WO1995028463A1

WO1995028463A1 - Detergents with reduced peroxygen bleach levels containing a chelant and enzymes

Info

Publication number: WO1995028463A1
Application number: PCT/US1995/002732
Authority: WO
Inventors: Michael Alan John Moss; Graham Alexander Sorrie; Christian Arthur J. K. Thoen; Gerard Marcel Baillely; Elsie Christina Urdaneta-Schmidt; Luis Alberto Amestica; Francisco R. Figueroa
Original assignee: The Procter & Gamble Company
Priority date: 1994-04-13
Filing date: 1995-03-30
Publication date: 1995-10-26
Also published as: MA23507A1; BR9507377A; CN1150452A; HU219179B; GB9407536D0; EP0755430A1; PE796A1; EP0755430A4; HU9602814D0; HUT76033A; JPH09512290A; CZ295896A3; AU2226995A; CA2187307A1

Abstract

There is provided a Biological Bleach Index ('BBI') by which bleach containing detergent compositions are defined which contain lower levels of bleach and bleach activator along with particular levels of chelants and enzymes. The detergent compositions of the invention have a Biological Bleach Index of greater than 65 as defined by a particular formula. In another aspect of the present invention, bleach-containing detergent compositions are provided which contain lower levels of bleach and bleach activator and higher levels of chelant and preferably higher levels of enzymes. Particularly, the level of bleach/activator reduction is represented by the equation [X]f= a[X]o where 'a' is less than 1, the amount of chelant increase is represented by the equation [Y]f > 2/a [Y]o, and the amount of enzyme increase is represented by the equation [Z]f > 1/a [Z]o.

Description

DETERGENTS WITH REDUCED PEROXYGEN BLEACH LEVELS CONTAINING A CHELANT AND ENZYMES

TECHNICAL FIELD

The present invention relates to bleach-containing detergent compositions. In particular, the invention relates to detergent compositions which provide effective bleaching performance using lower levels of bleach and bleach activator.

BACKGROUND OF THE INVENTION

The addition of bleach to detergents is often desirable because of the performance benefits bleach can provide. For example, laundry detergents containing bleach provide improved stain removal, dingy clean-up and whiteness maintenance.

Unfortunately, high bleach levels in laundry detergents can, in certain circumstances, fade the color of fabrics. High levels of bleach in automatic dishwashing detergents can, in certain circumstances, give rise to silverware tarnishing problems. Further, high levels of bleach and bleach activators increase the cost of the detergents to consumers. On the other hand, low bleach levels can lead to poor performance.

Therefore, there is a need for detergents which provide the improved performance of bleach, but which contain a lower level of bleach. It is an object of the present invention to provide such bleach-containing detergents in a manner described in detail hereinbelow. SUMMARY OF THE INVENTION

One aspect of the present invention is the establishment of a Biological Bleach Index ("BBI") by which bleach-containing detergent compositions, including those formulated for use in laundry and automatic dishwashing methods, are provided which contain lower levels of bleach and bleach activator along with particular levels of chelants and enzymes. The detergent compositions of the invention have a Biological Bleach Index of greater than 65 as defined by the formula BBI = 4[C] + 26([E] - [BAH + fB PBI

320 12 wherein [C] = [chelant level (weight percent) x (number of chelating groups in the chelant)] ÷ (molecular weight of the chelant) x 1000, wherein [E] = weight percent of enzymes selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof, in the detergent composition assuming standard activities of protease 13 KNPU, amylase 300 KNU, lipase 165 KLU, and cellulase 2000 Cevu, wherein [BA] = [(weight percent of bleach activator) x (a factor of 6 for BOBS, a factor of 6 for cationic activators, a factor of 550 for dinuclear manganese complex activators, and a factor of 4 for all other bleach activators)] ÷ (molecular weight of the bleach activator) x 1000, and wherein [PB] = (weight percent of peroxygen bleach) x (percent available oxygen from the peroxygen bleach) ÷ 100.

In another aspect of the present invention, bleach-containing detergent compositions are provided which contain lower levels of bleach and bleach activator and higher levels of chelant and preferably higher levels of enzymes. Particularly, the level of bleach/activator reduction is represented by the equation [X]f = a[X]₀ where "a" is less than 1 , the amount of chelant increase is represented by the equation [Y]f > 2/a [Y]₀, and the amount of enzyme increase is represented by the equation [Z]f >_1/a [Z]₀. This is described in more detail hereinbelow.

DETAILED DESCRIPTION OF THE INVENTION

It has now been found, surprisingly, that higher levels of chelant and enzymes can compensate for lower levels of bleach in a detergent composition. In other words, the cleaning benefits of improved stain removal, dingy clean-up and whiteness maintenance provided by a certain level of bleach can be obtained at lower levels of bleach by using higher levels of chelant and enzymes. (1 ) Biological Bleach Index

More particularly, one aspect of the present invention relates to the establishment of a Biological Bleach Index ("BBI") which defines a formula which relates the lower levels of perborate bleach and bleach activator with particular required levels of chelant and enzymes. According to this aspect of the present invention, provided is a bleach-containing detergent composition comprising from from 5% to 95% by weight detergent surfactant; from 0% to 80% by weight detergency builder; from 0.5% to 40% by weight peroxygen bleach; from 0.01% to 10% by weight bleach activator; from 0.1% to 10% by weight chelant; and from 0.05% to 5% by weight enzymes selected from the group consisting of proteases, amylases, lipases, cellulases, and mixtures thereof; wherein the detergent composition has a Biological Bleach Index ("BBI") of greater than 65 as defined by the formula: BBI = 4[C] + 26([E] - [BAD + fBAIfPBI

320 12 wherein [C] = [chelant level (weight percent) x (number of chelating groups in the chelant)] ÷ (molecular weight of the chelant) x 1000, wherein [E] = weight percent of the said enzymes in the detergent composition assuming standard activities of protease 13 KNPU, amylase 300 KNU, lipase 165 KLU, and cellulase 2000 Cevu, wherein [BA] = [(weight percent of bleach activator) x (a factor of 6 for BOBS, a factor of 6 for cationic activators, a factor of 550 for dinuclear manganese complex activators, and a factor of 4 for all other bleach activators)] ÷ (molecular weight of the bleach activator) x 1000, and wherein [PB] = (weight percent of peroxygen bleach) x (weight percent available oxygen from the peroxygen bleach) ÷ 100.

The Biological Bleach Index defines a particular relationship between the level of chelant, the level of enzymes, the level of peroxygen bleach and the level of bleach activator. By following the relationships defined in the formula, detergent compositions can be provided containing lower levels of peroxygen bleach and bleach activator, but which still provide the benefits of bleach- containing laundry detergents. Detergent compositions according to the invention have a Biological Bleach Index of greater than 65, preferably greater than 75, and more preferably greater than 80.

As seen in the formula, [C] is defined by [chelant level (weight percent) x (number of chelating groups in the chelant)] ÷ (molecular weight of the chelant) x 1000. The number of chelating groups in the chelant are factored into the formula as a way to factor in the chelating efficiency of the chelant (i.e., the chelating efficiency is believed to be influenced by the number of these chelating groups). By 'chelating groups' herein it is meant functional groups having chelating capacity including for example, phosphonate and carboxylate groups. It is noted that such chelating groups often comprise, in solution, anionically charged oxygen. By way of example, EDTA has four chelating (carboxylate) groups.

Again as seen in the formula, [E] is defined as the weight percent of the total enzymes present in the detergent composition assuming standard activities of protease 13 KNPU, amylase 300 KNU, lipase 165 KLU, and cellulase 2000 Cevu. If the actual activities of these enzymes in the detergent compositions are different from their standards activities, the factor [E] is adjusted accordingly. For example, if protease is used having an activity of 26 KNPU instead of the standard 13 KNPU, the factor [E] is multiplied by 2 to compensate for the extra ^' activity of the enzyme. The same applies for the amylases, lipases and cellulases. KNPU denotes kilo Novo protease units; KNU are kilo Novo units used for measuring amylase activity; KLU are standard kilo units defined by Novo for measuring lipase activity; CEVU are standard units for measuring cellulase activity. These units of standard activity of enzymes are well understood by persons skilled in the art. The detergent compositions of the present invention can also include other types of enzymes (e.g., peroxidases or lignases).

The factor [BA] in the formula defines the level of bleach activator as adjusted by a factor indicating its peractivity. A factor of 6 is assigned for BOBS and for cationic activators, a factor of 550 for dinuclear manganese complex activators, and a factor of 4 is assigned to all other bleach activators.

Again in the formula, with [PB] the peroxygen bleach level is adjusted by the weight percent available oxygen from the peroxygen bleach. The weight percent "available oxygen" or percent "active oxygen" of peroxygen bleach compounds is well understood by persons skilled in the art. For example, percarbonates have a percent available oxygen of 13.5%, perborate monohydrates have a percent available oxygen of 5.5%, and perborate tetrahydrates have a percent available oxygen of 10.5%.

In summary, [C] is the millimols chelant/100g of detergent corrected for the number of chelating groups, [E] is the total enzyme level corrected for the activity level of the enzymes, [BA] is the millimols bleach activator/1 OOg of detergent corrected for activity, and [PB] is the weight percent of available oxygen from the peroxygen bleach.

(2) Detergent Compositions Having Reduced Bleaching Agent and Increased

Chelants/Enzvmes According to another aspect of the present invention, provided are bleach- containing detergent compositions which are defined by a reduction in the level of bleaching agent and an increase in the level of chelants and/or enzymes. In particular, provided is a bleach-containing detergent composition comprising from 5% to 95% by weight detergent surfactant, from 0% to 80% by weight detergency builder, bleaching agent, and chelant and/or enzymes, wherein the levels of ingredients are defined as follows.

It has been found that the cleaning benefits provided for a given amount [X]₀ of bleach can be also obtained at reduced levels of bleach, [X]f, if the levels of chelant agent [Y] are increased and/or increasing the levels of enzymes [Z] according to the following correlations:

[X]f = a[X]₀

[Y]_f > 2/a[X]₀

[Z]_f > 1/a[X]₀

Increasing both, the levels of chelant and enzymes, will result in improved removal of certain stains relative to the high-bleach product. In the above formulas, "f ' means 'final", i.e., the amounts in the final claimed detergent composition of the present invention, while "o" means "original" i.e., the amounts that were present before reductions/increases according to the present invention.

Here: [X] is the sum of bleaching agents by weight % levels in the product, considering 100% activity, for the bleaching agents. The bleaching agents are either a peroxygen bleach and a bleach activator, an organic peroxy acid, or mixtures thereof. For example, the bleach reduction may come from decreasing the peroxygen bleach and/or bleach activator level in the detergent.

[Y] is the sum of chelant(s) by weight % in the product. Increases in chelant level may come from increasing the level of the type of chelant present in the high-bleach level product (if any), or by adding other type(s) of chelant(s) to the product, or both. If the product with high-bleach level of bleach; i.e., [X]₀, does not contain any chelant then preferably: [Y]f>([X]o-[X]f)/3-

[Z] is the sum of the total enzymes by weight % in the product, assuming enzymatic activities as: Proteases: 13 KNPU, Amylases: 300 KNU Lipolases: 165 KLU Cellulases: 2000 Cevu

The enzyme wt. % levels can be corrected for other enzymatic activities as: wt % protease (13KNPU) = wt. % protease ("P" KNPU) x (P/13); wt. % amylase (300 KNU) = wt. % amylase ("A" KNU) x A/300); and similarly for lipolases and cellulases. Other types of enzymes (e.g., peroxidases or lignases), where present, are used at standard activities.

Increases in enzyme levels may come from increases of all or some of the enzymes in the high-bleach formula, or from adding different enzymes, or both.

In the above formulas, "a" is less than 1 , [X]₀ is between 3% and 80%, [Y]₀ is between 0% and 10%, and [Z]₀ is between 0.01% and 10%. Preferably 0.2 < a < 1 , more preferably 0.5 < a <1, preferably [Y]₀ is between 0% and 3%, and preferably [Z]₀ is between 0.05% and 5%. Examples of formulas:

Ingredients a = 1 a = 0.75 a = 0.50 a = 0.50 high-bleach low-bleach low-bleach low-bleach

PB1 + 4.0 3.0 2.0 2.0

NOBS 3 ZΛ 6 16

[X]: 7.2 5.4 3.6 3.6

[Y]: DTPA ^" 0.4 1.2 1.6 1.6

Savinase + 0.18 0.24 0.36 0.18

BAN + 0.23 0.31 0.46 0.23

Lipolase 0.07 0.09 0.14 0.07

Cellulase* - - - -

[Z]: 0.48 0.65 0.96 0.48

With a low-bleach product, [X]f, with increases of cellulase enzyme levels the detergent should preferably have a robust anti-redeposition system.

(3) Bleaching agent

An essential feature of the invention is an oxygen bleaching system. In one preferred execution the bleaching system contains a peroxygen compound and an organic bleach activator compound. The production of the organic peroxyacid occurs by an in situ reaction of the activator with the hydrogen peroxide which is provided by the peroxygen compound. Preferred peroxygen compounds include inorganic perhydrate bleaches. Compositions containing mixtures of a peroxygen compound and bleach activator in combination with a preformed organic peroxyacid are also envisaged.

Peroxyoen compounds

Inorganic perhydrate salts are preferred peroxygen bleach compounds herein. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 0.5% to 40% by weight, more preferably from 1 % to 30% by weight and most preferably from 1 % to 7% by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, particularly perborate monohydrate and perborate tetrahydrate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metai salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.

Sodium perborate can be in the form of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate NaBθ2H2θ2-3H2θ.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for inclusion in compositions in accordance with the invention. Compositions containing percarbonate, have been found to have a reduced tendency to form undesirable gels in the presence of surfactants and water than similar compositions which contain perborate. It is believed that this is because typically percarbonate has a lower surface area and lower porosity than perborate monohydrate. This low surface area and low porosity acts to prevent the co-gelling with fine particles of surfactant agglomerates and is therefore not detrimental to dispensing.

Sodium percarbonate is an addition compound having a formula corresponding to 2Na2Cθ3.3H2θ2# and is available commercially as a crystalline solid. The percarbonate is most preferably incorporated into such compositions in a coated form which provides in product stability. A suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB- 1 ,466,799, granted to Interox on 9th March 1977. The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO n.Na2Cθ3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.

Bleach activator

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

O

II

X-C-L

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

O X-C-OOH

Bleach activator compounds are preferably incorporated at a level of from 0.01 % to 10% by weight, more preferably from 0.2% to 7% by weight, most preferably from 0.5% to 4% by weight of the detergent compositions.

Suitable bleach activator compounds typically contain one or more N- or O- acyl groups, which activators 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.

The bleach activator is preferably selected from the group consisting of tetraacetylethylenediamine ("TAED"), sodium nonanoyloxybenzene sulfonate ("NOBS"), sodium benzoyloxybenzene sulfonate ("BOBS"), benzoyl caproiactam, (6-Nonanamidocaproyl)oxybenzene sulfonate ("NACA-OBS"), quaternary ammonium- and phosphonium-substituted bleach activators, cationic nitriles, dinuclear manganese (III) or (IV) complexes, and mixtures thereof. Most preferred is tetraacetylethylenediamine.

Leaving croups

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. In one preferred aspect fo the invention L is a leaving group where the conjugate acid of the anion formed on L has a pKa of from 4 to 13.

Preferred L groups are selected from the group consisting of:

— N-C-CH— R⁴

R³ Y

I I

-O-CH=C-CH=CH₂ -O— CH=C— CH=CH₂

R³ O Y

I II I -

-O-C=CHR⁴ . and — N— S— CH— R⁴

R³ O

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group

3 containing from 1 to 14 carbon atoms, R is an alkyl chain containing from

4 3

1 to 8 carbon atoms, R is H or R , and Y is H or a solubilizing group. Any

1 3 4 of R , R and R 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 , -SO M , -N ⁺ (R³)₄X^" and O < --N(R³)₃ and most preferably -SO₃ ^"M ⁺ and -CO₂ ^"M ⁺ wherein R 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 I I

potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Perbenzoic acid activator

Perbenzoic acid activator compounds provide perbenzoic acid on perhydrolysis.

Suitable O-acylated perbenzoic acid activator compounds include the substituted and unsubstituted benzoyi oxybenzene sulfonates, including for example benzoyi oxybenzene sulfonate:

Also suitable are the benzoγlation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example:

Ac = COCH3; Bz = Benzoyi

Perbenzoic acid activator compounds of the imide type include N-benzoyl succinimide, tetrabenzoyi ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid activators include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group- containing perbenzoic acid activators include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyi pyroglutamic acid. Other perbenzoic acid activators include the benzoyi diacyl peroxides, the benzoyi tetraacyl peroxides, and the compound having the formula:

Phthalic anhydride is another suitable perbenzoic acid activator compound herein:

Suitable N-acylated lactam perbenzoic acid activators have the formula:

g wherein n is from 0 to 8, preferably from 0 to 2, and R is a benzoyi group.

Perbenzoic acid derivative activators

Perbenzoic acid derivative activators provide substituted perbenzoic acids on perhydrolysis.

Suitable substituted perbenzoic acid derivative activators include any of the herein disclosed perbenzoic activators in which the benzoyi group is substituted by essentially any non-positively charged (ie; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups. A preferred class of substituted perbenzoic acid activator compounds are the amide substituted compounds of the following general formulae:

_R1 — _c — _N — _R2 _c 1_ _R1 _N — _c — _R2 — _c — 1_

O R⁵ 0 or R⁵ 0 O

wherein R¹ is an aryl or alkaryl group with from 1 to 14 carbon atoms, R^ is an arylene, or alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R¹ preferably contains from 6 to 12 carbon atoms. R^ preferably contains from 4 to 8 carbon atoms. R¹ may be aryl, 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. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is^" preferably H or methyl. R¹ and R^ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Cationic bleach activators

Cationic bleach activator compounds produce cationic peroxyacids on perhydrolysis.

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

The bleach activator compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, activator compound as described hereinbefore. Alternatively, the bleach activator compound may Y\

be an alkyl percarboxylic acid activator compound or an amide substituted alkyl bleach activator as described hereinafter

Cationic bleach activators 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 bleach activators 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 bleach activators include any of the ammonium or alkyl ammonium substituted alkyl or benzoyi oxybenzene sulfonates, N-acylated caproiactams, and monobenzoyltetraacetyl glucose benzoyi peroxides.

A preferred cationically substituted benzoyi oxybenzene sulfonate is the 4- (trimethγl ammonium) methyl derivative of benzoyi oxybenzene sulfonate:

A preferred cationically substituted alkyl oxybenzene sulfonate has the formula:

Preferred cationic bleach activators of the N-acylated caprolactam class include the trialkyi ammonium methylene benzoyi caproiactams, particularly trimethyl ammonium methylene benzoyi caprolactam: IS

Other preferred cationic bleach activators of the N-acylated caprolactam class include the trialkyi ammonium methylene alkyl caproiactams:

where n is from 0 to 12.

Another preferred cationic bleach activator is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.

Alkyl percarboxylic acid bleach activators

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

Preferred alkyl percarboxylic activator compounds of the imide type include the N-,N,N1 N^"! 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. Tetraacetylethylenediamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid activators include sodium 3,5,5-tri- methyl hexanoyioxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose. Amide substituted alkyl peroxyacid bleach activators

Amide substituted alkyl peroxyacid bleach activator compounds are also suitable, including those of the following general formulae:

R¹ — C — N — R² — C L R¹ N — C — R² C L

O R⁵ 0 or R⁵ 0 0

wherein R¹ is an alkyl group with from 1 to 14 carbon atoms, R² is an alkylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R¹ preferably contains from 6 to 12 carbon atoms. R² preferably contains from 4 to 8 carbon atoms. R^ may be straight chain or branched alkyl 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. The substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituenrgroups or organic compounds. R*> is preferably H or methyl. R¹ and R^ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Benzoxazin organic peroxyacid activators

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

including the substituted benzoxazins of the type

wherein R- is H, alkyl, alkaryl, aryl, arylalkyi, and wherein R₂_ 3. R4, and Rc may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COORg (wherein Rg is H or an alkyl group) and carbonyl functions.

An especially preferred activator of the benzoxazin-type is:

Dinuclear manganese complex activators

Other preferred bleach activators are a dinuclear manganese (III) or manganese (IV) complex as described, for example, in US Patent Application Nos. 5,246,621 and 5,244,594. Preferred activators of this class are those referred to as having the following formulae:

1 ) [Mn^lv ₂(m-O)₃(Me-TACN)2](PF6)2

2) [Mn^I 2(m-O)₃(Me/Me-TACN)₂](PF6)2

3) [Mn 2(m-O)(m-OAc)2(Me-TACN)2](PF₆)2

4) [Mn 2(m-O)(m-OAc)2(Me/Me-TACN)₂](PF6)2 wherein Me-TACN is 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane, and Me/Me- TACN is 1 ,2,4,7-tetramethyl-1 ,4,7-triazacyclononane

Preformed organic peroxyacid

The bleaching system may contain a preformed organic peroxyacid , typically at a level of from 0.1 % to 20% by weight, more preferably from 0.2% to 10% by weight, most preferably from 0.3% to 5% by weight of the composition.

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

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

O R⁵ 0 or R⁵ 0 O

wherein R¹ 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 > is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. R1 preferably contains from 6 to 12 carbon atoms. R² preferably contains from 4 to 8 carbon atoms. R¹ 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. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. R^ and R^ should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A- 0170386.

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

(4) Chelant

Suitable chelants have the ability to sequester heavy metal ions (such as Mn⁺⁺, Fe⁺⁺ and Cu⁺⁺) in solution. Such chelants include amino carboxylates, amino phosphonates, and polyfunctionally-substituted aromatic chelants.

Amino carboxylates useful as chelating agents in compositions of the invention can have one or more, preferably at least two, units of the substructure

CH₉

__ N — (CH₂)_χ- COOH

wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to 3, preferably 1. Preferably, these amino carboxylates do not contain alkyl or alkenyl groups with more than 6 carbon atoms. Operable amino carboxylates include ethylenediaminetetraacetates, N- hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine disuccinates, ethylenediamine-N, N'-diglutamates, 2-hydroxypropylenediamine- N,N'-disuccinates, ethylenediamine tetraproprionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions. Compounds with one or more, preferably at least two, units of the substructure

wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to 3, preferably 1 , are useful and include ethylenediamine tetramethylenephosphonates, hexamethylenediamine tetramethylenephosphonates, aminotetramethylenephosphonates, nitrilo trimethylenephosphonates and diethylenethamine pentamethylenephosphonates. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms. Alkylene groups can be shared by substructures.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. These materials can comprise compounds having the general formula 2θ

wherein at least one R comprises -SO3H or -COOH chelating groups or soluble salts thereof and mixtures thereof. U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al., incorporated herein by reference, discloses polyfunctionally- substituted aromatic chelating and sequestering agents. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5- disulfobenzene. Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substituted ammonium (e.g. mono- or triethanol-amine) salts.

Other suitable chelants include hydroxy-1,1-ethylidene diphosphonic acid and derivatives; ethylenediamine disuccinate; tri-sodium salt of S,S, ethylene diamine disuccinate; iminodiacetic acid-N-2-hydroxypropyl sulphonic acid and aspartic acid-N-carboxymethyl-N-2-hydroxypropyl-3-sulphonic acid (see EP 516,102 by Dow Chemicals); beta alanine N,N-diacetic acid, aspartic acid N,N- diacetic acid, aspartic acid N-monoacetic acid and iminodisuccinic acid (see EP 509,382 by Grace Co.); alkyl iminodiacetic acid (see EP 526,959 by Grace Co.); iso serine diacetic acid (BASF); 2-phosphonobutane-1 ,2,4-tricarboxylic acid (Bayer); dipicolinic acid; protein derived from collagen, keratin or casein (see EP 510,331 by Huls); amino acid based chelants (see EP 476,257 by Huls); and chelants having the following structure (see DE 4024552 by Henkel):

Preferred chelants according to the present invention are selected from the group consisting of diethylenetriamine pentamethylenephosphonates, ethylenediamine tetramethylenephosphonates, diethylenetriamine pentaacetates, ethylenediamine disuccinates, ethylenediamine tetraacetates, and mixtures thereof.

The amount of chelant used in the present detergent compositions is typically from 0.1 % to 10% by weight, preferably from 0.2% to 7%, more preferably from 0.4% to 3%, and most preferably from 1 % to 1.8%. (5) Enzymes

The enzymes suitable for use in the present invention are proteases, amylases, lipases, cellulases, or mixtures thereof, and optionally other enzyme types. Preferred are proteases and amylases.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis. B.lentus and B.licheniformis. Another suitable protease is a modified bacterial serine protease enzyme obtained from Bacillus subtilis or Bacillus licheniformis. having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S (Denmark) under the registered tradename ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1 ,243,784 of^" Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S and MAXATASE by International Bio- Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al., published January 9, 1985). Most preferred is what is called herein "Protease C", which is a variant of an alkaline serine protease from Bacillus, particularly Bacillus lentus. in which arginine replaced lysine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958:4, U.S. Patent No. 5,185,250 and U.S. Patent No. 5,204,015, which are incorporated herein by reference. Genetically modified variants, particularly of Protease C, are also included herein.

Amylases include, for example, a-amylases described in British Patent Specification No. 1,296,839 (Novo); RAPIDASE, International Bio-Synthetics, Inc.; and TERMAMYL and BAN (bacterial a-amylase), Novo Industries.

The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS- 2.247.832.

Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1 ,372,034. See also lipases in Japanese Patent Application 53-20487, laid open to public inspection on February 28, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P". Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp. U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme, derived from the fungus Humicola lanuginosa and expressed in Aspergillus orvzae as host and commercially available from Novo (see also E.P. Patent 341,947) is a preferred lipase for use herein.

Other enzymes such as peroxidases and/or lignases can also be used in the present detergent compositions. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.

The detergent compositions of the invention preferably contain from 0.05% to 5% by weight enzymes, more preferably from 0.1 % to 3%, more preferably from 0.2% to 2%, and most preferably from 0.5% to 1.5%.

(6) Detergent Surfactant

Detergent surfactants useful herein are listed in U.S. Patents 3,664,961 , Norris, issued May 23, 1972, and 3,919,678, Laughlin et al., issued December 30, 1975, both incorporated herein by reference. The following are representative examples of detergent surfactants useful in the present compositions.

Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from 8 to 24 carbon atoms, and preferably from 12 to 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.

Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cβ-Ciβ carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. Especially preferred are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, C-|2^_18 Primary and secondary alkyl sulfates, and methyl ester sulfonates.

Other anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.

Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water- soluble salts of 2-acyloxyalkane-1 -sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety. 3

Water-soluble nonionic surfactants are also useful in the compositions of the invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

One particular class of adjunct nonionic surfactants especially useful herein comprises the polyhydroxy fatty acid amides of the formula:

wherein R-! is H, C-j-Cs hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C-1-C4 alkyl, more preferably C-j or C2 alkyl, most preferably C-j alkyl (i.e., methyl); and R² is a C5-C32 hydrocarbyl moiety, preferably straight chain C7-C-19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C-19 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) 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 moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of -CH2-(CHOH)_n-CH2θH,-CH(CH2θH)-(CHOH)_n.₁-CH₂OH_; and -CH₂- (CHOH)2(CHOR')(CHOH)-CH2θH, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2- (CHOH)4CH₂OH. In Formula (I), R1 can be, for example, N-methyl, N-ethyl, N- propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. For highest sudsing, R¹ is preferably methyl or hydroxyalkyl. If lower sudsing is desired, R¹ is preferably C2-C8 alkyl, especially n-propyl, iso-propyl, n-butyl, isobutyl, pentyl, hexyl and 2-ethyl hexyl. R²-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

Other suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 15 carbon atoms, in either a straight chain or branched configuration, w'th from 3 to 12 moles of ethylene oxide per mole of alkyl phenol.

Preferred nonionics are the water-soluble and water-dispersible condensation products of the aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 4 to 8 moles of ethylene oxide per mole of alcohol.

Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.

Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.

Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium and sulfonium compounds in which one of the aliphatic substituents contains from 8 to 18 carbon atoms.

The detergent compositions of the invention contain from 5% to 95% by weight detergent surfactant, preferably from 5% to 50%, and most preferably from 10% to 30%. 2G>

The detersive surfactants used in the present detergent compositions are preferably a mixture of anionic and nonionic surfactants. (6) Optional Detergency Builder

Optional detergent ingredients employed in the present invention are inorganic and/or organic detersive builders. Inorganic detersive builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phopshates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, nonμho p ate builders are required in some locales.

Examples of silicate builder? are the alkali metal silicates, particularly those having a Siθ2:Na2θ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U. S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, available from Hoechst under the trademark "SKS"; SKS-6 is an especially preferred layered silicate builder.

Carbonate builders, especially a finely ground calcium carbonate with surface area greater than 10 m²/g, are preferred builders that can be used in granular compositions. The density of such alkali metal carbonate built detergents can be in the range of 450-850 g/l with the moisture content preferably below 4%. Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973.

Aluminosiiicate builders are especially useful in the present invention. Preferred aluminosilicates are zeolite builders which have the formula: Na₂[(Alθ2)_z(Siθ2)y] xH₂O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and x is an integer from 15 to 264. Useful aluminosiiicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminoosilicates or synthetically derived. Methods for producing aluminosiiicate ion exchange materials are disclosed in U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976, and U.S. Patent 4,605,509, Corkill, et al., issued August 12, 1986. Preferred synthetic crystalline aluminosiiicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B) (including those disclosed in EPO 384,070), and Zeolite X. Preferably, the aluminosiiicate has a particle size of 0.1-10 microns in diameter.

Organic detersive builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds, such as ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071 , issued to Bush et al., on May 5, 1987. Suitable ether polycarboyxlates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detersive builders include the ether hydroxy- polycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 ,3,5-trihydroxy benzene-2,4,6-trisulphonic acid, and carboxymethyl- oxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt) are preferred polycarboxylate builders that can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1 ,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.

In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1 ,1-diphosphonate and other known phosphates (see, for example, U.S. Patents 3,159,581 ; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

If detergent builders are used in the present detergent compositions, they are used at levels from 1 % to 80% by weight, preferably from 5% to 60% by weight, and more preferably from 10% to 50% by weight. (8) Optional Detersive Adjuncts

Optionally, the detergent ingredients can include one or more other detersive adjuncts or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition. Usual detersive adjuncts of detergent compositions include the ingredients set forth in U.S. Patent No. 3,936,537, Baskerville et al., incorporated herein by reference. Such adjuncts which can be included in detergent compositions employed in the present invention, in their conventional art-established levels for use (generally from 0% to 30% of the detergent ingredients, preferably from 0.5% to 20%), include colored speckles, suds boosters, suds suppressors, antitamish and/or anticorrosion agents, soil- suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, perfumes, solvents, solubilizing agents, clay soil removal/anti-redeposition agents, polymeric dispersing agents, processing aids, fabric softening components, static control agents, etc.

The present detergent compositions can be in any of the different physical forms known to persons skilled in the art, for example granules/powders, liquids, bars, gels or pastes. The detergents can be laundry detergents, including those - suitable for use in machine laundering, or hand laundering methods or both, dishwashing detergents including automatic dishwashing detergents, hardsurface cleaners, or other known detergents, preferably laundry detergents.

EXAMPLE 1

In the following example, "Comparative A" and "Comparative B" are used in detergent compositions outside the scope of the present invention, while "Example 1" is used in a detergent made according to this invention. The whiteness performances of Comparative A and B are poor in comparison with Example 1. Further, Example 1 has less color fading than Comparative A because it uses a lower level of TAED.

Data: Laundry washing test

Test method - whiteness

The performance of the three compositions (Comaparative A and B and Example 1 ) was compared in full scale six cycle washing machine tests using Miele 701 washing machines. Each full wash-cycle comprised only a main-wash cycle. The 40°C temperature setting was selected for each wash cycle and water of 25° German Hardness (Ca : Mg = 3 : 1 ) was employed. Each laundry load comprised four 15 cm x 30 cm pieces of each of clean white terry towel, knitted cotton and cotton fabrics. Before the commencement of the first full wash cycle the laundry load together with a stained fabric strip as sold by the EMPA Institute, Switzerland under the tradename 'combined EMPA wash test strip no. 103' comprising a strip of 8 cotton test swatches, each of size 12cm x 12cm being cotton, bleached without optical brightener, cotton EMPA standard soiling, cotton soiled with blood, cotton soiled with cocoa, cotton soiled with blood/milk/carbon black, cotton dyed with sulphur black, cotton raw and cotton soiled with red wine together with a dispensing device of the "granulette" type containing 75 g of the detergent product was placed in the drum of the washing machine. For each of the subsequent five full wash cycles the same amount of detergent product and stained fabric strip was used. At the end of the sixth full wash cycle the laundry load was removed from the machine, dried in air and then an assessment of the whiteness/dinginess of the three types of fabric was made.

Whiteness

The whiteness/dinginess of each piece of fabric was assessed by an expert panel. The combined averaged results of the sets of comparisons are as set out below, with Comparative composition A being used as the common reference.

Comparative A Comparative B Example 1

Reference 37:63 73:27*

= statistically significant at the 95% confidence level.

Test method - fabric color fading

The 'fabric color fading' performance of the three compositions (Comparative A and B and Example 1 ) was compared in full scale washing machine tests using Miele 698 washing machines. The shortwash setting (temperature = 40°C) was selected and water of 25° German Hardness (Ca : Mg = 3 : 1 ) was employed.

For each product type, the laundry load comprised a single 43 cm x 43 cm purple wool (bleach sensitive) fabric swatch and a ballast load of 2 white sheets. Before the commencement of the first full wash cycle the laundry load together with a dispensing device of the "granulette" type containing 75 g of the detergent product was placed in the drum of the washing machine. The purple wool swatch was positioned such as to be adjacent to the dispensing 'mouth' of the granulette.

After the first tumble of the shortwash cycle a stop watch was started. The cycle was interrupted after 10 minutes from this time and and the laundry load removed from the drum. The purple wool swatch was then dried prior to an assessment of any color fading to the wool swatch being made.

The above procedure was repeated four times for each product type, each time using a fresh purple wool swatch.

Color Fading Assessment

The color fading of each of the four purple wool swatches obtained from the above procedure for each product type was assessed by an expert panel, using an unwashed purple wool swatch as the reference. The combined averaged results of the sets of comparisons are as set out below.

Comparative A Comparative B Example 1

Color fading 30% 30% 50% (% damage)

EXAMPLE 2

Inqredient {%}

Linear Alkylbenzene Sulfonate 21

Sodium Tripolyphosphate 31.5

Acrylic Maleic Acid 1

Sodium Carbonate 18

Sodium Silicate 8.6

Sodium Perborate Monohydrate 2.0

NonanoyI Oxybenzene Sulfonate 1.6

Diethylene Triamine Penta Acetic Acid 1.6

Savinase/Ban 6.0/170T 0.8

Carboxymethyl Cellulose 0.4

Lipolase 100T 0.12

Miscellaneous balance

EXAMPLE 3

Claims

WHAT IS CLAIMED IS :

1. A bleach-containing detergent composition comprising from 5% to 95% by weight detergent surfactant; from 0% to 80% by weight detergency builder; from 0.5% to 40% by weight peroxygen bleach; from 0.01% to 10% by weight bleach activator; from 0.1% to 10% by weight chelant; and from 0.05% to 5% by weight enzymes selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof; wherein the detergent composition has a Biological Bleach Index ("BBI") of greater than 65 as defined by the formula:

BBI = 4[C] + 26([E] - fBAI + fBAUPBI

2. A detergent composition according to Claim 1 which has a Biological Bleach Index of greater than 75.

3. A detergent composition according to Claim 1 wherein the peroxygen bleach comprises an alkali metal percarbonate.

4. A detergent composition according to Claim 1 wherein the bleach activator is selected from the group consisting of tetraacetyl ethylene diamine, benzoyi caprolactam, (6-Nonanamidocaproyl)oxybenzene sulfonate, sodium nonanoyloxybenzene sulfonate, sodium benzoyloxybenzene sulfonate, quaternary ammonium- and phosphonium-substituted bleach activators, cationic nitriles, dinuclear manganese (III) or (IV) complexes, and mixtures thereof.

5. A detergent composition according to Claim 4 wherein the bleach activator is tetraacetyl ethylene diamine.

6. A detergent composition according to Claim 1 wherein the bleach activator has the formula

O

R — C— L

wherein L is a leaving group where the conjugate acid of the anion formed on L has a pKa from 4 to 13.

7. A detergent composition according to Claim 1 wherein the chelant is selected from the group consisting of diethylenetriamine pentamethylenephosphonates, ethylenediamine tetramethylenephosphonates, diethylenetriamine pentaacetates, ethylenediamine disuccinates, ethylenediamine tetraacetates, and mixtures thereof.

8. A detergent composition accord.ng to Claim 1 wherein the enzymes are selected from the group consist'ng of proteases, amylases, and mixtures thereof.

9. A detergent composition according to Claim 1 comprising from 1 % to 30% by weight peroxygen bleach.

10. A detergent composition according to Claim 1 comprising from 0.2% to 7% by weight bleach activator.

11. A detergent composition according to Claim 1 comprising from 0.2% to 7% by weight chelant.

12. A detergent composition according to Claim 1 comprising from 0.1 % to 3% by weight enzymes.

13. A bleach-containing detergent composition comprising from 5% to 95% by weight detergent surfactant; from 0% to 80% by weight detergency builder; bleaching agent; and chelant and/or enzymes; wherein the levels of bleaching agent, chelant and ezymes are defined by the formulas:

[X]f = a[X]₀, Mf > 2/a [Y]₀, and [Z]f > 1/a[Z]₀, wherein "f ' means "final" and "o" means "original", wherein [X] is the sum of bleaching agents by weight percent in the composition, calculated at 100% activity, wherein the bleaching agents are selected from the group consisting of (i) peroxygen bleach and bleach activator, (ii) organic peroxy acid; and (iii) mixtures thereof; wherein [Y] is the sum of chelants by weight percent in the composition; wherein [Z] is the sum of enzymes by weight percent in the composition, wherein weight percent is calculated on the basis of standard enzyme activities of 13 KNPU for proteases, 300 KNU for amylases, 165 KLU for lipases, and 2000 Cevu for cellulases, and standard activities for other enzyme types; wherein "a" is less than 1 , wherein [X]₀ is between 3% and 80%, wherein

[Y]₀ is between 0% and 10%, and wherein [Z]₀ is between 0.01% and 10%.

14. A detergent composition according to Claim 13 wherein 0.5 < "a" < 1.

15. A detergent composition according to Claim 13 wherein [Y]₀ is between 0% and 3%.

16. A detergent composition according to Claim 13 wherein [Z]₀ is between 0.05% and 5%.

17. A detergent composition according to Claim 13 wherein [Y]₀ is O, and wherein [Y]f > ([X]₀ - [X]f)/3.

18. A detergent composition according to Claim 13 which comprises from 1 % to 30% by weight peroxygen bleach compound.

19. A detergent composition according to Claim 13 wherein the bleaching agent is peroxygen bleach and a bleach activator, and wherein the detergent composition comprises from 1 % to 7% by weight peroxygen bleach and from 0.2% to 7% by weight bleach activator.

20. A detergent composition according to Claim 13 which comprises from 0.2% to 7% by weight chelant.

21. A detergent composition according to Claim 13 which comprises from 0.05% to 5% by weight enzymes selected from the group consisting of proteases, amylases, lipases, cellulases, and mixtures thereof.

22. A detergent composition according to Claim 13 wherein the peroxygen bleach is selected from the group consisting of alkali metal percarbonates, alkali metal perborate monohydrates, alkali metal perborate tetrahydrates, and mixtures thereof.

23. A detergent composition according to either of Claim 13, wherein the chelant is selected from the group consisting of amino phosphonate chelating agents, amino carboxylate chelating agents, and mixtures thereof.