WO1997007193A1 - Perfumed bleaching detergent compositions - Google Patents

Abstract

There is provided a perfumed cleaning composition containing: (a) a bleaching system selected from: i) hydrogen peroxide or a source thereof in amount of from 1 % to 40 % by weight of the composition in combination with an organic peroxyacid bleach precursor compound in amount of from 0.5 % to 20 % by weight of the composition; ii) a preformed organic peroxyacid in amount of from 1 % to 15 % by weight of the composition; iii) hypohalite in amount of from 1 % to 15 % by weight of the composition; and any mixtures thereof; and (b) a perfume composition, present in amount of from 0.01 % to 5 % by weight of the cleaning composition, comprising: (i) lavender oils, and ii) fabric substantive ingredients selected from: esters with a moleuclar weight of 180 to 350 AMU, ethers with a molecular weight of 200 to 350 AMU, aliphatic ketones with a molecular weight of 150 to 350 AMU, naturals oils, and mixtures thereof.

Description

PERFUMED BLEACHING DETERGENT COMPOSITIONS

Field ofthe invention

The present invention relates to perfumed cleaning compositions which may be of use in the laundry or hard surface cleaner area. More particularly, it relates to cleaning compositions comprising a bleaching system and a stabilised lavender perfume composition.

Background ofthe invention

Perfumes are an important and desirable part of detergent compositions. They are used to cover up the chemicals odours of the cleaning ingredients and provide an aesthetic benefit to the wash process and, preferably the cleaned fabrics. Of these, lavender type perfumes are perfumes which provide a fresh and clean character to the laundered fabrics and/or the washed surfaces.

It is known to the formulator of a cleaning composition that cleaning compositions comprising strong bleaches such as hypohalites or activated bleach such as a peroxyacid, or a source of hydrogen peroxide and a precursor of a peroxyacid together with a perfume composition are difficult to formulate. In presence of such strong bleach systems, many perfume ingredients can be destroyed or damaged by contact on storage and/or during the washing process.

The Applicant has now surprisingly found that the provision of specific substantive ingredients in the perfume composition overcomes these problems.

For the purpose of the invention, by substantive ingredients is meant ingredients which sufficiently counteract residual malodours and which when combined with lavender oils components still produce in a bleach containing cleaning composition the fresh and clean character associated with lavender type perfume on the laundered fabric or cleaned surface.

Experimental determination of substantive ingredients may be done according to the residual malodour test determination described in EP-A-0,430,315.

It is therefore an object ofthe invention to provide a perfumed cleaning composition which gives an excellent fragrance on the laundered fabrics or cleaned surfaces as well as an excellent perfume stability in presence of the bleaching ingredients in the wash liquor and in the product during storage. For the purpose of the present invention, a perfumed cleaning composition consists of a cleaning composition and a perfume composition, both as defined hereinafter, wherein said perfume is incorporated by any means in a composition selected from: i)-the cleaning composition as a finished product, ii)-the cleaning composition during its making process, or any mixtures thereof.

Processes for incorporating the perfume in the cleaning composition are not critical to the present invention. This can be done by spray-on, admixture with one or more components of the cleaning composition or other means known to the man skilled in the art. A preferred process for granular detergent compositions, for cost and practicability reasons, is a spray-on process.

Summary ofthe invention

The present invention relates to a perfumed cleaning composition containing:

a- a bleaching system selected from: i)-hydrogen peroxide or a source thereof in amount of from 1% to 40% by weight of the composition in combination with an organic peroxyacid bleach precursor compound in amount of from 0.5% to 20% by weight ofthe composition; ii)-a preformed organic peroxyacid in amount of from 1% to 15% by weight ofthe composition; iii)-hypohalite in amount of from 1% to 15% by weight ofthe composition;

and any mixtures thereof; and

b- a perfume composition, present in amount of from 0.01% to 5% by weight of the cleaning composition, comprising i)-lavender oils, and ii)-substantive ingredients selected from

-esters with a molecular weight of 180 to 350 AMU -ethers with a molecular weight of 200 to 350 AMU -aliphatic ketones with a molecular weight of 150 to 350 AMU -naturals oils, and -mixtures thereof. In preferred embodiments ofthe invention where the perfumed cleaning composition contains substantive ingredients of at least two of the above mentioned classes, an enhanced substantivity of the perfume on the laundered fabrics or cleaned surfaces is perceived.

Detailed description ofthe invention

The present invention contemplates cleaning compositions having an excellent perfume stability.and fragrance

Bleaching svstem

An essential component ofthe invention is a bleaching system.

In a preferred embodiment of the invention, the bleaching system is capable of providing organic peroxyacid bleach to a wash solution .

In one preferred execution the bleaching system contains a hydrogen peroxide or a source thereof and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with hydrogen peroxide or a source thereof. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution a preformed organic peroxyacid is incoφorated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.

Inorganic perhydrate bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form ofthe alkali metal, preferably sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight ofthe compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal 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. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. Sodium percarbonate, being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise. 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 Na2SO4.n.Na2CO3 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 cleaning compositions 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 perhydrolysis the structure ofthe peroxyacid produced is

O X - C OOH

Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 5% to 10% by weight ofthe cleaning compositions.

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:

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 is 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

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.

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, including for example benzoyl oxy benzene sulfonate:

Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoy lating agents, including for example:

Ac = COCH3; Bz = Benzoyl

Perbenzoic acid precursor compounds of the imide type include 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 and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:

Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

Suitable N-acylated Iactam perbenzoic acid precursors have the formula:

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

Perbenzoic acid derivative precursors

Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.

Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl 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 precursor compounds are the amide substituted compounds ofthe following general formulae:

R N — R' R N

R^ or R° O O wherein R 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 R^ 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 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R* 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 R^. 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 bleach activator compounds of this type are described in EP-A-0170386.

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 of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.

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

A preferred cationically substituted alkyl oxybenzene sulfonate has the formula:

Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:

O

Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene alkyl caprolactams: O O

^{~~ ^} N+ ^ (^CH2)ⁿ

where n is from 0 to 12.

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

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 of the 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.

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 alkyl peroxyacid precursors

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

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

O R⁵ O or R⁵ O O

wherein R^ is an alkyl group with from 1 to 14 carbon atoms, R^ 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. R* preferably contains from 6 to 12 carbon atoms. R^ preferably contains from 4 to 8 carbon atoms. Rl 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 R^. The substitution can include alkyl, 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 bleach activator compounds of this type are described in EP-A-0170386.

Benzoxazin organic peroxyacid precursors

Also suitable are precursor 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 ofthe type

wherein R, is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R^, R3, R . and R- may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR,- (wherein R.- is H or an alkyl group) and carbonyl functions.

An especially preferred precursor ofthe benzoxazin-type is:

Preformed organic peroxyacid

The organic peroxyacid bleaching system 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% 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

O R⁵ O

or

R 1 N R' C — OOH

wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R^ is an alkylene, arylene, and 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. RΪ preferably contains from 6 to 12 carbon atoms. R^ preferably contains from 4 to 8 carbon atoms. R 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 R^. 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 diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid, and N-phthaloylaminoperoxicaproic acid are also suitable herein. Hvpohalites bleaches

In another preferred execution, the bleaching system may comprise as an alternative or in addition to one or both of the category mentionned above bleaching agents of the hypohalite type that are oxidative bleaches and subsequently lead to the formation of halide ion. Hypohalites bleaches are typically at a level of from 1% to

15% by weight, more preferably from 1% to 10% by weight ofthe composition.

Common among these types of bleaches are the alkaline metal and alkaline earth metal hypochlorites, hypobromites and hypoiodites although other bleaches that are organic based sources of halide, such as chloroisocyanurates, are also applicable.

Preferred bleach has the formula M(OX)_v where:

M is member selected from sodium, potassium, magnesium, calcium and mixtures thereof;

O is an oxygen atom;

X is member selected from chlorine, bromine, iodine and mixtures thereof; and y is 1 or 2 depending on the charge of M.

Preferred hypohalite bleaches for the purpose of the invention are sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, magnesium hypochlorite, sodium hypobromite, potassium hypobromite, calcium hypobromite, magnesium hypobromite, sodium hypoiodite and potassium hypoiodite , more preferably sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, magnesium hypochlorite, most preferably sodium hypochlorite.

Perfume composition

Another essential component of the invention is a perfume composition comprising lavender oils together with substantive ingredients.

The perfume composition is incorporated in the cleaning composition of the invention at a level of from 0.01% to 5% by weight, preferably from 0.01% to 2% by weight and more preferably from 0.05% to 1% by weight of the cleaning composition

Lavender oils

Lavender type of oils are well known to the man skilled in the art. These oils provide the fresh and clean character of the perfume to the housewife. Lavender type of oils may be natural or synthetic. Such oils are preferably selected from Lavandin Grosso oil, Lavandin Abrailis oil, Spike Lavender oil, reconstitutions of these and mixtures thereof.

Lavender oils are present within the perfume composition in amount from 20% to 70%, preferably from 35% to 50% by weight ofthe perfume composition.

Substantive ingredients

Substantive ingredients are ingredients which sufficiently counteract residual malodours and which when combined with lavender oils components still produce in a bleach containing cleaning composition the fresh and clean character associated with lavender type perfume on the laundered fabrics or cleaned surfaces.

More specifically, determination of substantive ingredients may be done according to the following steps:

a-Soiling test:

1 Og of dairy product is applied to white cotton swatches which are then sealed in plastic bags for 1 hour. Thereafter, the swatches are line dried overnight.

b-Wash procedure:

The resulting soiled fabrics are then loaded in a Terg-O-Meter together with 1 litre of water at 40°C, 6g of a bleach system (as described herein before) containing cleaning composition and comprising 0.1% of the fragrance to be tested and thereafter subject to one wash of 10 minutes at 150 rpm. After wringing out, the swatches are line dried for 24 hours. The dried swatches are placed into plastic bags and left to equilibrate for 1 hour at room temperature. Control samples of swatches, washed in unperfumed bleach containing laundry powder without fabric substantive ingredients, are prepared in the same way.

c-Sensory analysis:

The perceived intensity of residual malodour and residual character of the fragrance material to be tested on the swatches is carried out by a panel of 6 expert judges, trained to use sensory evaluations. In this instance, expert is defined as a person having at least 6 months training with demonstrated evidence of olfactive sensitivity. The data were averaged to give a consensus value for the perceived intensity of residual malodour. Once the substantive ingredients have been defined, the said substantive ingredients are then tested according to the method described above in a lavender composition of the invention versus a lavender perfume without the defined substantive ingredients.

The same steps are applied for determination of substantive ingredients on the cleaned surface in hard surface cleaner, with minor and obvious changes made by the skilled person to adapt to the circumstances.

From the method described above, the classes selected from -esters with a molecular weight of 180 to 350 AMU -ethers with a molecular weight of 200 to 350 AMU -aliphatic ketones with a molecular weight of 150 to 350 AMU -naturals oils, and -mixtures thereof,

were found to be substantive and also to produce the fresh and clean character associated to lavender perfumes when combined with lavender oils.

Preferred esters from the range mentioned above are selected from hexyl salicylate, benzyl salicylate and mixtures thereof.

Preferred ethers from the range mentioned above are selected from 1,3,4,6,7,8- hexahydro-4,6,6,7,8,8-hexamethyl-cyclo penta-gamma-2-benzopyran (Galaxolide 50%), 3α-methyl-dodecahydro-6,6,9a-trimethyl naphtho 2 (2, 1-b) fiiran and mixtures thereof.

Preferred aliphatic ketones from the range mentioned above are selected from 7- Acetyl,l,2,3,4,5,6,7,8 octahydro-1,1,6,7 tetra methyl naphthalene (iso E Super), Methyl Cedryl Ketone and mixtures thereof.

A preferred natural oil is patchouli oil.

In a preferred embodiment of the invention, perfume composition which comprises substantive ingredients from at least two of the above mentioned classes were found to produce an enhanced substantivity benefit. Substantive ingredients are present within the perfume composition in amount from 20% to 80%, preferably from 25% to 50% by weight ofthe perfume composition.

Additional aroma chemicals

Additional aroma chemicals may be added to optimise the odour character of the perfume. Said optimisation process, aroma chemicals and levels of said aroma chemicals which may be used advantageously in lavender type perfumes are well known to the skilled person.

Non limiting examples of additional aroma chemicals which may be of use herein for optimisation of the odour character include Coumarin, Methyl Amyl Ketone, Geranium oil or reconstitution of this, Methyl Hexyl Ketone, Methyl Ionones and mixtures thereof

Additional cleaning components

The cleaning compositions of the invention may also contain additional cleaning components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature ofthe cleaning operation for which it is to be used.

The composition of the invention preferably contains one or more additional cleaning components selected from surfactants, builders, chelants, enzymes (especially lipases), enzymes stabilisers and additional adjuncts ingredients.

Surfactants

Cleaning compositions incorporating the perfumed bleaching composition of the invention ofthe present invention will include one or more surfactants.

The total amount of surfactants will be generally up to 70%, typically 1 to 55%, preferably 1 to 30%, more preferably 5 to 25% and especially 10 to 20% by weight ofthe total composition.

Nonlimiting examples of surfactants useful herein include the conventional C\ j-Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random

C10-C20 alkyl sulfates ("AS"), the C] o-C 18 secondary (2,3) alkyl sulfates of the formula CH₃(CH2)x(CHOSO₃-M⁺) CH3 and CH₃(CH2)_y (CHOSO₃-M⁺)

CH2CH3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates ("AExS"; especially EO 1-7 ethoxy sulfates), CJQ-CI S alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the Cjθ"18 glycerol ethers, the CJO-CJ S alkyl polyglycosides and their conesponding sulfated polyglycosides, and C12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE"), including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C1 betaines and sulfobetaines ("sultaines"),

amine oxides, and the like, can also be included in the overall compositions. The CJO-CJS N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cjo-Ci N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C \ 0-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain CiQ-Cjg soaps may be used. Other suitable surfactants suitable for the purpose of the invention are the anionic alkali metal sarcosinates of formula:

R-CON(R¹)CH₂COOM wherein R is a C9-C17 linear or branched alkyl or alkenyl group, Rj is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the lauroyl, cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in the form of their sodium salts. Still another class of surfactant which may be suitable for the purpose of the invention are the cationic surfactant. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C6-Cj6- preferably C -C\Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.

Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.

The level of builder can vary widely depending upon the end use of the composition and its desired physical form. Granular formulations typically comprise from 1% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded. Inorganic or phosphate-containing detergent 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-phosphates).

Non-phosphate builders may also be used. These can include, but are not restricted to phytic acid, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulphates, aluminosilicates, monomeric polycarboxylates, 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 than two carbon atoms, organic phosphonates and aminoalkylene poly (alkylene phosphonates).

The compositions herein also function in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.

Examples of silicate builders are the so called 'amorphous' alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and crystalline layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminium. NaSKS-6 has the delta-Na2Si2θ5 moφhology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3 ,417,649 and DE- A-3, 742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi_xθ2_x+ι yH2θ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2Si2θ5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilising agent for oxygen bleaches, and as a component of suds control systems.

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. Such carbonate builders act as builders to remove divalent metal ions such as calcium and additionally provides alkalinity and aids in soil removal. Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

Na_z[(AlO₂)_z(SiO₂)_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 aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amoφhous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669. Prefeπed synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially prefeπed embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na₁₂[(Alθ2)i2(Siθ2)i2] xH₂O wherein x is from 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter.

Organic detergent builders suitable for the pmposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralised salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also "TMS/TDS" builders of U.S. Patent 4,663,071. Suitable ether polycarboxylates 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 detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic 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 polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.

Also suitable in the compositions containing the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly prefeπed compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the prefeπed builders of this group, and are described in EP 0,200,263.

Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat. 3,723,322.

Fatty acids, e.g., C12-C18 monocarboxylic acids, can also be incoφorated into the compositions alone, or in combination with the aforesaid builders, especially citrate and or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.

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 phosphonates (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. Chelants

Chelating agents generally comprise from 0.1% to 10% by weight of the compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1% to 3.0% by weight of such compositions.

A chelating agent can be selected from amino carboxylate, organic phosphonate, polyfunctionally-substituted aromatic compound, nitriloacetic acid and mixture thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove transition metal ions such as iron and manganese ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, ethylenediamine disuccinate, N-hydroxyethylethylenediaminetriacetates,

2-hydroxypropylene diamine disuccinate, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, ethylene triamine pentaacetate, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein. Prefeπed amino carboxylates chelants for use herein are ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, ethylenediamine-N,N'-diglutamate (EDDG) and 2-hydroxypropylene- diamine-N,N'-disuccinate (HPDDS) compounds. A most prefeπed amino carboxylate chelant is ethylenediamine disuccinate.

Organic phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) available under the trademark DEQUEST from Monsanto, diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate), α-hydroxy-2 phenyl ethyl diphosphonate, methylene diphosphonate, hydroxy 1,1-hexylidene, vinylidene 1,1 diphosphonate, 1,2 dihydroxyethane 1,1 diphosphonate and hydroxy- ethane 1,1 diphosphonate.

Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.

Prefeπed chelants are the diphosphonate derivatives selected from α-hydroxy-2 phenyl ethyl diphosphonate, methylene diphosphonate, hydroxy 1,1-hexylidene, vinylidene 1,1 diphosphonate, 1,2 dihydroxyethane 1,1 diphosphonate and hydroxy- ethane 1,1 diphosphonate. A most prefeπed is hydroxy-ethane 1,1 diphosphonate. Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044. Prefeπed compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.

Enzymes - Enzymes can be included in the formulations herein for a wide variety of fabric laundering puφoses, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of fugitive dye transfer, and for fabric restoration. The enzymes to be incoφorated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability and stability versus active detergents and builders. In this respect bacterial or fungal enzymes are prefeπed, such as bacterial amylases and proteases, and fungal cellulases.

Enzymes are normally incoφorated at levels sufficient to provide up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5% by weight of a commercial enzyme preparation.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in GB 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 (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see EP 130,756) and Protease B (see EP257189). Prefeπed levels of proteases are from 0.01% to 4.0% by weight of the cleaning composition herein.

Amylases include, for example, α-amylases described in GB 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries. Fungamyl (Novo) is especially useful. Prefeπed levels of amylases are from 0.01% to 2.0% by weight ofthe cleaning composition herein.

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, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM 1800 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. ENDO A, CAREZYME both from Novo Industries A/S are especially useful. Preferred levels of cellulases are from 0.01% to 1.0% by weight of the cleaning composition herein.

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 GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter refeπed 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 Coφ., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP 341,947) is a prefeπed lipase for use herein. Preferred levels of lipases are from 0.01% to 2.0% by weight ofthe cleaning composition herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. 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. A wide range of enzyme materials and means for their incoφoration into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139. Enzymes are further disclosed in U.S. Patent 4,101,457 and in U.S. Patent 4,507,219. Enzyme materials useful for liquid detergent formulations, and their incoφoration into such formulations, are disclosed in U.S. Patent 4,261,868. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. Patent 3,600,319 and EP 0 199 405. Enzyme stabilisation systems are also described, for example, in U.S. Patent 3,519,570.

The perfumed cleaning composition of the invention was also seen to produce a noticeable perfume benefit as well as a noticeable coverage of residual malodour arising from the use of enzymes, especially lipases.

Enzyme Stabilisers - The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are prefeπed herein if only one type of cation is being used.) Additional stability can be provided by the presence of various other art-disclosed stabilisers, especially borate species: see Severson, U.S. 4,537,706. Typical detergents, especially liquids, will comprise from 1 to 30, preferably from 2 to 20, more preferably from 5 to 15, and most preferably from 8 to 12, millimoles of calcium ion per litre of finished composition. This can vary somewhat, depending on the amount of enzyme present and its response to the calcium or magnesium ions. The level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition. Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the conesponding magnesium salts. A small amount of calcium ion, generally from 0.05 to 0.4 millimoles per litre, is often also present in the composition due to calcium in the enzyme slurry and formula water. In solid detergent compositions the formulation may include a sufficient quantity of a water¬ soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice. It is to be understood that the foregoing levels of calcium and/or magnesium ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions can be added to the compositions to provide an additional measure of grease removal performance. Accordingly, as a general proposition the compositions herein will typically comprise from 0.05% to 2% by weight of a water-soluble source of calcium or magnesium ions, or both. The amount can vary, of course, with the amount and type of enzyme employed in the composition.

The compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers will be used at levels in the compositions from 0.25% to 10%, preferably from 0.5% to 5%, more preferably from 0.75% to 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid). Boric acid is prefeπed, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid) can also be used in place of boric acid.

Adjunct Ingredients

The compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics ofthe cleaning composition (e.g., colorants, dyes, etc.).

Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously be utilized at levels from 0.5% to 8%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4.000 to 7,000 and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067.

Acrylic/maleic-based copolymers may also be used as a prefeπed component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1 :1, more preferably from 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol teφolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 teφolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these puφoses range from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000. Clav Soil Removal/Anti-redeposition Agents - The compositions according to the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01% to 5%.

The most prefeπed soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898. Another group of prefeπed clay soil removal-antiredeposition agents are the cationic compounds disclosed in EP 111,965. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in EP 111,984; the zwitterionic polymers disclosed in EP 112,592; and the amine oxides disclosed in U.S. Patent 4,548,744. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of prefeπed antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Soil Release Agent - Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. Polymeric soil release agents are characterised by having both 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 and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly( vinyl ester), e.g., Cj-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones (see EP 0 219 048). Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).

One type of prefeπed soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 and U.S. Patent 3,893,929.

Another prefeπed polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units which contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300- 5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857.

Another prefeπed polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580 and the block polyester oligomeric compounds of U.S. Patent 4,702,857.

Prefeπed polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.

If utilized, soil release agents will generally comprise from 0.01% to 10.0%, by weight, of the compositions herein, typically from 0.1% to 5%, preferably from 0.2% to 3.0%.

Still another prefeπed soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy- 1,2- propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly prefeπed soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.

Dye Transfer Inhibiting Agents

The compositions according to the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyπolidone polymers, polyamine N-oxide polymers, copolymers of N- vinylpyπolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01% to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.

More specifically, the polyamine N-oxide polymers prefeπed for use herein contain units having the following structural formula: R-A_x-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part ofthe polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1 ; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Prefeπed polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyπole, imidazole, pyπolidine, piperidine and derivatives thereof.

The N-O group can be represented by the following general structures: O O

(Rι -N-(R₂)y; =N-(R₁)_X

(R₃)z wherein R\, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen ofthe N-O group can be attached or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more prefeπed pKa <6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10: 1 to 1 : 1 ,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more prefeπed 1,000 to 500,000; most prefeπed 5,000 to 100,000. This prefeπed class of materials can be refeπed to as "PVNO".

The most prefeπed polyamine N-oxide useful in the compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1 :4.

Copolymers of N-vinylpyπolidone and N-vinylimidazole polymers (refeπed to as a class as "PVPVI") are also prefeπed for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113. "Modern Methods of Polymer Characterization".) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N- vinylpyπolidone from 1 :1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4: 1. These copolymers can be either linear or branched.

The present invention compositions also may employ a polyvinylpyπolidone ("PVP") having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000. PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A- 256,696. Compositions containing PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.

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

The hydrophilic optical brighteners useful in the present invention are those having the structural formula:

wherein R\ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxy ethyl; 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, Rj 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]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Coφoration. Tinopal-UNPA-GX is the prefeπed hydrophilic optical brightener useful in the 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]2,2'-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]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Coφoration.

Other specific optical brightener species which may be used in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA- GX, Tinopal 5BM-GX and or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context ofthe present invention.

Of course, it will be appreciated that other conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations. Conventional optical brighteners or other brightening or whitening agents known in the art can be incoφorated at levels typically from 0.005% to 5%, preferably from 0.01% to 1.2% and most preferably from 0.05% to 1.2%, by weight, into the cleaning compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6- membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982). Further optical brightener which may also be used in the present invention include naphthalimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof.

Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856. These brighteners include the PHOR WHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD; the 2-(4-styryl- phenyl)-2H-naptho[ 1 ,2-d]triazoles; 4,4'-bis( 1 ,2,3-triazol-2-yl)-stilbenes; 4,4'- bis(styryl)bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin; 1 ,2-bis(-benzimidazol-2- yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl- naptho-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho[l,2-d]triazole. See also U.S. Patent 3,646,015.

Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incoφorated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front-loading European-style washing machines.

A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347. The monocarboxylic fatty acids and salts thereof used 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.

The cleaning compositions herein may also contain non-surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1 -C40 ketones (e.g., stearone), etc. Other suds inhibitors include 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, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40°C and 50°C, and a minimum boiling point not less than 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100°C. The hydrocarbons constitute a prefeπed category of suds suppressor for cleaning compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another prefeπed category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779 and EP 354016.

Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incoφorating therein small amounts of polydimethylsiloxane fluids.

Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672 and in U.S. Patent 4,652,392. An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:

(i) polydimethylsiloxane fluid having a viscosity of from 20 cs. to 1 ,500 cs. at 25°C;

(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3SiOi[/2 units of Siθ2 units in a ratio of from (CH3)3 SiOι/2 units and to Siθ2 units of from 0.6: 1 to 1.2:1; and

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

In the prefeπed silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene- polypropylene glycol copolymers or mixtures thereof (prefeπed), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and preferably not linear.

To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from 0.001 to 1, preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin- producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471 and 4,983,316; 5,288,431 and U.S. Patents 4,639,489 and 4,749,740.

The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than 2 weight %, preferably more than 5 weight %.

The preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Prefeπed is a weight ratio of between 1 :1 and 1 :10, most preferably between 1 :3 and 1 :6, of polyethylene glycol :copolymer of polyethylene-polypropylene glycol.

The prefeπed silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L 101.

Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C]6 alkyl alcohols having a Cj-Cjg chain. A prefeπed alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5: 1.

For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.

The compositions herein will generally comprise from 0% to 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to 5%, by weight, of the cleaning composition. Preferably, from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight, of the cleaning composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from 0.01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1% to 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01% to 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight ofthe fmished compositions. Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10%, preferably from 0.5% to 2% by weight in the present compositions to provide fabric softener benefits concuπently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416 and U.S. Patent 4,291,071.

Other Ingredients - A wide variety of other functional ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, earners, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions.

The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH ofbetween 6.5 and 11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9- 11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

Other optional ingredients

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

Form ofthe compositions

The detergent compositions ofthe invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, and gels.

Liquid compositions

The detergent compositions of the present invention may be formulated as liquid detergent compositions. Such liquid detergent compositions typically comprise from 94% to 35% by weight, preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight of a liquid carrier, e.g., water, preferably a mixmre of water and organic solvent. Gel compositions

The detergent compositions ofthe present invention may also be in the form of gels. Such compositions are typically formulated with polyakenyl polyether having a molecular weight of from about 750,000 to about 4,000,000.

Solid compositions

The detergent compositions of the invention may also be in the form of solids, such as powders and granules.

The mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.4mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight ofthe sample would pass.

The bulk density of granular detergent compositions in accordance with the present invention are particularly useful in concentrated granular detergent compositions that are characterised by a relatively high density in comparison with conventional laundry detergent compositions. Such high density compositions typically have a bulk density of at least 400 g/litre, more preferably from 650 g/litre to 1200 g/litre, most preferably from 800g/litre to lOOOg/litre.

Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface ofthe base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml. To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.

Making processes - granular compositions

In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.

The invention is illustrated in the following non limiting examples, in which all percentages are on a weight basis unless otherwise stated.

In the compositions ofthe invention, the abbreviated component identifications have the following meanings:

LAS : Sodium linear C_j2 alkyl benzene sulphonate TAS : Sodium tallow alcohol sulphate

TAE 80 : Tallow alcohol ethoxylated with 80 moles of ethylene oxide per mole of alcohol C45E7 : A C14 5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C25 E3 A C 12-15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide STPP Anhydrous sodium tripolyphosphate

MA/AA : Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000. Zeolite A : Hydrated Sodium Aluminosilicate of formula

Nai2(A10₂SiO )i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 HEDP 1 , 1 -hydroxyethane diphosphonic acid

CMC Sodium carboxymethyl cellulose

PB4 Sodium perborate tetrahydrate of nominal formula

NaBO₂.3H₂O.H2θ2

PB1 Anhydrous sodium perborate bleach of nominal formula NaBθ2-H2θ2

TAED Tetraacetyl ethylene diamine (86% active) agglomerated with MA/AA

Photoactivated Sulphonated Zinc Phthalocyanine bleach encapsulated in dextrin soluble polymer

Savinase proteolytic enzyme of standard activity 13KNPU/g

Carezyme Cellulytic enzyme of activity 1000 CEVU/g

Termamyl Amylolytic enzyme of activity 60KNU/g all sold by

NOVO Industries A S

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.

Sulphate : Anhydrous sodium sulphate

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

Silicate : Amoφhous Sodium Silicate (Siθ2:Na2θ; 2.0 ratio)

Brightener 1 : Disodium 4,4'-bis(4-anilino-6-moφholino- 1.3.5- riazin-2-yl)amino) stilbene-2 :2'-disulphonate.

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

Example 1

The following perfume formulation was prepared:

Components % by weight

Lavandin Grosso oil 25.0

Spike Lavender oil 15.0

Hexyl salicylate 25.0

Patchouli oil 5.0

Methyl Cedryl Ketone 10.0 3 α-methy l-dodecahydro-6,6,9a- 0.2 trimethyl naphtho 2 (2, 1-b) furan

Coumarin 5.0

Ionone Gamma Methyl 3.0

Geranium oil reconstitution 3.7

Methyl Hexyl Ketone 0.5

Methyl Amyl Ketone 0.1

Hexa-hydro-4,7 Methano-Inden-5-yl 5.0 Acetate

Hexa-hydro-4,7 Methano-Inden-5-yl 2.5 Propionate

Example 2

The following detergent compositions according to the invention were prepared, wherein the perfume as defined in Example 1 is sprayed onto each of the detergent compositions A and B.

Components A B

LAS 5.64 7.75

TAS 2.42 -

TAE80 0.08 -

C45E7 5.0 -

C25E3 - 3.90

STPP 20.70 -

Zeolite A - 0.30

MA/AA 1.67 0.30

CMC 0.29 0.22

DTPMP 0.36 0.24

HEDP - 0.22

PB1 1.96 -

Claims

What is claimed is:

1-A perfumed cleaning composition containing:

a- a bleaching system selected from: i)-hydrogen peroxide or a source thereof in amount of from 1% to 40% by weight of the composition in combination with an organic peroxyacid bleach precursor compound in amount of from 0.5% to 20% by weight ofthe composition; ii)-a preformed organic peroxyacid in amount of from 1% to 15% by weight ofthe composition; iii)-hypohalite in amount of from 1% to 15% by weight of the composition; and any mixtures thereof; and

b- a perfume composition, present in amount of from 0.01% to 5% by weight of the cleaning composition, comprising i)-lavender oils, and ii)-substantive ingredients selected from

-esters with a molecular weight of 180 to 350 AMU -ethers with a molecular weight of 200 to 350 AMU -aliphatic ketones with a molecular weight of 150 to 350 AMU -naturals oils, and -mixtures thereof.

2- A perfumed cleaning composition according to Claim 1, wherein said lavender oils are selected from Lavandin Grosso oil, Lavandin Abrailis oil, Spike Lavender oil, reconstitutions of these and mixtures thereof.

3- A perfumed cleaning composition according to either one of Claim 1 or 2, wherein said lavender oil is present in amount of from 20% to 70%, preferably from 35% to 50% by weight ofthe perfume composition.

4-A perfumed cleaning composition according to any one of Claim 1-3, wherein said substantive esters are selected from hexyl salicylate, benzyl salicylate and mixtures thereof.

5-A perfumed cleaning composition according to any one of Claim 1-4, wherein said substantive ethers are selected from l,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl- cyclo penta-gamma-2-benzopyran (Galaxolide 50%), 3α-methyl-dodecahydro- 6,6,9a-trimethyl naphtho 2 (2, 1-b) furan and mixtures thereof.

6-A perfumed cleaning composition according to any one of Claim 1-5, wherein said substantive aliphatic ketones are selected from 7-Acetyl, 1,2,3 ,4,5,6,7,8 octahydro- 1,1,6,7 tetra methyl naphthalene (iso E Super), Methyl Cedryl Ketone and mixtures thereof.

7-A perfumed cleaning composition according to any one of Claim 1-6, wherein said substantive natural oil is patchouli oil.

8-A perfumed cleaning composition according to any one of Claim 1-7, wherein said substantive ingredients are present in amount of from 20% to 80%, preferably from 25% to 50% by weight ofthe perfume composition.

9-A perfumed cleaning composition according to any one of Claim 1-8, wherein said perfume composition comprises substantive ingredients from at least two of the above mentioned classes.

10-A perfumed cleaning composition according to any one of Claim 1-9, wherein said source of hydrogen peroxide is an inorganic perhydrate salt selected from sodium perborate and percarbonate.

l l-A perfumed cleaning composition according to any one of Claim 1-10, wherein said organic peroxyacid bleach precursor compound is Tetraacetyl ethylene diamine (TAED).

12-A perfumed cleaning composition according to any one of Claim 1-11, wherein said composition further comprises additional cleaning components selected from surfactants, builders, chelants, enzymes, enzymes stabilisers and additional adjuncts ingredients.

13-A perfumed cleaning composition according to Claim 12, wherein said enzymes are lipases.

14- A perfumed cleaning composition according to any one of Claim 1-13, wherein said composition is a granular detergent composition.