by weight ofthe particulate component comprising the hydrogen peroxide source has a particle size which is 60% to 140% ofthe ofthe weight average particle size, preferably of between 70% to 130% ofthe weight average particle size.

2. A solid component according to claim 1 whereby the hydrogen peroxide source comprises a percarbonate salt.

3. A solid detergent composition according to claim 2 whereby the percarbonate salt is such that 75%o ofthe theoretical maximum available oxygen (AvO) ofthe percarbonate salt is delivered in less than 10 minutes, preferably in less than 6 minutes.

4. A solid detergent composition according to any preceding claim wherein the average particle size ofthe hydrogen peroxide source is from 800 microns to 950 microns.

5. A solid composition according to any preceding claim comprising and one or more bleach activators, whereby preferably of at least one ofthe bleach activators is present in a particulate component having an average particle size, by weight, of from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns.

6. A solid detergent composition according to claim 5, comprising a hydrophobic organic peroxyacid bleach precursor and a hydrophilic organic peroxy acid bleach precursor, the hydrophilic organic peroxyacid bleach precursor preferably comprising TAED and the hydrophobic precursor preferably comprising an oxy benzene sulphonate group, preferably being NACA-OBS or NOBS or mixtures thereof.

7. A solid detergent composition according to any preceding claim which is a granular composition wherein at least 80% ofthe granules ofthe composition have an average particle size, by weight, of from 700 microns to 1400 microns, preferably from 750 microns to 1000 microns.

8. A detergent composition according to any preceding claim wherein the bleach- sensitive component comprises a perfume, a soil release polymer, a dispersant, a chelant, a dye, a photo-bleaching agent or a brightener or mixtures thereof.

9. A detergent composition according to any preceding claim comprising a spray-on component comprising a bleach-sensitive component.

10. A detergent composition according to any preceding claim comprising an effervescence component, preferably being a particulate effervescence component having an average particle size, by weight, of from 700 microns to 1400 microns, preferably from 750 microns to 1100 microns.