CZ134897A3 - Detergents containing a peroxide source, bleaching precursor and hydrogen peroxide trap - Google Patents

Abstract

There is provided a detergent composition containing: (a) a source of peroxide compounds, (b) a peroxyacid bleach precursor composition comprising i) an organic peroxyacid bleach precursor compound, ii) an H2O2 scavenging material, wherein said organic peroxyacid bleach precursor compound and said H2O2 scavenging material are in close physical proximity within said composition. The composition is useful in the bleaching of stains from stained coloured fabrics. The H2O2 scavenging material acts to inhibit "patchy" fabric discolouration to said fabrics during the stain bleaching process.

Description

BACKGROUND OF THE INVENTION

The satisfactory removal of bleachable impurities / stains such as tea, fruit juice and vegetable stains from stained fabrics is a particular challenge for the formulator of the bleaching agents used in washing. Typically, the bleaching of such bleaches is accomplished using bleaching components such as oxygen bleaches containing hydrogen peroxide and organic peroxyacids. Organic peroxyacids are often obtained by in situ perhydrolysis, i.e., a reaction between hydrogen peroxide and a bleach precursor of organic peroxyacids.

The increased use of organic peroxyacid bleach precursors is reflected in a decrease in fabric wash temperatures, accompanied by an increase in the proportion of colored fabrics. A problem that becomes important as a result of these trends is the bleached paints on fabrics and materials caused by high local concentrations of bleaching compounds. High transient concentrations may occur for several reasons. The bleaching compounds themselves may have intrinsically low solubility, their solubility may be prevented by the presence of other materials, such as viscous surfactants, or the mixing mode in the immediate vicinity of the bleaching compounds is not high enough to disperse the dissolved bleach. If the peroxyacid bleach precursor forms part of the composition, the possible problems will be increased. Further, local high concentrations of perhydroxyl ion, resulting from the dissolution of the inorganic perhydrate, typically contained in laundry detergent compositions, perhydrolysis of the peroxyacid bleach precursor can substantially increase local peroxyacid bleach concentrations. This is particularly true when the detergent composition contains high levels (e.g. greater than 3% by weight) of the peroxyacid bleach precursor and / or when sodium percarbonate is used as the hydrogen peroxide source.

Applicants have found that a bleached paint problem can be particularly difficult to solve using peroxyacid bleach precursor compounds which, after perhydrolysis, provide a peroxyacid which is perbenzoic acid or non-cationic substituted derivatives thereof or a cationic peroxyacid. It has been found that benzoxazine-type precursor compounds in particular increase this problem.

The development of so-called concentrated products and their dosing by a device placed directly in the drum together with the fabric filling serve only to highlight these problems.

Accordingly, there is a need for detergent compositions wherein the organic peroxyacid bleach precursor is added in a form that minimizes or even suppresses bleached stains on fabrics during its dissolution and perhydrolysis in the wash liquid while acceptably removing bleachable stains / dirt from soiled fabrics.

The state of the art discloses a number of examples of organic peroxyacid bleach precursors coated or agglomerated in order to increase their storage stability and / or the effect of their behavior in solution.

ΕΡ-Α-0 070 474 claims granulated organic peroxyacid bleach precursors prepared by spray drying an aqueous pumpable dispersion containing an N-acylated or O-acylated compound with at least one water-soluble cellulose ether, starch or starch derivative in a coating activator ratio of 98: 2 to 90:10.

GB-A-1 507 312 claims coatings of organic peroxyacid bleach precursors with a mixture of C8-C22 fatty acid salts in admixture with the corresponding fatty acids. GB-A-1 381 121 uses molten coatings of mixtures of C14-C18 fatty acids to protect precursors of bleaching organic peroxyacids. GB-A-1 441 416 claims a similar process using a mixture of C 12 to C 24 fatty acids and C 10 to C 20 aliphatic alcohols. EP-A-0 375 421 describes stabilized extrudates of organic peroxyacid bleach precursors in which the precursors are

-C 1-6 -alkyl peroxycarboxylic acids are mixed with a binder selected from anionic or nonionic surfactants, film-forming fatty acid polymers, or mixtures of such binders.

EP-A-0 356 700 claims compositions comprising an organic peroxyacid bleach precursor, a water-soluble film-forming polymer and 2 to 15% of a Cg-Cg polyvalent carboxylic acid or hydroxycarboxylic acid to enhance stability and facilitate dispersion and / or solubility formation. The carboxylic acid, preferably citric acid, is dry blended with the organic peroxyacid bleach precursor and then granulated with the film-forming polymer. Citric acid is used to increase the dissolution rate of the granules of the organic bleach precursors with eine.

EP-A-0 382 264 relates to a process for coating or encapsulating solid particles comprising bleaching compounds and organic peroxyacid bleach precursors in which a melt of coating material is formed in which the particles form a dispersed phase, the melt is destabilized and comminuted, wherein the dispersed phase particles are deposited in a continuous (coating) phase. A number of coating materials are disclosed and some materials such as polyacrylic acid and cellulose acetate phthalate are considered useful when the release of the coated material is pH dependent.

The overall emphasis in the prior art is to protect the bleaching organic peroxyacid precursor against harmful environment during storage, and relatively little attention is paid to the dissolution characteristics of the coated agglomerated material. If the coatings and / or agglomerations are carried out by poorly dissolving materials such as fatty acids, this results in the perhydrolysis rate of the peroxyacid bleach precursor being slower than if it were not protected, thereby reducing the peroxycarboxylic acid bleaching efficiency. Any use of more rapidly soluble materials, such as citric acid, is in the context of an agglomerate component that has been targeted to dissolve the peroxyacid bleach precursors more rapidly. A further solution to the problem of fabric damage is disclosed in JP 57 296, wherein the water-insoluble mineral, peroxyacid bleach precursor and bleach compound are mixed together, wherein the ratio of said mineral to said precursor and bleach compound is 1:99 to 90:10, preferably 20:80 to 65:35. The water-insoluble mineral is selected from acidic clay, activated clay, kaolin, bentonite, diatomaceous earth and perlite and is said to inhibit fading without inhibiting the whitening effect. EP 0 028 432 relates to damage resulting in small and localized damage sites (usually no more than 2 to 5 mm in diameter) on fabrics due to the slow dissolution of the bleaching system. Said document claims granules comprising a detergent composition comprising 5% to 80% peroxyacid bleach precursor, 15% to 60% water-insoluble silicates and 5% to 40% nonionic binder within the solid detergent composition. This water-insoluble silica compound, preferably smectite clay, is admixed with a peroxyacid bleach precursor and further bound with a nonionic surfactant. This combination is used to rapidly generate peroxycarboxylic anions when added to a source of hydrogen peroxide. In any case, since perhydrolysis begins as soon as the detergent product begins to dissolve and forms an alkaline hydrogen peroxide environment, the problem of localized peroxyacid bleach concentrations remains unresolved.

One solution to this problem could be to delay the onset of perhydrolysis in order to avoid damaging the fabric color associated with the dissolution of other detergent products. By way of example, WO 92/13798 may be used where acidic materials having specific characteristics for peroxyacid bleach precursors may be used to delay the onset of perhydrolysis during the initial stages of dissolution and / or dispersion of the product in an aqueous wash liquid.

However, compositions containing such acidic coating materials are expensive and require complex processes. Further, protection of fabric dye damage has been found to limit the presence of high levels of organic peroxyacid bleach precursors.

Applicants have found that the problem of spotting caused by impairing the colourfastness of the fabric can be significantly suppressed by the physical proximity of the hydrogen peroxide scavenger and the organic peroxyacid bleach precursor. It has been found that the inclusion of a hydrogen peroxide scavenger does not substantially compromise the release of the peroxyacid in the wash liquid as well as the ability of the composition to remove bleachable stains.

Further, it has been found that the physical proximity of the hydrogen peroxide scavenger to the bleaching organic peroxyacid precursor increases the storage stability of said precursor material.

By physical proximity is meant an agglomerate or extrudate in which said hydrogen peroxide scavenger and bleach precursor organic peroxyacid are intimately mixed. It also means that the bleach precursor particles are coated with at least one layer in which at least one layer comprises a hydrogen peroxide scavenger. Proximity is to be understood so that the peroxyacid bleach scavenger and precursor do not form two separate discrete particles in the detergent composition.

For the purposes of the present invention, the hydrogen peroxide scavenger contained in the peroxyacid bleach precursor in the detergent composition is defined as follows:

A hydrogen peroxide scavenger is a compound that reduces the level of hydrogen peroxide produced by an active oxygen source in an aqueous scrubbing liquid by reacting said hydrogen peroxide by any of the following methods:

decomposition, neutralization and adsorption, and any combination thereof, and which do not form an organic peroxyacid compound.

All compounds cited in the specification are incorporated herein by reference.

SUMMARY OF THE INVENTION

The present invention includes a detergent composition comprising:

(a) a source of peroxide compounds; (b) a bleaching acid precursor composition comprising

i) an organic peroxyacid bleach precursor compound, ii) a hydrogen peroxide scavenger, wherein said organic peroxyacid bleach precursor compound and said hydrogen peroxide scavenger are physically close to said composition.

Preferably, said organic peroxyacid bleach precursor compound and said hydrogen peroxide scavenger are in intimate contact, most preferably in intimate admixture in said bleach precursor composition.

The hydrogen peroxide scavenger is selected from hydrogen peroxide reacting compounds with decomposition and / or neutralization and / or adsorption.

Preferably, hydrogen peroxide scavengers are selected from decomposition compounds, particularly heavy metal ions (HMI) and catalase and peroxydase type enzymes.

The invention also provides a process for preparing a detergent composition by the following steps:

(a) preparing a peroxyacid bleach precursor agglomerate by mixing the peroxyacid bleach precursor agglomerate with a hydrogen peroxide scavenger to which a binder is then admixed;

b) treating said agglomerates with a coating material,

(c) drying said agglomerates; and

d) introducing said dry coated agglomerates into a detergent composition comprising a source of peroxide compounds.

DETAILED DESCRIPTION OF THE INVENTION

An essential feature of the present invention is a source of peroxide compounds combined with a peroxyacid bleach precursor into a detergent composition. A preferred peroxide compound is hydrogen peroxide. A preferred source of hydrogen peroxide comprises percarbonate and perborate. Sources of the peroxide compound also include bleaching inorganic perhydrates, perphosphates, persulphates, and perborates.

Bleaching inorganic perhydrates

Inorganic perhydrate salts are preferred sources of hydrogen peroxide. These salts are normally in the form of a metal salt, preferably a sodium salt in an amount of from 1% to 40% by weight, more preferably from 2% to 30% by weight, most preferably from 5% to 25% by weight. detergent composition.

Examples of inorganic perhydrate salts include perborates and percarbonate. Inorganic perhydrate salts are usually alkali metal salts. The inorganic perhydrate salt can be used as a crystalline solid without further protection. However, for some perhydrate salts, it is preferred to provide granular compositions that utilize coated forms that provide better storage stability of the perhydrate salt in the granular composition.

Sodium perborate can be in the form of the monohydrate of nominal formula NaBO ₂ H ₂ O ₂ or the tetrahydrate NaBO ₂ H ₂ O ₂ .3H ₂ O. Sodium percarbonate, which is a preferred perhydrate for inclusion in compositions of the invention is an addition compound of the formula 2Na ₂ CO _3rd 3H ₂ O ₂ and which is commercially available in crystalline form. Percarbonate is preferably incorporated into the formulations in a coated form which ensures product stability.

Suitable coating materials to ensure product stability include mixed salts of dally soluble alkali metal sulfate and carbonate. Such coatings together with coating processes are described in GB Pat. No. 1,466,799, issued to Interox on March 9, 1977. The weight ratio of the mixed salt of the coating material to the percarbonate ranges from 1: 200 to 1: 4, preferably 1:99 to 1: 9 and most preferably 1:49 to 1:19. A preferred mixed salt is sodium sulfate and sodium carbonate having the general formula Na ₂ SO ₄ .n.Na ₂ CO ₂ , wherein n is 0.1 to 3, preferably 0.3 to 1.0, most preferably 0.2 to 0. , 5.

Other non-limiting examples of coatings containing silicate (alone or with borate salts or boric acids or other inorganic substances), waxes, oils, fatty soaps can also be used advantageously according to the present invention.

Peroxyacid bleach precursor

The peroxyacid bleach precursor comprises, as an essential component, an organic peroxyacid bleach precursor and a hydrogen peroxide scavenger.

Precursor bleaching organic peroxyacids

The compositions of the present invention also include peroxyacid bleach precursors (bleach activators). Peroxyacid bleach precursors are typically added in an amount of from 30% to 95% by weight. % of a bleach precursor, preferably at least 55% and most preferably at least 60% by weight of a bleach precursor; bleach precursor. Under absolute conditions, the peroxyacid bleach precursor is typically 1% to 20% by weight, more preferably 1% to 10% by weight, most preferably 1% to 7% by weight. a detergent composition.

Organic peroxyacid bleach precursors for use in the composition of the present invention typically contain one or more N- or O-acyl groups and thus the precursors may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, nitriles and acylated derivatives of imidazoles and oximes, and examples of such useful substances are described in GB-A-1 586 789.

Suitable esters are described in GB-A-836 988, 864 798,

147,871, 2,143,231 and EP-A-0 170 386. Acylation products of sorbitol, glucose and all carbohydrates with benzoylating agents and acetylating agents are also suitable.

Specific O-acylated precursor compounds include

3,5,5-trimethylhexanoyloxybenzenesulfonates, benzoyloxybenzenesulfonates, cationic benzoyloxybenzenesulfonates, nonanoyl-6-aminocaproyloxybenzenesulfonates, monobenzoyltetraacetylglucose and pentaacetylglucose. Phthalic anhydride is a suitable type of anhydride precursor. Suitable N-acyl compounds are disclosed in GB-A-855 735, 907 356 and GB-A-1 246 338.

Preferred imide-type precursor compounds include N-benzoylsuccinimide, tetrabenzoylethylenediamine, N-benzoyl substituted ureas and N, N-N'N 'tetraacetyl alkylenediamines wherein the alkylene group contains 1 to 6 carbon atoms, especially those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. A particularly preferred precursor compound is Ν, Ν-ΝΝΝ tetraacetylethylenediamine (TAED).

N-acylated lactam class precursor compounds are described generally in GB-A-955 735. While the broadest aspect of the invention contemplates the use of any lactam useful as a peroxyacid precursor, preferred materials include caprolactams and valerolactams.

Suitable caprolactam bleach precursors have the formula:

wherein R ¹ represents a hydrogen atom, an alkyl, aryl, alkoxyaryl, or alkylaryl group having 1 to 12 carbon atoms, preferably 6 to 12 carbon atoms.

Suitable valerolactams have the formula:

C CH-CH 2 x

II

R ¹ - C

CH ₂ - CH ₂ wherein R ¹ represents a hydrogen atom, an alkyl, aryl, alkoxyaryl or alkaryl group containing 1 to 12 carbon atoms, preferably 6 to 12 carbon atoms. In a particularly preferred embodiment, R ^{1 is} selected from the group consisting of phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.

Particularly preferred materials are those which are normally solid at <30 ° C, especially phenyl derivatives, for example benzoylvalerolactam, benzoylcaprolactam and substituted benzoyl analogs thereof such as chloro, amino, nitro, alkyl, aryl and alkoxy derivatives.

Caprolactam and valerolactam precursor materials, wherein the R ¹ moiety contains at least 6, preferably 6 to 12 carbon atoms, provide peroxyacids in perhydrolysis with a hydrophobic nature that allows nucleophilic and body soiling cleansing. Precursor compounds wherein R ¹ is from 1 to 6 carbon atoms provide hydrophilic bleaching species which are particularly effective for bleaching beverage stains s.

Mixtures of hydrophobic and hydrophilic caprolactams and valerolactams, usually in a weight ratio of 1: 5 to 5: 1, preferably 1: 1, can be used for satisfactory stain removal.

Another preferred class of bleach precursor materials includes cationic bleach activators derived from valerolactam and caprolactam compounds of the formula:

+

CH ₂ -CH ₂ where X is 0 or 1, R, R ¹ and R are each C 1 -C 10 alkyl or C 2 -C 4 hydroxyalkyl or [(C _y H _2y O)] _n - R ''', where y = 2-4, n = 1 to 20 and R' represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom and X represents an anion.

Suitable imidazoles include N-benzoylimidazole and N-benzoylbenzimidazole and other useful N-acyl-containing peroxyacid precursors include

N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Another preferred class of peroxide bleach activators are the amide substituted compounds of the following general formula:

R ¹ N (R ⁵ ) C (O) R ² C (O) L or R 1 -C (O) N (R ⁵ ) R ² C (O) L wherein R ¹ is an aryl or alkylaryl group having 1 to 14 atoms of

R ⁵ is H or an alkyl, aryl or C 1 -C 10 alkylaryl group and L can be essentially any leaving group. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains from 4 to 8 carbon atoms.

R ¹ is a straight chain or branched alkyl, substituted aryl or alkylaryl containing a branching, substitution or both and the source is either synthetic or natural, including, for example, tallow fat. For R ² , structural variations are analogous. The substituent is alkyl, aryl, halogen, nitrogen, sulfur or other typical substituent groups or organic compounds. Preferably R is hydrogen or methyl. R ¹ and R ^{5 should} not contain more than a total of 18 carbon atoms. Amide-substituted bleach activator compounds of this type are described in EP-A-0 170 386.

Precursors of benzoxazine organic peroxyacids

Also preferred are compounds of the benzoxazine type as described, for example, in EP-A-0 332 294 and EP-A-0 482 807, in particular with the general formula

including substituted benzoxazines of the type:

Wherein R 1 is hydrogen, alkyl, alkylaryl, aryl, arylalkyl, secondary or tertiary amines and wherein R ₂ , R 3, R 4 and R ₅ are the same or different substituents selected from hydrogen, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COOR 8 (where R 8 is hydrogen or alkyl) and carbonyl functions.

Particular preference is given to the benzoxazine-type precursor:

N

Hydrogen peroxide trap

The bleach precursor compositions useful for the purposes of the present invention comprise a hydrogen peroxide scavenger. In an essential aspect, the hydrogen peroxide scavenger and the organic peroxyacid bleach precursor are closely related, particularly in close contact, most preferably in intimate admixture with said composition to form a bleach precursor particle.

The hydrogen peroxide scavenger is selected from compounds that react with hydrogen peroxide via a decomposition, neutralization or adsorption process or combinations thereof.

Hydrogen peroxide scavengers reacting via decomposition process

Suitable compounds for the purposes of the invention that react with hydrogen peroxide via a decomposition process are selected from heavy metal ions, catalase enzymes, peroxidase enzymes, and nitroso compounds or mixtures thereof.

Heavy metal ions (HMI)

Heavy metal ions are present in the precursor composition as salts alone, in the form of a metal oxide or supported by a mineral compound.

When the heavy metal ions are used as the salt itself in the bleaching agent, it is preferred to separately add a heavy metal ion sequestrant to the detergent composition to mask the heavy metal ion, especially after the first stage of dissolution and / or dispersion of the peroxygen bleach precursor.

Preferably, the heavy metal ion sequestrant as described below is present in the detergent composition in a molar excess of the heavy metal ion. Preferably, the hydrogen peroxide scavenger is a heavy metal ion and is present in the precursor composition in an amount of less than 5 wt%, preferably less than 1 wt%, more preferably less than 0.1 wt%. a bleach precursor.

These heavy metal ions are selected from the elements contained in the third and fourth rows of the third to the twelfth columns of the periodic table. Preferred heavy metal ions are Fe, Cu, and Mn. The amount of iron, copper and manganese in the bleaching agent should be less than 5,000 ppm, preferably 1,000 ppm. The amount of copper should be less than 50 ppm.

Heavy metal ions can also be supported by mineral compounds. Suitable carrier materials for heavy metal ions are mineral materials that contain at least 200 ppm heavy metal ions, preferably at least 500 ppm.

A possible carrier material is a non-dimensional, phyllosilicate mineral material.

The non-dimensional phyllosilicate mineral material is preferably present such that the weight ratio of the non-dimensional phyllosilicate mineral material to the bleaching organic peroxyacid precursor or to said pretreated organic peroxyacid in the bleaching composition is from 1: 1 to 1:99, preferably from 1: 2 to 1:49 more preferably from 1: 3.5 to 1:19.

A non-three-dimensional phyllosilicate mineral material herein is a mini silicate mineral material that is a substantially flat (two-dimensional) film and which is formed by sharing three of the four oxygen atoms in each silicate tetrahedron with adjacent tetrahedra. This definition does not include those silicates that have more complex three-dimensional silicate binding structures that are occasionally assigned to skeletal minerals. Preferred non-dimensional phyllosilicate mineral materials herein include clay mineral materials and crystalline layered silicates. For clarity, it is to be understood that the term non-dimensional phyllosilicate mineral material as used herein does not include aluminosilicate sodium zeolite builders, which may, however, be included in the detergent compositions of the invention as optional builders.

The non-dimensional phyllosilicate mineral material is preferably present as a component of the agglomerate particle containing a bleach precursor of organic peroxyacids and optionally other detergent compounds, including polymeric organic binders.

λ / worthy carriers include crystalline layered silicates having the following formula:

NaMSi _x O _2x +, yH ₂ O where M represents sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are described in EP-A-0 164 514 and processes for their preparation are described in DE-A-34 17 649 and DE-A-37 42 043. Here, x in the above formula is usually 2, 3 or 4 and is preferably 2. Most preferred is 6-Na ₂ Si ₂ O ₅ , available from Hoechst AG as NaSKS-6.

The crystalline layered silicate material is preferably present in the granular detergent compositions as particles in intimate admixture with a solid, water-ionizable material. The solid, water-ionizable material is selected from organic acids, organic and inorganic acid salts, and mixtures thereof.

Enzymes as hydrogen peroxide scavengers.

Another preferred hydrogen peroxide scavenger with a hydrogen decomposition process is a catalase type enzyme. This enzyme, also called a heme-enzyme, catalyzes the decomposition of hydrogen peroxide into water and oxygen so that 1 mg of the enzyme breaks down at least 0.1 mmol of hydrogen peroxide / tin. at pH 7 and 25 ° C and is found in animal, plant cells, bacteria and fungi. The catalase comprises four tetrahedron-like subunits of the same size and approximate molecular weight of 240,000. Each subunit contains one polypeptide chain linked to one prosthetic group of gelatinous protophorphyrin IX. Catalase is usually introduced into the bleach precursor in an amount of less than 5%, preferably 1% of the precursor composition.

Preferred catalogs are Terminox ^R sold by NOVO Industries A / S and Fermocolase ^R sold by Finnsugar.

The peroxidase enzyme as a hydrogen peroxide scavenger is also suitable. The peroxidase enzyme includes, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chlorine and bromoperoxidase. When this enzyme is used, it is usually introduced into the bleach precursor in an amount of less than 5%, preferably less than 1% by weight. a precursor composition.

Another suitable compound as a hydrogen peroxide scavenger with a decomposition process is a nitro compound such as nitrosodimethylaniline.

Hydrogen peroxide scavengers reacting by the neutralization process

Suitable compounds for the purposes of the present invention which react with hydrogen peroxide by neutralizing said hydrogen peroxide are selected from the following, non-limiting list:

halogen compounds of formula Mx, wherein M is a metal and x is a halogen selected from Cl, Br and I

2. sulphite compounds (sodium sulphite or sodium bisulphite)

3. thiosulphates

4. thiols, of which thiourea and thioglycerol are preferred

5. Ascorbic acid

6. tertiary amines, of which nititanotriacetic acid is preferred

7. Sodium hypochlorite

8. Sodium triolybdate

9. glyoxylic acid

10. N-acetylcysteine

11. sulfide compounds

12. Barium hydroxide

When used, these compounds are incorporated into the bleach precursor in an amount of less than 10%, preferably less than 5% by weight. a bleach precursor.

Hydrogen peroxide scavengers reacting by adsorption process

Suitable hydrogen peroxide scavengers reacting with hydrogen peroxide by the absorption process are compounds selected from: activated carbon, especially NH4 activated carbon, dust and sand.

When used, these compounds are incorporated into the bleach precursor in an amount of less than 50%, preferably less than 20% by weight. a bleach precursor.

Any of the mixtures of hydrogen peroxide scavengers described above may also be used.

Preferred hydrogen peroxide scavengers suitable for the purposes of the present invention are those that react with and degrade hydrogen peroxide. Of these, heavy metal ions and catalase type enzymes are more preferred.

The introduction of additional components to the organic peroxyacid bleach precursor and to the hydrogen peroxide scavenger is particularly advantageous in processing the bleach precursor particles and also to increase the stability of the detergent compositions into which the particles are incorporated. In particular, some types of agglomerates require the addition of one or more binders to facilitate binding of the bleaching organic peroxyacid precursor and hydrogen peroxide scavenger to obtain particles with acceptable physical properties. The binders may be present in an amount of 0% to 40% by weight. particle. Preferably, the binders are in intimate admixture with the organic peroxyacid bleach precursor and hydrogen peroxide scavenger. The binders preferably have a melting point between 30 ° C to 70 ° C or a considerable water solubility. The binders are preferably present in an amount of 1 to 30 wt. particles, most preferably in an amount of 5 to 20% of the particle.

Preferred binders include C 10 to C 20 alcohol ethoxylates containing 5 to 100 moles of ethylene oxide per mole of alcohol, more preferably C 15 to C 20 primary alcohol ethoxylates containing 20 to 100 moles of ethylene oxide per mole of alcohol. Preferred ethoxylate binders are tallow alcohol ethoxylated with 15 moles of ethylene oxide per mole of alcohol (TAE 25) and tallow alcohol ethoxylated with 50 moles of ethylene oxide per mole of alcohol (TAE 50).

Other preferred binders include some polymeric materials. Plyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000 and polyethylene glycols with an average weight of 600 to 10,000 are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, wherein maleic anhydride constituting at least 20 mol% of the polymer are further examples of polymeric materials useful as binders. A preferred binder for use in the present invention is a copolymer of maleic acid and acrylic acid having a molecular weight of 70,000. An acrylic acid homopolymer is also suitable. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the above-mentioned C 10 -C 20 alcohol ethoxylates containing 5 to 100 moles of ethylene oxide per mole. Other examples of binder agents include C ₁₀ -C ₂₀ mono- and diglycerol ethers, as well as C ₁₀ -C ₂₀ fatty acids. Solutions of certain inorganic salts, including sodium silicate, are also suitable for these purposes.

Cellulose derivatives including nonionic alkylcellulose derivatives such as methylcellulose, carboxymethylcellulose, (hydroxypropylmethylcellulose) and hydroxyethylcellulose and homo- or copolymeric polycarboxylic acid or salts thereof are another example of suitable binders.

The particles may also contain other ingredients which are conventionally present in detergent compositions, provided that these ingredients are not incompatible per se. Examples of such ingredients include lime soap dispersants and fillers.

The bleach precursor particles may also be coated. Said coating material may be selected from polyacrylic acid, cellulose acetate, copolymer polycarboxylic acid and a monomeric aliphatic carboxylic acid such as citric acid. Examples are given in

EP 0 382 464 and WO 92/13 798. These ingredients and their amounts are described below, but the total amount of ingredients normally ranges from 5% to 50% by weight. a bleach precursor composition. Peroxyacid precursors should constitute the major component of the precursor composition, i.e. from 50% to 95% by weight. % particles, preferably at least 55 wt. % and most preferably at least 60 wt. particle.

If the bleach precursor particles are coated, the preferred optional component is a dusting agent which is used in an amount of from 1% to 5% by weight, especially for those compositions wherein said bleach precursor is in an agglomerated form. This dusting component improves the flow of the precursor composition and preferably takes the form of a water-insoluble inorganic compound having a particle size of < 50 microns, preferably 1 to 10 microns. Examples of such compounds include synthetic zeolites and hydrophobic silica. The application of the dusting agent can be carried out with or after application of the coating material.

Peroxyacid bleach precursor compositions can be prepared by a variety of methods using equipment known in the art, and the processes can be batch or continuous. In the batch process, an Eirich or Lodige FM agglomeration is used, while in a continuous process a Shugi mixer or a Lodige CB or KM mixer is used. The combination of Lodige CB and KM mixers is preferred.

A preferred process for preparing the detergent composition of the present invention comprises the following steps:

(a) preparing a peroxyacid bleach precursor agglomerate by mixing the peroxyacid bleach precursor agglomerate with a hydrogen peroxide scavenger and then adding a binder;

b) treating said agglomerates with a coating material,

(c) drying said coated agglomerates; and

d) introducing said dry coated agglomerates into a detergent composition comprising a source of peroxide compounds.

Additional detergent components

The detergent compositions of the invention may also contain other detergent ingredients. The precise properties of these additional ingredients and the amount used will depend upon the physical form of the composition and the nature of the cleaning operation for which it will be used.

The compositions of the invention may be formulated, for example, as detergent compositions for hand and machine washing, as additional laundry compositions, and as pre-cleaners for soiled fabrics.

The compositions of the invention preferably comprise one or more additional detergent ingredients selected from the following: surfactants, fillers, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, clay suspending and anti-redeposition agents (anti-redeposition agents) and corrosion inhibitors and optical brighteners.

Surfactants

The optional detergent composition of the invention comprises a surfactant, anionic, cationic, nonionic ampholytic, amphoteric and zwitterionic, and mixtures thereof.

A typical surfactant content is 0.1 to 60% by weight. More preferred is 1 to 35 wt%, most preferably up to 20 wt%.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes and species is disclosed in USP 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Other examples are in Surface Active Agents and Detergents (Vol. I and II, Schwartz, Perry, and Berch). Suitable cationic surfactants are listed in USP 4,259,217 issued to Murphy on March 31, 1981.

When ampholytic, amphoteric and zwitterionic surfactants are used, they are generally used in combination with one or more nonionic surfactants.

Tionic surfactants

Substantially any anionic surfactant useful for cleaning purposes can be used in the detergent compositions herein. These may be salts (eg, Na, K, ammonium, substituted ammonium salts such as mono-, di- and triethanolamine) of anionic sulfate, sulfonate, carboxylate, and sarcosinate surfactant.

Other anionic surfactants are isethionates such as acyl isethionates, N-acyltaurates, methyltauride fatty amides, alkyl succinates and sulfosuccinates, sulfo succinate monoesters (especially saturated and unsaturated C 1-6 alkylsulfonates). C₁₈monoesters), diesters of sulfosuccinate (in particular saturated and unsaturated C_G- C₁₄diesters), N-acyl sarcosinates. Also suitable are optionally hydrogenated resin acids such as rosin, hydrogenated rosin, and optionally hydrogenated resin acids contained in or derived from body oil.

Anionic sulfate surfactants

Anionic sulfate surfactants for use in the invention include linear and branched primary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerine sulfates, alkylphenol ethylene oxide ether sulfates, C ₅ -C ₁₇ -alkyl-N- (C ₁ -C ₄ -alkyl), and -N- (C 1-6). -C ^-hydroxyalkylglucamine sulfates, and alkyl polysaccharide sulfates, such as alkyl polyglucoside sulfates, (nonionic unsulfated compounds described herein).

The alkyl ethoxy sulfates are preferably selected from the group of C 8 -C 18 -alkyl sulfates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. A more preferred alkyl ethoxylate surfactant is a C8-C8-alkylsulfate which has been ethoxylated with 0.5 to 20, preferably 0.5 to 5 moles of ethylene oxide per molecule.

Anionic sulfonate surfactants

The anionic sulfonate active agents useful herein are salts of C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C ₈ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerin sulfonates, fatty oleyl glycerin sulfonates, and any mixtures thereof, and any mixtures thereof. .

Anionic carboxylic surfactants

Anionic carboxylic surfactants suitable for use herein include alkyl ethoxycarboxylates, alkyl polyethoxy polycarboxylates, and soaps (alkylcarboxylates), particularly some of the secondary soaps described herein.

Preferred alkyl ethoxycarboxylates for use herein include those of formula RO (CH ₂ CH ₂ O) _X CH ₂ COO-M ⁺ , wherein R is C 8 -C 8 alkyl, x is 0 to 10, and the ethoxylate distribution is such that the amount of material at X = 0 is less than 20 wt%, at X > 7 it is below 25 wt%; an average X is 2 to 4 when the average R is ^C 13 or less, and an average X is 3 to 10 when the average R is greater than C ₁₃ ; and M is a cation, preferably an alkali metal, a caustic earth metal, ammonium, mono-, dia-triethanolammonium, most preferably sodium, potassium, ammonium, and mixtures thereof with magnesium ions. Preferred alkyl ethoxycarboxylates are those wherein R is C ₁₂ -C ₁₈ alkyl.

As the alkyl polyethoxy polycarboxylate surfactants having the formula RO- (CHR ₁ -CHR ₂ -O) -R ₃ wherein R is an alkyl group of ^C 6 ^_C 18 ^{'x e} j ^{1 and} 25, R -, ^ and _R2 are selected from hydrogen, methyl, succinic or hydroxysuccinic acid radicals and mixtures thereof, wherein at least one of R 1 or R ₂ is a succinic or hydroxy succinic acid radical, and R ₃ is selected from hydrogen, substituted or unsubstituted hydrocarbon having 1; up to 8 carbon atoms, and mixtures thereof.

Anionic secondary soaps as surfactants

Preferred soap actives are secondary soaps containing a carboxyl unit attached to the secondary carbon. The secondary carbon may be in a ring structure such as p-octylbenzoic acid, or in alkyl substituted cyclohexyl carboxylates. Preferred secondary soaps should contain no ether or ester linkages, and no hydroxyl groups. Even in the parent group (in the amphiphilic part) there must be no nitrogen atoms. Secondary soaps as surfactants usually contain a total of 11 to 15 carbon atoms, although up to 16, e.g., p-octylbenzoic acid, can be tolerated.

The following general structures further illustrate some secondary soaps as surfactants:

A. A highly preferred class of secondary soaps comprises secondary carboxyl materials of the formula R ³ CH (R ⁴ ) COOM, where R ³ is

- 27 CHg (CH 2) x and CH ₃ (CH) ₃ y, wherein y may be 0 or an integer from 1 to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6 to 10, preferably 7 to 9, most preferably 8.

B. Another preferred class of secondary soaps are carboxyl compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit, i.e., they are secondary soaps of the formula R ⁵ -R ⁶ -COOM, wherein R ⁵ is C ⁷ -C ¹⁰ alkyl or alkenyl, more preferably CC, and R is a ring structure such as benzene, cyclopentane or cyclohexane. (Note: R ⁵ may be ortho, meta or para relative to the ring carboxyl.)

C. Yet another preferred class of secondary soaps consists of secondary carboxyl compounds of the formula

CH ₃ (CHR) _k - (CH ₂ ) _m - (CHR) _n -CH (COOM) (CHR) _θ - (CH ₂ ) _p - (CHR) _q -CH ₃ , wherein each R is C ₃ -C alkyl ₄ , wherein k, n, o, q are integers from 0 to 8, provided that the total number of carbon atoms (including carboxyl) is in the range of 10 to 18.

In each of the above formulas A, B, C, M is any suitable counterion, especially promoting water solubility.

Highly preferred secondary soaps for use herein are water-soluble members of the group consisting of water-soluble salts of 2-methyl-1-undecanoic acid,

2-ethyl-1-decano, 2-propyl-1-nonanoic, 2-butyl-1-octane and 2-pentyl-1-heptane.

Alkali metal sarcosinates as surfactants

Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CONI ¹ ) CH 2 -COOM, wherein R is a linear or branched alkyl or alkenyl C ¹ -C 17, R ¹ is a C 1 -C ₄ alkyl, and M is an alkali metal ion . Preferred examples are myristyl and oleyl methyl sarcosinates in the form of their sodium salts.

Nonionic surfactants

Essentially any nonionic surfactant may be used in the detergent compositions herein. The following are non-limiting examples of individual classes of these substances.

Nonionic amides of polyhydroxy fatty acids as surfactants

Nonionic polyhydroxy fatty acid amides suitable for

The uses herein have the structural formula RCONR ^X Z, wherein: R is H, hydrocarbyl C 1 -C 4, 2-hydroxyethyl, 2-hydroxypropyl, or mixtures thereof, preferably C 1 -C 4 alkyl, more preferably C 1 -C 4 or C 2 alkyl, most preferably C 8 alkyl (i.e. methyl); R ² is hydrocarbyl C 5 -C ₂₁ , preferably unbranched C ₈ -C ₁₈ -alkyl or alkenyl, more preferably straight C ₁₁ -C ₁₇ -alkyl or alkenyl, or mixtures thereof; Z is a linear chain polyhydroxyhydrocarbyl with at least 3 hydroxyls attached directly to the chain, or alkoxylated derivatives thereof (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar by reductive amination; most preferably Z is glycityl.

Nonionic condensates of alkylphenols as surfactants

Preferred for use herein are the condensates of polyethylene, polypropylene, and polybutylene oxide and alkylphenols. Polyethylene oxide condensates are generally preferred. These compounds form the condensation products of alkylphenols having an alkyl of 6 to 18 carbon atoms, optionally in a branch, and alkylene oxide.

Nonionic ethoxylated alcohols as surfactants

Suitable for use herein are the alkyl ethoxylate condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may optionally be branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Most preferred are the condensation products of alcohols with an alkyl of 8 to 20 carbons, 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic ethoxylated / propoxylated fatty alcohols as surfactants

Suitable ethers for use herein are ethoxylated C8-C18 fatty alcohols and mixed ethoxy / propoxylated fatty alcohols, especially those soluble in water. Of the ethoxylated alcohols, C ^-C ^ g alcohols are preferred at an ethoxylation degree of 3 to 50, most preferably C jsou-C ^g alcohols at an ethoxylation degree of 3 to 40. Of the mixed ethoxy- / propoxylated fatty alcohols, preference is given to those having an alkyl of 10 to 18 carbon atoms at an ethoxylation degree of 3 to 30 and a propoxylation degree of 1 to 10.

The nonionic EO / PO condensates with propylene glycol λ / suitable for the use described herein are the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a preferred molecular weight in water. Examples of compounds of this type are some of the commercially available Pluronic surfactants sold by BASF.

Nonionic EO condensation products with propylene oxide / ethylenediamine adducts

Suitable for use herein are the condensation products of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. The hydrophobic half of these products consists of ethylene diamine reaction products and an excess of propylene oxide, and typically has a molecular weight of 2,500-3,000. Examples of nonionic surfactants of this type are some of the commercially available Tetronic ™ compounds sold by BASF.

Nonionic alkyl polysaccharide surfactants

Alkylpolysaccharides suitable for use herein are described in USP 4,565,647 (Llenado) of Jan. 21, 1986, wherein the hydrophobic group has 6 to 30 carbon atoms, preferably 10 to 16, and the polysaccharide, e.g., polyglycoside, and the hydrophilic group has

1.3 to 10, more preferably 1.3 to 3, and most preferably 1.3 to 2.7 carbohydrate units. Any reducing carbohydrate having 5 or 6 carbon atoms may be used, e.g., glucose, the galactose moiety and the galactosyl moiety may be replaced by the glucosyl moiety. (The hydrophobic moiety can optionally be attached to the 2-, 3-, 4-, etc. position, thereby bringing glucose or galactose to the glucoside or galactoside.) The intersaccharide linkages may be, for example, between one position of another carbohydrate unit and the 2-, 3-position. -, 4-, and / or 6- previous carbohydrate units.

Preferred alkyl polyglycosides have the formula

R ² O (C _n H 2 _n O) t (glycosyl) _χ , wherein R ² is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof wherein the alkyls have 10 to 18, more preferably 12 to 14 carbon atoms; n is 2 or 3, t is 0 to 10, preferably 0, and X is 1.3 to 8, more preferably 1.3 to 3, most preferably 1.3 to 2.7. Glycosyl is preferably derived from glucose.

Nonionic fatty acid amides as active substances

The fatty acid amides for use herein have the formula R 1 CON (R ⁷ ) 2 wherein alkyl is 7 to 21, more preferably 9 to 17 carbon atoms and each R ⁷ is selected from the group consisting of hydrogen, C ₄ -C ₄ alkyl, hydroxyalkyl C _{4 - 4} , and - (C ₂ H ₄ O) _X H, where x is 1 to 3.

Amphoteric surfactants

Suitable amphoteric active agents for use herein include amine oxides and alkylamphocarboxylic acids.

A suitable example of an alkylamphocarboxylic acid for use herein is Miranol (TM) C2M Conc, manufactured by Miranol, Inc, Dayton, NJ.

Amine oxide surfactants

Amine oxides useful herein include compounds of formula R ³ (OR ⁴ ) χΝθ (R ⁵ ) 2 wherein R ³ is selected from alkyl, hydroxyalkyl, acylamidopropoyl and phenyl or mixtures thereof containing from 8 to 26 carbon atoms, preferably from 8 to 18 C atoms; R ⁴ is alkylene or hydroxyalkylene of 2 to 3, more preferably 2 C atoms, or mixtures thereof; x is 0 to 5, more preferably 0 to 3; and each R ⁵ is alkyl or hydroxyalkyl of 1 to 3, more preferably 1 to 2 C atoms, or is a polyethylene oxide group having 1 to 3, more preferably 1 ethylene oxide group. The R ⁵ groups can be linked to each other, e.g. via an oxygen or nitrogen atom, to form a cyclic structure.

Amine oxide active substances comprise C ₄ q_ ₄ and q alkyldimethylamine Cg_ ₄ g alkoxyethyldihydroxyethyl oxide. Examples of such materials are: dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, dimethyldodecylamine oxide, dipropyl-tetradecylamine oxide, methylethyl hexadecylamine oxide, dodecylamidopropyl dimethylamino oxide, cetyl dimethylamino oxide, stearyl dimethylamine oxide, stearyl dimethylamine oxide, stearyl dimethylamine oxide -octadecylamine oxide. Preferred are C ₄ G_ _G-4 alkyl dimethylamine oxide, and C ₁ g_-acylamido32 ₁ g alkyl dimethylamine oxide.

Zwitterionic surfactants

It is also possible to import zwitterionic active ingredients into the detergent compositions of the present invention. These may be briefly described as derivatives of secondary or tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium and tertiary sulfonium compounds. Examples of zwitterionic active agents useful herein are betaine and sultain.

Surface active betaines

Betaines useful herein are compounds having the formula R (R ¹ ) ² N ⁺ R ² COO ', wherein R is C 8 -C 18 -carbyl, preferably C ₁ -C 18 -alkyl or C ₁₀ -C ₁₆ -acylaminoalkyl, each R ¹ π.

is typically C ₁₃ -alkyl, preferably methyl, and R is

_L _ C ₅ hydrocarbyl, preferably C ₁ _ ₃ alkylene, and preferably

C ₁ _2-alkylene. Examples of suitable betaines are: coconut acylamidopropyldimethyl-betaine;

C 14-14 acylamidohexyldiethyl-betaine;

4 [C ₁₄ _ ₁₆ -acylmethylamidodiethylamonio] -1-carboxybetaine;

^c i6 -18 ^-ac yl ° ^am id cli ^m ethyl betaines;

^c i2 -16 ~ ^AC yl ^am ičlopentandiethyl betaines;

Ci2_ie ^_ac yl ^methyl thylamidodi ^{methyl-betaine.} Preferred betaines are C ^ -ig-dimethylamoniohexanoát _C4 and ₁ g g_-acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaines are also suitable for use herein.

Surface-active sultains

According to the present invention are useful sultaines are compounds of the formula R (R ¹⁾ 2 N ⁺ R ² SO 3 "wherein R is a _Cg _ _g hydrocarbyl, preferably C ₁₀ _ ₁₆ -alkyl / preferably C ₁₂ _ ₁₃ -alkyl, each R ¹ typically it is

C - ^ - j-alkyl, preferably methyl, and R ² is C ₁ _ ₆ hydrocarbyl, preferably C ₁ _3-alkylene or hydroxyalkylene.

Ampholytic surfactants

Ampholytic surfactants can be used in the detergent composition of the invention. These can be broadly described as aliphatic derivatives of secondary or tertiary amines, or as aliphatic derivatives of heterocyclic secondary and tertiary amines. amines in which the aliphatic radical may be a straight or branched chain.

Cationic surfactants

Cationic surfactants may also be used in detergent compositions, of which suitable are quaternary ammoniums derived from mono- ^C 6-16 ', more preferably ^C 6-10 -alkyl or alkenylammonium active materials, wherein the remaining N-positions are substituted with methyl , hydroxyethyl or hydroxypropyl.

Water-soluble binder (carrier) compound

The detergent compositions of the present invention comprise as a preferred optional component a water-soluble binder (parent) present in a typical amount of 1-80%, more preferably 10-70%, and most preferably 20-60% by weight of the composition.

Preferred water-soluble binder (base) components are water-soluble monomeric polycarboxylates or acid forms thereof, homo- or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid consists of at least two carboxylic radicals separated by no more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, silicates, and mixtures of any of the foregoing.

The carboxylate or polycarboxylate component may be of a monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and efficiency.

Suitable single-carboxylate carboxylates are the water-soluble salts of lactic acid and glycolic acid, and ether derivatives thereof. The two carboxylate polycarboxylates are the water-soluble salts of succinic, malonic, (ethylenedioxy) diacetic, maleic, diglycolic, tartaric, tartronic and fumaric acids, as well as ether carboxylates and sulfinyl carboxylates. In particular, the three carboxylate polycarboxylates are the water-soluble citrates, aconitates and citraconates, as well as amber derivatives such as the carboxymethyloxysuccinates described in British Patent No. 5,601,549.

379 241, the lactoxysuccinates disclosed in BP No. 1 389 732 and the amino succinates disclosed in Dutch application 7205873, and oxoypolycarboxylates such as the 2-oxy-1,3,3-propanetricarboxylates disclosed in BP No. 1 387 447.

Polycarboxylates containing four carboxylates are the oxydisuccinates disclosed in BP No. 1,261,829, 1,1,2,2-ethanethetracarboxylates, 1,1,3,3-propanetetracaroboxylates, and 1,1,2,3-propane tetracarboxylates.

Polycarboxylates with sulfosubstituents are sulfosuccinic acid derivatives disclosed in BP 1 398 421 and BP 1 398 422, and in USP 3 936 448, and the sulfonated pyrolyzed citrates described in BP 1 439 000.

Alicyclic and heterocyclic polycarboxylates are cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadiene pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2 5,5-tetrahydrofurantetracarboxylates,

2,3,4,5,6-hexanehexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.

Aromatic polycarboxylates are mellitic acid, pyromellitic acid and phthalic acid derivatives reported in BP

425 343.

Among the polycarboxylates mentioned above, hydroxycarboxylates having up to three carboxyl groups per molecule, in particular citrates, are preferred.

The starting acids of the monomeric and oligomeric polycarboxylate chelating agents or mixtures thereof and mixtures of their salts, such as citric acid or mixtures thereof and citrates, are also considered to be useful binding (carrier) components.

Borate binders as well as the borate-forming binder components during detergent storage or washing are also useful, but are not preferred under washing conditions below 50 ° C, especially below 40 ° C.

Examples of carbonate binder components are the alkaline earth and alkali metal carbonates, including n- and acidic sodium carbonate, and mixtures thereof with ultrafine calcium carbonate, described in German application no.

321,001, published Nov. 15, 1973.

Specific examples of water-soluble phosphate binder components are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymer / phosphate having a degree of polymerization of 6 to 21, and phytic acid salts.

Suitable silicates are water-soluble sodium silicate having a SiO ₂ : Na ₂ O ratio of 1.0 to 2.8, more preferably 1.6 to 2.4, and most preferably 2.0. The silicates may be in the form of an anhydride or a hydrated salt. Sodium silicate with a ratio of 2.0 is the most preferred silicate.

Silicates are present in the detergent composition of the invention in an amount of 5 to 50%, more preferably 10 to 40% by weight of the composition.

Partially soluble and impermeable binder (carrier) component

The detergent compositions of the invention may comprise a partially soluble or insoluble carrier component in a typical amount of 1-80%, more preferably 10-70%, and most preferably 20-60% by weight of the composition.

An example of a partially soluble component are crystalline layered silicates. Examples of water-insoluble components are sodium aluminosilicates.

Crystalline layered sodium silicates have the general formula ^NaMSi 2x + ly ^H 2 ° 'where M is sodium or hydrogen, x is a number from 1.9 to 4, and is a number from 0 to 20. Crystalline layered sodium silicates of this type are described in EP- A-0 164 514, and methods for their preparation in DE-A-34 17 649 and DE-A-37 42 043. For the purposes of the present invention, x in the formula above has a value of 2, 3, or 4, preferably 2.

The most preferred material is delta-Na ₂ Si ₂ O ₅ , available from Hoechst AG under the designation NaSKS-6.

The crystalline layered sodium silicate material is preferably used in granular detergent compositions as particles in intimate admixture with a solid, water-soluble ionizable material for which some of the organic acid, organic and inorganic acid salts, and mixtures thereof are selected.

Suitable aluminosilicate zeolites have the unit on the formula _of [(A10 _{2) z} (SiO ₂₎ y] H ₂ O, the emanations are at least 6; the molar ratio of ky is 1.0: 0.5, and is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate material is in hydrated form and preferably crystalline, containing 10 to 28, more preferably 18 to 22. % wt. bound water.

The aluminosilicate ion exchange materials may be of natural origin, but synthetic is preferred. Synthetic crystalline aluminosilicate ion exchangers are available under the designation Zeolite A, Zeolite B,

Zeolite P, Zeolite X, Zeolite HS, and mixtures thereof.

Zeolite A has the formula:

₁₂ I (A1O _{2) 12} 12 - ^xH 2 ° 'where x is about 30, especially about 27. Zeolite X has the formula

Per _g6 [(A1O ₂ ) _g6 (SiO ₂ ) ₁₀ g] - ^276H 2 ° Masking of heavy metal ions

The detergent compositions of the present invention preferably comprise a heavy metal ion masking agent. By this is meant components useful herein to form a chelate (complex) with heavy metal ions, especially after the first degree of dissolution and / or dispersion of the peroxyacid bleach precursor. For this purpose, the heavy metal ions are present in the detergent compositions as a component separate from the peroxyacid bleach precursor. These components also have a chelating capacity for calcium and magnesium, but preferably exhibit selectivity in binding heavy metal ions such as iron, manganese and copper.

These heavy metal ion maskers are usually present in an amount of 0.005 to 20%, preferably 0.1 to 10%, more preferably 0.25 to 7.5%, and most preferably 0.5 to 5% by weight of the composition.

These heavy metal ion sequestrants are acidic in nature, e.g. having phosphonium and carboxyl functional groups, and may be present either in their acid form or as a complex / salt with a suitable countercation such as an alkali metal alkali, ammonium, or substituted ammonium ion, or any mixtures thereof. Water-soluble complex / salt is preferred. The molar ratio of said countercation to the chelate is preferably at least 1: 1.

Suitable heavy metal ion sequestrants for use herein are organic phosphonates such as aminoalkylene polyes (alkylene phosphonates), ethane-1-hydroxy diphosphonates, and alkali metal nitrilotrimethylene phosphonates.

Of the above, diethylenetriamine penta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexymethylenediaminetetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate are preferred.

Other suitable chelating agents are nitrilotriacetic acid and polyaminocarboxylic acids, such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediaminindiantar, ethylenediaminindiglutaric,

2-hydroxypropylenediamine disuccinate, and salts thereof.

Particularly preferred is ethylenediamine-N, N-disuccinic acid (EDDS) or its alkali metal, caustic earth, ammonium or substituted ammonium salts thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt, or a complex thereof. Examples of preferred sodium EDDS salts are Na ₂ EDDS and Na 2 EDDS. Examples of preferred magnesium EDDS complexes are MgEDDS and Mg ₂ EDDS.

Other preferred heavy metal masking ions for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryliminodiacetic acid as described in EP-A-0 317 542 and EP-A-0 399 133.

Also preferred are iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid as described in EP-A-0 516 102. Beta-alanine-N, Ν'- di-acetic, asparagyl-N, Ν'-di-acetic, aspargyl-N-monoacetic and imino-disuccinic acids described in EP-A-0 509 382.

EP-A-0 476 257 discloses amine-based maskers.

EP-A-0 510 331 discloses suitable collagen, keratin or casein derived maskers. EP-A-0 528 859 discloses an alkylimino diacetic acid as a suitable masker. Also suitable are dipicolinic and 2-phosphonobutane-1,2,4-tricarboxylic acid as well as glycinamide-N, Ν'-disuccinic acid (GADS).

Bleaching catalyst

Preferably, the composition comprises a bleach catalyst comprising a transition metal.

One type of bleaching catalyst is a catalytic system consisting of a heavy metal cation with a defined bleaching catalytic activity, such as copper, iron or manganese, a cationic metal cation with little or no catalytic activity, such as zinc or aluminum, and a masker with a defined catalytic stability constant. and auxiliary cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are described in U.S. Patent 4,430,243.

Another type of bleach catalyst is the manganese-based complexes disclosed in U.S. Patent 5,246,621 and U.S. Patent 5,244,594. Preferred examples of such catalysts are Mn ^iv 2 (u-0) ₃ (1,4,7-trimethyl-1,4). 7-triazacyclononane) ₂ - (PF _g ) ₂ ,

1η ¹ - ^ 2 ( ^µ- °) i (µ-OAc) 2 (η 4,7-trimethyl-1,4,7-triazacyclononane) 2 (C104) 2 # Mn ^IV 4 (µ-0) g (1 4,7-triazacyclononane) ₄ - (C _{10 4} ) 2, ^η ¹ - ( ¹ -O) (µ-OAc) ₂ - (1,4,7-trimethyl-1,4,7-triazacyclononane) _2- (C10 ₄ ) ₃ and mixtures thereof. Others are described in European Patent Application No. 0 549 272. Other ligands suitable for this use are 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 1,1,9-triazacyclododecane. 2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

Examples of suitable bleach catalysts are disclosed in U.S. Patent 4,246,612 and U.S. Patent 5,227,084. See also U.S. Patent 5,194,416, which discloses mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4). 7-Triazacyclononane) (OCH4) 4 - (PFg) Yet another bleach catalyst disclosed in U.S. Patent 5,114,606 is the water soluble manganese (III) and / or (XV) complex with a ligand that is a non-carboxylic polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands are sorbitol, idite, dulsit, mannitol, xylite, arabite, adonite, meso-erythrite, meso-inosit, lactose and mixtures thereof.

U.S. Patent 5,114,611 discloses a bleach catalyst consisting of a complex of transition metals, including Mn, Co, Fe, and Cu, with a non-(macro) -cyclic ligand. These ligands have the formula:

R ² R ³

R ¹ -N = CBC = NR ⁴ wherein any of R ¹ , R ² , R ³ and R ⁴ is selected from the group consisting of hydrogen, a substituted alkyl or aryl group such that each R ¹ -N = CR ² and R ³ -C = NR ⁴ form a five or six membered ring. This ring may be further substituted. B is a bridging group selected from the group consisting of O, S, CR ⁵ R ⁶ , NR ⁷ and C = O, wherein each R ⁵ , R ⁶ and R ⁷ may be H, alkyl or aryl, including substituted or unsubstituted groups . Preferred ligands are pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. These rings may preferably be substituted with substituents such as alkyl, aryl, alkoxy, halogen and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts are Co, Cu, Mn, Fe, -bispyridylmethane and -bispyridylamine complexes. Very preferred catalysts are Co (2,2'-bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine cobalt (II), trisdipyridylamine cobalt (II) perchlorate, Co (2,2-bispyridylamine) ₂ 0 ₂ C10 ₄ , bis - (2,2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof.

Other examples are binuclear manganese complexes with tetra-N-dentate and bi-N-dentate as ligands, including N ^ Mn ¹¹¹ (u-0) 2Mn ^IV N4) ⁺ and [Bipy2Mn ¹¹¹ (u-0) 2Mn ^Iv byte ₂ l] - (C1O _{4) 3rd}

Other bleach catalysts are described in European Patent Application No. 0 408 131 (cobalt complex catalysts), European Patent Application Nos. 0 384 503 and 0 306 089 (metal-poryphyrin catalysts), in US Patent 4,728,455 (manganese / multidentate) ligand), U.S. Pat. No. 4,711,748 and European Patent Application No. 0 224 952 (manganese absorbed on an alumino-silica catalyst), U.S. Pat. No. 4,601,845 (aluminosilicate carrier with manganese and a zinc or magnesium salt), U.S. Pat. U.S. Patent 4,626,373 (manganese / ligand catalyst), U.S. Patent 4,119,557 (ferric complex catalyst), DE 20,540,019 (cobalt chelate catalyst), Canadian Patent 866,191 (transition metal salts), U.S. Patent 4,430 243 (chelates with manganese cations and non-catalysing metal cations) and US Patent 4,728,455 (manganese gluconate catalyst).

In the compositions of the invention, a bleach catalyst is used in a catalytically effective amount. By catalytically effective amount is meant an amount sufficient under any conditions of the comparative test to enhance the whitening effect and to remove the stain or stains from the substrate under investigation. Test conditions vary depending on the washing equipment and user's habits. Some users choose very hot water for washing machine operations, others choose hot or cool water. It goes without saying that these considerations affect the catalytic efficiency of the bleach catalyst and accordingly the amount of bleach catalyst in detergent and bleach formulation formulations needs to be adjusted accordingly. In practice, and not for limitation, the compositions and processes disclosed herein can be adjusted to the order of at least 1 part of active bleach catalyst to 10 million parts of scrubbing fluid, preferably a ratio of 1 to 200 ppm of catalyst in the scrubbing fluid. To illustrate this point, the order of magnitude of 3 micromoles of manganese catalyst at 40 ° C, pH 10 are effective under European conditions using a perborate and a bleach precursor. To achieve the same results under US conditions, it is necessary to increase the concentration 3 to 5 times.

Enzyme

Another preferred ingredient to be used in detergent compositions is one or more enzymes.

Suitable enzymes are commercially available lipases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases, which are commonly incorporated into detergent compositions. Suitable enzymes are described in U.S. Patents 3,519,570 and 3,533,139.

Preferred, commercially available protease enzymes are sold under the trade names Alcalase, Savnas, Primase, Durazy and Esperase by Novo Industries AS (Denmark), under the trademarks Maxatase, Maxacal and Maxap by Gist-Brocades, further sold by Genecor International and finally by Solvay Enzymes under the trade names Opticlean and Optimase. The protease enzyme is incorporated into the compositions of the invention in an amount of 0.0001% to 4% active enzyme by weight of the composition.

Preferred amylases are, for example, alpha-amylases obtained from a particular strain of B. licheniformis, described in more detail in GB patent 1,269,839 (Novo). Preferred commercially available amylases are, for example, the preparations sold under the trade name Rapidase by Gist-Brocades and under the name Termamyl and BAN by Novo Industries A / S. The amylase enzyme is used in the composition of the invention in an amount of 0.0001% to 2% active enzyme by weight of the formulation.

The lipolytic enzyme (lipase) is used in an amount of active lypolytic enzyme of 0.0001 to 2% by weight, more preferably 0.001 to 1% by weight, most preferably 0.001 to 0.5% by weight. per weight of preparations.

The lipase may be of fungal or bacterial origin, such as from a lipase-producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp., including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipases from chemically or genetically modified mutants of these strains may also be used.

A preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in European patent EP-B-0 218 272.

Another preferred lipase is obtained by cloning the z gene

Humicola lanuginosa and inserting (squeezing) this gene into Aspergillus oryzae as a host as described in European patent application EP-A-0 258 068, which lipase is commercially available from Novo Industries A / S Bagsvaerd, Denmark under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al., Issued March 7, 1989.

Organic polymer compounds

Organic polymeric compounds are particularly preferred components of the detergent compositions herein. By this is meant essentially any polymeric organic compound commonly used in detergent compositions as a dispersant and anti-redeposition agent and anti-dirt suspending agent, in addition to the high molecular weight organic polymeric compounds described as clay flocculants.

The organic polymeric compound is used in a detergent composition of the invention in a typical amount of 0.1 to 30%, more preferably 0.5 to 15%, and most preferably 1 to 10% by weight of the composition.

Examples of organic polymeric compounds are the water-soluble organic homo- and co-polymeric polycarboxylic acids and their salts, in which the polycarboxylic acid consists of at least two carboxyl radicals separated by no more than two carbon atoms. Polymers of this latter type are described in GB-A-1 596 756. Examples of salts are polyacrylates having a molecular weight of 2,000-5,000, and their copolymers with maleic anhydride, and such copolymers have a molecular weight of from 20,000 to 100,000, more preferably 40,000 to 1,000,000. 000-80 000.

Other suitable organic polymers are copolymers of acrylamide and acrylates having a molecular weight of 3,000-100,000, and copolymers of acrylates and fumarate with a mol. weight 2 000-80 000.

Also useful herein are the polyamino compounds including aspartic acid derivatives disclosed in EP-A-0 305 282,

EP-A-0 305 283 and EP-A-0 351 629.

Also suitable herein is the use of terpolymers composed of maleic, acrylic, polyaspartic and vinyl alcohol, especially those with an average molecular weight of 5,000-10,000.

Other useful organic polymeric compounds are polyethylene glycols, especially polyethylene glycols having a molecular weight of 1,000 to 10,000, more preferably 2000 to 8,000, most preferably 4000.

Soap suppression system

The detergent formulations of the invention formulated for machine washing preferably contain some suds suppressant system in an amount of 0.01 to 15%, more preferably 0.05 to 10%, and most preferably 0.1 to 5% by weight of the composition.

Suitable soap suppressor systems may include any known antifoam compound, including, for example, silicone 2-alkyl and alkanol antifoam compounds.

By antifoam compound is meant any compound or mixture of compounds which acts to suppress foaming or suds formation caused by a detergent solution solution, especially when mixing the solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any silicone component containing compounds. These silicone antifoam compounds also typically contain a silica component. The term silicone as used herein and as commonly used in industry includes various, relatively high molecular weight polymers containing siloxane units and a hydrocarbyl group of various types. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes containing trimethylsilyl terminal blocking units.

Other suitable antifoam compounds include monocarboxylic fatty acids and salts thereof. These materials are described in U.S. Patent 2,954,347, issued September 27, 1960,

Wayne St. John. Monocarboxylic fatty acids and salts thereof for use in suppressing suds formation typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g., fatty acid triglycerides), monovalent alcohol fatty acid esters, aliphatic C ₁₈ -C ₄₀ ketones (e.g., stearone), N-alkylated aminotriazines, such as tri- to hexa-alkylmelamines, or di- tetraalkyldiamine chlorotriazines formed as cyanuric acid chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, stearic amides and monostearyl phosphates and phosphate esters with two alkali metal atoms (e.g. sodium, potassium and lithium).

Copolymers of ethylene oxide and propylene oxide, in particular mixed ethoxylated / propoxylated fatty alcohols having an alkyl chain of 10 to 16 carbon atoms and an ethoxylation degree of 3 to 30 and a propoxylation degree of 1 to 10 are also suitable antifoam compounds for use in the invention.

- 47 Suitable 2-alkyl alkanols as antifoam compounds for use herein are described in DE 40 21 265. The 2-alkyl alkanols suitable for use herein include Cg-C ^ g alkyl chain carrying a terminal hydroxy group, said alkyl chain is substituted with _one C to C 1-6 alkyl chain. Mixtures of 2-alkyl alkanols can be used in the compositions of the present invention.

A preferred suds suppression system consists of:

(a) an antifoam compound, more preferably a silicone antifoam compound, and most preferably a silicone antifoam compound consisting of a combination of (i) a polydimethylsiloxane in an amount of 50 to 99%, more preferably 75 to 95% by weight of a silicone antifoam compound; and (ii) silica (silica) in an amount of 1 to 50%, more preferably 5 to 25% by weight of the silicone / silica antifoam compound, wherein said silica / silicone antifoam combination is provided in an amount of 5 to 50%, more preferably 10 to 40% by weight;

(b) dispersing compounds, most preferably consisting of a rake silicone-glycol copolymer having a polyoxyalkalene content of 72 to 78% by weight, and an ethylene oxide to propylene oxide ratio of 1: 0.9 to 1: 1.1 in an amount of 0.5 to 10% by weight. %, more preferably 1 to 10 wt%; a particularly preferred silicone-glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the trade designation DCO544;

(c) an inert carrier fluid compound, most preferably comprising a C ₁₆ ethoxylated alcohol _ ₁₈ with degree of ethoxylation of 5-50, preferably 8-15, in an amount of 5-80%, preferably 10-70 wt%.

A preferred suds suppression system for use herein comprises a mixture of an alkylated siloxane of the above type, and a solid silica.

The solid silica may be fumed, precipitated, or prepared by a gel forming technique. Its particles have an average size of 0.1 to 50 microns, preferably 1 to 20 microns, and a surface area of at least 50 m ² / g. These particles can be made hydrophobic by the action of dialkylsilyl and / or trialkylsilyl groups, either by coupling directly or by means of a silicone resin. Particles hydrophobised with dimethyl and / or trimethylsilyl groups are preferred. The antifoam compound suitable for the detergent compositions of the invention preferably comprises an amount of silica such that the weight ratio of silica: silicone is in the range of 1: 100 to 3:10, more preferably 1-50 to 1: 7.

Another suitable soap suppression system is hydrophobically silane (most preferably trimethylsilane) silica having a particle size of 10 to 20 nanometers and a specific surface area above 50 m ² / g, intimately mixed with fluid dimethylsilicone having a molecular weight of 500 to 200,000 at a silicon: silane weight ratio. 1: 1 to 1: 2 oxide.

A very preferred soap suppression system is described in EP-A-0 210 731 and consists of a silicone antifoam compound and an organic carrier having a melting point of 50 to 85θ <2, wherein the organic carrier consists of a glycerin monoester and a 12 to 12 carbon chain fatty acid. 20 carbon atoms. Another such preferred system is described in EP-A-0 210 721, wherein the organic carrier is a fatty acid or alcohol having a chain of 12 to 20 carbon atoms, or mixtures thereof, with a melting point of 45 to 80 ° C.

Another highly preferred suds suppression system is disclosed in related European Application 91870007.1 to Procter and Gamble Co .; these systems comprise a silicone antifoam compound, a carrier material, an organic coating material, and glycerin with a glycerin: silicone weight ratio of 1: 2 to 3: 1. Related European Application 91201342.0 also discloses as a highly preferred suds suppression system consisting of a silicone antifoam compound, a carrier material, an organic coating and a crystalline or amorphous aluminosilicate at an aluminosilicate: silicone weight ratio of 1: 3 to 3: 1. Starch is the preferred carrier in both of the highly preferred granular soap control agents described.

An exemplary soap suppression system is an agglomerated component formed by an agglomeration process consisting of:

(i) 5 to 30%, preferably 8 to 15% by weight component with a silicone antifoam compound, preferably consisting of a combination of polydimethylsiloxane and silica.

(ii) 50 to 90%, preferably 60 to 80% by weight of a component comprising a carrier material, preferably starch;

(iii) 5 to 30%, preferably 10 to 20% by weight of a component comprising an agglomerating binder, wherein the binder may be any compound or mixture typically used as an agglomerating binder; The most preferred such agglomeration bonding compound is an ethoxylated ^C 16-18 alcohol ^Stu pňem ethoxylation of from 50 to 100; and (iv) 2-15%, preferably 3-10% by weight of hydrogenated fatty acids _C12 _22 ·

Flocculating agent for clay

The compositions of the invention may also contain a flocculating agent for clay, preferably present in an amount

0.005% to 10%, more preferably 0.05% to 5%, most preferably 0.1% to 2% by weight of the composition.

The weight ratio of the mineral clay compound to the clay flocculating agent is preferably from 300: 1 to 1: 1, more preferably from 80: 1 to 10: 1, most preferably from 60: 1 to 20: 1.

The clay flocculating agent acts to precipitate clay compound particles into the scrubbing solution and facilitate their settling on the fabric surface during washing. This functional requirement is therefore different from clay dispersants, which are typically added to laundry detergent compositions to help remove soil stains from fabrics and allow them to disperse in the laundry solution.

Preferred flocculating agents for the clay of the invention are organic polymeric materials having an average weight of 100,000 to 10,000,000, preferably 150,000 to 5,000,000, more preferably 200,000 to 2,000,000.

Suitable organic polymeric materials include homopolymers or copolymers containing monomer units selected from alkylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinylpyrrolidone and ethyleneimine. Homopolymers of ethylene oxide, acrylamide and acrylic acid are preferred.

European Patent Nos. EP-A-0 299 575 and EP-A-0 313 146 of the Procter and Gamble Company disclose preferred organic polymeric clay flocculants for use herein.

Inorganic clay flocculating agents are also suitable, examples include lime and alum.

Polymeric dye transfer inhibitors

The detergent compositions of the invention may also contain from about 0.01% to about 10%, preferably from about 0.05% to about 0.5%, by weight of a polymeric dye transfer inhibitor.

Polymeric N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, and combinations thereof are preferably selected as polymeric dye transfer inhibiting agents.

a) Polymers of polyamine N-oxide

Polyamine N-oxide polymers suitable for use in the present invention include cells having the following structural formula:

P

I (·) Ax

AND

R wherein P is a polymerizable unit to which the group R-N-O may be attached, or the group R-N-O is part of a polymerizable unit or a combination of both;

II ii

A is NC. WHAT. C. -O-. -WITH-. -N-; x is 0 or 1;

R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group, or a combination thereof, to which the N-O group may be attached or in which the N-O group is part of these groups.

The N-0 group is represented by the following structural formula:

(R 6 x N- ^R 6 y ( ^R 3 z) or

Where R p R ₂ ^and R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or / and y or / az is zero or 1, and wherein the nitrogen of the N-O group may be attached to these groups , or is part of them. The N-O group may be part of a polymerizable unit (P) or may be attached to the polymer backbone, or a combination of both.

Suitable polyamine N-oxides in which the N-O group forms part of the polymerizable unit are polyamine N-oxides in which aliphatic, aromatic, alicyclic or heterocyclic groups are selected as R. Preferred polyamine-N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidone, piperidine, quinoline, acridine, and derivatives thereof.

Another class of these polyamine-N-oxides is the group of polyamine-N-oxides in which the nitrogen of the N-O group is attached to the R group. Other suitable polyamine-N-oxides are those in which the N-0 group is attached to the polymerizable unit .

A preferred class of polyamine N-oxides are those having the general formula (I) and R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the N-O function is part of the R group. Examples of this class are polyamine N-oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole, and derivatives thereof.

Another preferred class of polyamine N-oxides are those having the general formula (I) and R is an aromatic, heterocyclic or alicyclic group in which the nitrogen functional group N-O is attached to said R group. Examples of this class are polyamine oxides, wherein the R groups are aromatic, such as phenyl.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has color transfer inhibiting properties. Examples of suitable backbones are polyvinyl, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.

The amine-N-oxide polymers of the present invention typically have a ratio of amine to amine-N-oxide of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups in the polyamine oxide polymer can be varied by appropriate copolymerization or by a suitable degree of N-oxidation. Preferred is an amine to amine N-oxide ratio of 2: 3 to 1: 1 000 000, more preferably 1: 4 to 1: 1 000 000, and most preferred is 1: 7 to 1: 1 000 000. The polymers of this invention include non-oriented or block copolymers in which one monomer type is an amine N-oxide and the other is either an amine N-oxide or nothing. The polyamine N-oxide amine oxide cell has a PKa < 10, more preferably PKa < 7, most preferably PKa < 6.

The polyamine oxides can be obtained at any degree of polymerization. The degree of polymerization is not critical provided the material has the necessary water solubility and color retention capability. A typical average molecular weight is 500 to 1,000,000, preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and most preferably 3,000 to 20,000.

b) N-vinylpyrrolidone and N-vinylimidazole copolymers

Preferred polymers of the invention are copolymers

N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight of 5,000 to 50,000, more preferably 8,000 to 30,000, and most preferably 10,000 to 20,000. Preferred N-vinylimidazole-Nvinylpyrrolidone copolymers have a molar ratio

N-vinylimidazole to N-vinylpyrrolidone 1: 0.2, more preferably 0.8: 0.3, and most preferably 0.6: 0.4.

c) Polyvinylpyrrolidone

Polyvinylpyrrolidone (PVP) having an average molecular weight of 2,500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000 is also used in the detergent compositions of the invention. Suitable polyvinylpyrrolidone is commercially available from ISP Corporation, New York and Montreal, Canada, under the trade names PVP K-15 (average molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000), and PVP K-90 (average molecular weight 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones commercially available from BASF Cooperation are Sokalan HP 165 and Sokalan HP 12.

Polyvinylpyrrolidone is used in the detergent compositions of the invention in an amount of 0.01 to 5%, preferably 0.05 to 3%, and more preferably 0.1 to 2% by weight of the detergents. The amount of polyvinylpyrrolidone supplied to the scrubbing solution is 0.5 to 250 ppm, more preferably 2 to 150 ppm, and most preferably 5 to 100 ppm.

d) Polyvinyloxazolidone

Also used in the detergent compositions herein are polyvinyloxazolidones as polymeric dye transfer inhibiting agents. These are polyvinyloxazolidones with an average molecular weight of 2,500 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000.

Polyvinyloxazolidone is used in the detergent compositions of the invention in an amount of 0.01 to 5%, more preferably 0.05 to 3% and most preferably 0.1 to 2% by weight of the detergent. The amount of polyvinyloxazolidone fed to the scrubbing solution is 0.5 to 250 ppm, more preferably 2.5 to 150 ppm, and most preferably 5 to 100 ppm.

(e) Polyvinylimidazole

Polvinylimidazole is also used as a polymeric dye transfer inhibiting agent in the detergent compositions of the present invention. These polyvinylimidazoles have an average molecular weight of 2,500 to 400,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 15,000.

Polyvinylimidazole is used in the detergent composition in an amount of 0.01 to 5%, more preferably 0.05 to 3%, and most preferably 0.1 to 2% by weight of the detergent. The amount of polyvinylimidazoles fed to the scrubbing solution is 0.5 to 250 ppm, more preferably 2.5 to 150 ppm, and most preferably 5 to 100 ppm.

Optical brightening

Detergent compositions also use from about 0.005% to about 5% by weight of a particular type of hydrophilic optical brightener which also has a color transfer inhibiting effect. If used, the composition of the invention will preferably contain from 0.01 to 1% by weight of the optical brightener.

The hydrophilic optical brighteners used according to the present invention have the structural formula:

wherein R 1 is selected from the group consisting of anilino,

N-2-bis-hydroxymethyl and NH-2-hydroxyethyl; R ₂ is selected from the group consisting of N-2-bis-hydroxyethyl,

N-2-hydroxyethyl-N-methylamino, morpholino, chloro, and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula R 1 is anilino, R ₂ is N-2-bis-hydroxyethyl and M is cation eg sodium, then the brightener is 4,4'-bis [(4-anilino-6- (N-2-bis) (hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and the disodium salt. This special type of brightener is sold under the trade name Tinopal-UNPA-GX by Ciba-Geigy.

Tinopal-UNPA-GX is the preferred hydrophilic optical brightener used in the detergent compositions of the invention.

If R 1 in the above formula is anilino, and when R _{2 is} N-2-hydroxyethyl-N-2-methylamino and M is a cation, e.g. sodium, the brightener is 4,4 ¹ -bis - [(4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid disodium salt. This type of brightener is sold under the trade name Tinopal 5BM-GX by Ciba Geigy.

When R in the above formula is anilino, R ₂ is morpholino and M cation such as sodium, the brightener is 4,4'-bis - [(4-anilino-6-morpholino-s-triazine-2-yl) amino] - 2,2'-stilbenedisulfonic acid-sodium salt. This type of brightener is sold under the trade name Tinopal AMS-GX by Ciba Geigy.

The specific type of optical brightener selected for use in the present invention provides the advantage of a particularly effective color transfer inhibitor when used in combination with the polymeric color transfer inhibiting agents described above. The combination of these selected polymeric materials (eg, PVNO and / or PVPVI) with these selected optical brighteners (eg, Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significantly better inhibition of color transfer in aqueous wash solutions than each of the two detergent components when used alone. Without wishing to be bound by theory, it is believed that these brighteners work in this manner because they have a high affinity for the textile material in the wash solution and therefore deposit thereon relatively quickly. The extent to which the brighteners are deposited on the fabric in the wash solution can be defined by a parameter called the exhaustion coefficient. This coefficient is generally the ratio of a) the fabric-brightener material to b) the initial brightener concentration in the wash solution. In the context of the present invention, brighteners with a relatively high exhaustion coefficient are most suitable for inhibiting color transfer.

It will be appreciated, however, that other conventional optical brighteners may be selected and used in detergent compositions to achieve conventional brightening of the textile material rather than actual inhibition of color transfer. Such use is conventional and well known to detergent formulators.

Cationic fabric softening agents

According to the present invention, cationic fabric softeners are also incorporated into the laundry detergent composition.

These agents may be present as different components or as components of the hydrophobically activated clays described above. Suitable cationic fabric softening agents include water-insoluble tertiary amines and amides as described in GB-A-1 514 276 and EP-B-0 011 340. Cationic fabric softening agents are used in an amount of from 0.5% to 15% %, usually from 1% to 5%.

Other optional ingredients

Other optional ingredients suitable for incorporation into the detergent compositions of the invention include fragrances, colorants and filler salts, with sodium sulfate being a suitable filler.

Form of detergent compositions

The detergent compositions of the invention may be formulated in any desired form, such as powders, granules, pastes and tablets.

It is preferred that the particle size of the granular composition be such that at most 5% of the particles are larger than 1.4 mm in diameter and at most 5% of the particles are smaller than 0.15 mm in diameter.

The bulk density of the granular detergent composition of the present invention is typically at least 450 g / liter, more typically 600 g / liter, and most preferably 650 to 1200 g / liter.

Production processes - granular means

In general, the granular detergent compositions of the present invention are manufactured in a variety of ways, including cold mixing, spray drying, agglomeration, and granulation.

Washing methods

The compositions of the invention can be used in virtually any washing or cleaning process, including hand washing, soaking and machine washing.

The machine washing methods comprise washing the dirty laundry with an aqueous washing solution in a washing machine in which an effective amount of the machine washing detergent composition of the present invention is dissolved or dispersed. The detergent can be added to the washing solution either through the dispersion drawer of the washing machine or through a distributor device. By effective amount of detergent composition is meant 40 to 300 g of product dissolved or dispersed in a wash solution of 5 to 65 liters, which are typical product and solution volumes commonly used in conventional machine washing methods.

In a preferred washing method, a dispensing device containing an effective amount of a detergent composition introduces it into the drum of the washing machine, preferably with a front loading, before the start of the washing cycle.

The dispensing device is a detergent container used to deliver the product directly to the washing machine. Its volume must be such that it contains sufficient detergent composition in the amount normally used in washing.

After the washing machine has been filled with laundry, the dispensing device containing the detergent composition is placed in a drum. At the beginning of the washing cycle of the machine, water is introduced into the drum, which begins to rotate periodically. The design of the dispensing device must be such as to allow it to be filled with a dry detergent composition, but thereafter to allow release of the composition during the wash cycle as a result of agitation as the drum rotates and also as a result of immersion in the wash water.

For this release of the detergent product during washing, the dispensing device must have a number of openings through which the product can pass. Alternatively, the device may be made of a material which is liquid pervious and impermeable to the solid product, allowing release of the dissolved product. It is preferred that the detergent product is rapidly released at the beginning of the wash cycle and that a transient locally high product concentration is formed in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed so that their integrity is maintained both in the dry state and in the wash cycle. Particularly preferred dispensing devices used in accordance with the present invention have been described in the following patents: GB-B-2,157,717, GB-B2 157,718, EP-A-0 201 376, EP-A-0 288 345 and EP-A- J. Bland's article, Manufacturing Chemist, November 1989, pp. 41-46 also discloses a highly preferred dispensing device for granular laundry detergents of the type commonly known as granulate.

Very preferred dispensing devices are disclosed in European Patent Publication Nos. 0 343 069 and 0 343 070. This last application discloses a device consisting of a flexible bag attached to a support ring forming an opening, the opening being adapted to allow a sufficient amount of means to the bag per wash cycle of the washing process. A portion of the washing medium flows through the opening into the bag, dissolves the detergent and the solution then flows out through the opening into the washing medium. The carrier ring is provided with a mask preventing the wetted undissolved agent from flowing out; the mask arrangement consists of radial walls extending from the central protrusion in the form of a spoke wheel or the like in which the walls are helical.

Alternatively, the dispensing device may be a flexible container such as a sachet. This bag may be a fibrous structure coated with a water impermeable protective material to retain the contents as described in European Patent Application No. 0 018 678. Alternatively, it may be formed as a water-insoluble synthetic material provided with an edge seal or closure designed to break in an aqueous medium as disclosed in European Patent Application Nos. 0 011 500, 0 011 501, 0 011 502 and 0 011 968.

A suitable form of water-repellent closure is a water-soluble adhesive applied along and a sealing edge of a bag made of a water-impermeable polymer film such as polyethylene or polypropylene.

Packaging of funds

The commercially available bleaching composition is packaged in any suitable package made of paper, cardboard, plastic materials and any suitable laminates. A preferred embodiment is described in European Patent Application Publication No. 93970141.4.

The identification abbreviations of the detergent composition components have the following meanings:

LAS: Linear ^C 12 -alkylbenzenesulfonate sodium

TAS: Sodium alcohol derived from tallow alcohol

XYAS: sodium C ₁ -C 1 _Y -alkyl sulfate

25EY: Predominantly linear primary C _{12 - 15 -} alcohol condensed on average with Y moles of ethylene oxide

XYEZ: Predominantly linear primary C _{1 x} -C _1Y -alcohol condensed on average with Z moles of ethylene oxide

XYEZS: C _{1 x} -C 1 _Y -alkylsulfate condensed on average with Z moles of ethylene oxide per mole

QAS R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) where R = C ₁₂ -C ₁₄ Soap : Sodium linear alkyl carboxylate derived from a mixture of 80/20 tallow and coconut oils TFAA : ^C 16 ^C 18 -alkyl N-methylglucamide Silicate : Amorphous sodium silicate (SiO ₂ : Na ₂ O = 2.0 ratio) NaSKS-6 Crystalline layered silicate of the formula δ - Na ₂ Si ₂ 0g Bicarbonate : Anhydrous sodium bicarbonate with particle size between 400 gm and 1 200 gm Carbonate : Anhydrous sodium carbonate MA / AA : 1: 4 maleic acid / acrylic acid copolymer, average molecular weight 70 000 STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated sodium aluminosilicate of the formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O with a primary particle size of 1 to 10 microns

Acid lemon : Anhydrous citric acid Citrate : Tri-sodium citrate dihydrate Percarbonate : Whitening anhydrous sodium percarbonate coated with sodium silicates (SiO ₂ : Na ₂ O = 2: 1 ratio) at a percarbonate to sodium silicate weight ratio of 39: 1 PB1 : Bleaching anhydrous sodium perborate of the formula NaBO ₂ .H ₂ O ₂

PB4 : Sodium perborate tetrahydrate of the formula NaBO ₂ .3H ₂ OH ₂ O ₂ TAED Tetraacetylethylenediamine particle formed by agglomeration of TAED formed with a 1: 4 maleic acid / acrylic acid copolymer having an average molecular weight of 70,000 at a TAED: copolymer weight ratio of 85:10 and coated with said agglomerate coated with said copolymer at an agglomerate weight ratio: coating 95: 5 NOBS : Nonanoyloxybenzenesulfonate in the form of the sodium salt Protease : Proteolytic enzyme sold under the trade name Savinase by Novo Nordisk A / S having an activity of 13 KNPU / g Protease # : Proteolytic enzyme sold under the trade name Savinase by Novo Nordisk A / S having an activity of 4 KNPU / g Protease # # : Proteolytic enzyme sold under the trade name called FN3 by Genencor Alkalase : Proteolytic enzyme sold by Novo Industries A / S with an activity of 3 AU / g Amylase : Amylolytic enzyme sold under the trade name Termamyl 60T by Novo Industries A / S with an activity of 300 KNU / g Amylase # : Amylolytic enzyme sold under the trade name Termanyl 120T by Novo Industries A / S with an activity of 600 KNU / g Cellulase : Cellulose enzyme sold by Novo Industries A / S with an activity of 1,000 CEVU / g

Lipase : Lipolytic enzyme sold under the trade name Lipolase by Novo Industries A / S with an activity of 165 KLU / g Endolase : Endoglucanase A sold by Novo INDUSTRIES A / S CMC - Carboxymethylcellulose - sodium salt DETPMP : Diethylene triamine penta (methylenephosphonic acid) sold under the name Dequest 2060 by Monsanto HEDP : Hydroxyethane 1,1 diphosphonic acid EDDS : Ethylenediamine-N, N'-disuccinic acid [S, S] isomer in the form of sodium salt PVNO : Polyesters of (4-vinylpiridine) -N-oxide, a copolymer of vinylimidazole and vinylpyrrolidone having an average molecular weight of 10 000 PVPVI : Copolymer of polyvinylpyrrolidone and vinylimidazole Clay Calcium Montmorillonite sold by Colin Stewart Minchem Ltd and containing 50 ppm Cu, 8,000 ppm Fe and 80 ppm Mn Acid clay : Organic acid-treated Montmorillonite sold by Sud Chemie AG

Granular Soap Suppressor: 12% silicon / silica, 18% stearyl alcohol, 70% starch in granular form

SRA (Solvent Release Agent): Sulfobenzoyl-terminated esters with oxyethyleneoxy and terephthaloyl linkages

Metolóa : Carboxymethoxyether Sulphate : Anhydrous sodium sulphate Brightener 1 Disodium 4,4'-bis (2-sulfostyryl) biphenyl Brightener 2 : Disodium 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilbene-2: 2 '- disulfonate

Photoactivated bleach Sulfonated zinc phtylocyanin encapsulated in dextrin soluble polymer

Silicone

a foaming agent Polydimethylsiloxane foam regulator with a siloxane-oxyalkylene copolymer as a dispersant with a ratio of said foam regulator to said dispersant 10: 1 to 100-1.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

An agglomerate having the following formulation is prepared in an Eirich mixer model RV02 (trade name) wt. %

TAED 85

Clay ** 5

MA / AA * molecular mass. 70,000 10

100 * supplied as Sokolan 45 (tradename) BASF ** bentonite type from Colin Stewart Minchem Ltd and containing 8,000 ppm Fe, 50 ppm Cu and 80 ppm Mn.

TAED and clay are added to the Eirich mixer and premixed. The powder temperature is 25 ° C. An aqueous MA / AA binder solution at 60 ° C in an Eirich mixer was added to the powder mixture over 30 seconds while the blades and vessel were rotating. The resulting mixture was further stirred for 30 seconds. Stirring is stopped and the agglomerated product is removed from the Eirich mixer and then dried in a fluid bed dryer to a humidity of 2%. The product is sieved and materials greater than 1,180 microns and less than 250 microns are discarded.

Example 2

The above procedure was repeated except that the clay was replaced with an equal amount of Tonsil P acid clay supplied by Sud Chemie AG.

Example 3

An agglomerate having the following formulation is prepared in an Eirich mixer model RV02 (trade name) wt. %

TAED 80

Clay ** 5

MA / AA * molecular mass. 70 000 10 * supplied as Sokolan 45 (tradename) BASF ** bentonite type from Colin Stewart Minchem Ltd and carrying 8,000 ppm Fe, 50 ppm Cu and 80 ppm Mn.

TAED and clay are added to the Eirich mixer and premixed. The powder temperature is 25 ° C. The molten binder is added to the powder mixture within 30 seconds at 60 ° C in an Eirich mixer while the blades and the container rotate. The resulting mixture was further stirred for 30 seconds. Stirring is stopped and the agglomerated product is removed from the Eirich mixer and then dried in a fluid bed dryer. The product is sieved and materials greater than 1,180 microns and less than 250 microns are discarded. The resulting agglomerate is coated with an MA / AA copolymer in an amount of coating: agglomerate 5:95.

Example 4

An agglomerate having the following formulation is prepared by a continuous dual Lodig process in a CB Lodig high shear mixer and then in a KM Lodig low shear mixer.

wt. %

TAED 75 Clay ** 10 MA / AA * molecular weight 70 000 10 * supplied as Sokolan 45 (tradename) BASF ** bentonite type from Colin Stewart Minchem Ltd and carrying 8,000 ppm Fe, 50 ppm Cu and 80 ppm Mn.

TAED and clay are added continuously to the inlet of a CB Lodig mixer, the powder temperature being 25 ° C. The molten binder temperature of 60 ° C is added continuously to the CB Lodig mixer. The resulting mass is transferred to a KM Lodig mixer for final size increase. The wet agglomerated product is dried in a fluid bed dryer to a moisture content of 2%. The product is sieved and materials greater than 1700 microns and less than 425 microns are discarded. The resulting agglomerate was coated with an MA / AA copolymer in an amount of coating: agglomerate of 5:95 in a KM Lodig mixer.

The following laundry detergent compositions A are prepared,

B, C, D and E, wherein A and B are comparative means and C to C

E are compositions according to the invention.

Example 5

AND (B) C D E 45AS / 25AS 9.1 9.1 9.1 9.1 9.1 35AE3S 2.3 2.3 2.3 2.3 2.3 24E5 4,5 4,5 4,5 4,5 4,5 TFAA 2,0 2,0 2,0 2,0 2,0 Zeolite A 10.2 10.2 10.2 10.2 10.2 For SKS-6 / citric acid 10.6 10.6 10.6 10.6 10.6 (79-21) Carbonate 7.6 7.6 7.6 7.6 7.6 TAED 5 6.67 - - - TAED / Clay particles (1) - - 6.67 - - TAED / Clay Particles (2) - - - 6.67 - TAED / Clay Particles (3) - - - - 6.67 Percarbonate 22.5 22.5 22.5 22.5 22.5 DETPMP 0.5 0.5 0.5 0.5 0.5 Protease 0.55 0.55 0.55 0.55 0.55 Lipase 0.15 0.15 0.15 0.15 0.15 Cellulase 0.28 0.28 0.28 0.28 0.28 Amylase 0.27 0.27 0.27 0.27 0.27 Polycarboxylate 3.1 3.1 3.1 3.1 3.1 CMC 0.4 0.4 0.4 0.4 0.4 PVNO 0.03 0.03 0.03 0.03 0.03 Granular suppressor 1.5 1.5 1.5 1.5 1.5 soap foam Tracks / miscellaneous up to 100%

* (1) as in Example 1 (2) as in Example 2 (3) as in Example 3

Example 5 - Comparative Efficacy Test

Protocol 1 - test for bleached stains on fabric

Formulations A through E are subjected to a complete wash test using 12 Miele washing machines (model WM W698) set for a short wash cycle at 40 ° C for each formulation. Water of 12 ° German hardness (= 1.8 mol Ca ⁺⁺ / liter) is used. The fabric samples are placed in automatic washing machines in pairs labeled 1 to 24 and made of garments obtained from the High Street warehouse as detailed below.

Sample number Type of clothing Color Type of fabric 1 & 4 cardigan sea. blue 50/50% wool / acrylic 2 & 3 5 & 8 6 & 7 men's shirt T-shirt zapocená pánská shirt dark green black black 100% cotton 100% cotton 10/90% cotton/ polyester 9 & 12 T-shirt black 100% cotton 10 & 11 denim shirt blue 100% cotton 13 & 16 T-shirt with long sleeve black 50/50% cotton/ polyester 14 & 15 jeans black 100% cotton 17 & 20 men's pants black 65/35% polyester / viscose 18 & 19 pánská manze- strová košile green 100% cotton 21 & 24 men's shirt dark green 100% cotton 22 & 23 leggings black 97/3% cotton / lycra

- 71 Each washing machine was filled with a load of approximately 1.9 kg of clean sheets with the following materials on the surface: fabric sample, 100 g of detergent dispensed from a granule dispenser of the type described in EP-A-0 343 070 and usually supplied for use with Ariel granular detergent Ultra (trade name) as sold by The Procter and Gamble Company and a second sample was given. The 30 cm x 30 cm samples were formulated to capture the granulate during the first stage of dissolution and dispersion of the detergent composition containing the bleach precursor. At the end of this cycle, the samples were removed and air dried.

The samples were evaluated visually for bleaching.

Color samples representing varying degrees of damage were used as standards for setting a six-point scale in which 0 means no color change and 5 extreme discoloration. The three standards are used to define midpoints between different bleaches

2 experts were used no discoloration very slight discoloration weak discoloration clearly discoloration significant discoloration extreme discoloration and results were averaged.

Comparative experiment 1 - bleached stains on fabric

Using Test Protocol 1, the following results of bleached stains on fabric were obtained using formulations A to E

% of samples having degree Formulation 0 1 2 3 4 5 total stamp AND 67 17 8 8 0 0 0.57 (B) 58 13 13 12 4 0 0.91 C 84 0 8 8 0 0 0.40 D 80 4 4 12 0 0 0.48 E 75 4 8 13 0 0 0.59

It will be appreciated that formulations C to E of the present invention cause markedly less blotchy discoloration than formulations A and B which are not according to the present invention.

Test report 2 - stain removal

Three white sheets were prewashed in strong powder without enzyme and bleach. One sheet was poured with tea, the other with wine and the third with coffee. 6 cm x 6 cm samples were cut from each sheet.

These samples were washed in one washing cycle in an automatic washing machine and the efficiency of removing stains from tea, wine and coffee was evaluated using a known method.

More specifically, the Miele 756 WM washer was used and a short cycle at 40 ° C was set. Hardness of used water 12 ° German (= 1.8 mol Ca ²⁺ / liter). 100 g of detergents were dispensed from the dosing device. One sample of each fabric type was washed together with a ballast load of about 1.9 kg of lightly soiled sheets.

The stain removal efficiency was evaluated by measuring brightness using an X-rite color spectrophotometer (trade name). An unclean bed sheet was used as a reference. The stain removal ratio, Δ R, was calculated using the following formula:

( ^L washed "^ not washed)! ^ ^ ^L REFERENCE unwashed ^{× 100} where the differential / IR below 4% are not significant.

Comparative test 2 - stain removal

Test Protocol 2 above was followed by comparing the efficacy of compositions B and C in removing various types of bleachable stains.

The results obtained were as follows:

ÚR (%) (B) C tea 78 76 wine 82 83 coffee 75 74

Stain removal for each of Compounds B and C is comparable. Thus, the presence of heavy metal ions as a hydrogen peroxide scavenger on the clay particles in composition C does not significantly affect the stain removal capability of the composition as compared to composition B. The same result was obtained for perhydrolysis of the bleach precursor.

74 Example 6

The following detergent compositions F to J have been prepared according to the invention:

F G H AND J LAS 2,0 2,0 2,0 2,0 2,0 TAS 0/5 0.5 0.5 0.5 0.5 4 5 AS 6.0 6.0 6.0 6.0 6.0 25E3S 2,0 2,0 2,0 2,0 2,0 24E5 5.0 5.0 5.0 5.0 5.0 TFAA 2,0 2,0 2,0 2,0 2,0 Zeolite A 15.0 15.0 15, 0 15.0 15.0 Acid 2,0 2,0 2,0 2,0 2,0 lemon NaSKS-6 9.0 9.0 9.0 9.0 9.0 Carbonate 14 14 14 14 14 Silicate 2,0 2,0 2,0 2,0 2,0 Sulphate 6.0 6.0 6.0 6.0 6.0 MA / AA 3.0 3.0 3.0 3.0 3.0 CMC 0.3 0.3 0.3 0.3 0.3 SRA 0.15 0.15 0.15 0.15 0.15 Metolóza 0.5 0.5 0.5 0.5 0.5 PVNO / PVPVI 0.02 0.02 0.02 0.02 0.02 Cellulase 0.5 0.5 0.5 0.5 0.5 Amylase # 0.2 0.2 0.2 0.2 0.2 Lipase 0.1 0.1 0.1 0.1 0, 1 Protease # # 0.4 0.4 0.4 0.4 0.4 TAED / particles - - 4,5 - - clay (1) TAED / particles - - - 4,5 - clay (2) TAED / particles - - - - 4,5 clay (3)

TAED / particles 4,5 4,5 - - - clay (4) DETPMP 0.4 - - - - MgS0 ₄ 0.3 0.3 0.3 0.3 0.3 Percarbonate 18.0 18.0 18.0 18.0 18.0 HEDP 0.5 0.5 0.5 0.5 0.5 EDDS - 0.3 0.3 0.3 0.3 Brightener 1 0.2 0.2 0.2 0.2 0.2 Photoactivated 0.003 0.003 0.003 0, 003 0.003 bleach Granular 0.3 0.3 0.3 0.3 0.3 suppressor soap foam Perfume 0.3 0.3 0.3 0.3 0.3 TOTAL 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN!

(1) as in Example 1 (2) as in Example 2 (3) as in Example 3 (4) as in Example 4

Example 7

According to the invention, the following detergent formulations have been prepared wherein formulation K is a phosphorous-containing detergent composition, formulation L is a zeolite-containing detergent composition, and formulation M is a compact detergent composition:

TO L M Blown powder STPP 24.0 - 24.0 Zeolite A - 24.0 - Sulphate 9.0 6.0 13.0 MA / AA 2,0 4.0 2,0 LAS 6.0 8.0 11.0 TAS 2,0 - - Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DETPMP 0.4 0.4 0.2 Spray 45E7 2.5 2.5 2,0 25E3 2.5 2.5 2,0 Silicone anti-foam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PBI 4.0 4.0 - TAED (3) 3.0 3.0 1, 0 Photoactivated bleach 0.02% 0.02% 0.02% Protease # 1.0 1.0 1.0

ΊΊ

Lipolase 0.4 0.4 0.4 Termamyl 0.25 0.30 0.15 Sulphate 3.0 3.0 5.0 Rest (Moisture & 100.0 100.0 100.0 other) Density (g / liter) 630 670 670

(4) as in Example 4

Example 8

The following N and O detergent formulations were prepared according to the invention:

N 0 Blown powder Zeolite A 22.0 6.0 Sulphate 10.0 7.0 MA / AA 3.0 6.0 LAS 12.0 22.0 4 5 AS 7.0 7.0 Silicate 1.0 5.0 Soap - 2,0 Brightener 1 0.2 0.2 Carbonate 16.0 20.0 DETPMP 0.4 0.4 Spray 45E7 1.0 1.0 Dry additives PVPVI / PVNO 0.5 0.5 Protease # 1.0 1.0 Lipolase 0.4 0.4 Termamyl 0.1 0.1 Carezym 0.1 0.1 NOBS (3) 6.1 4,5 PB1 5.0 6.0 Sulphate 6.0 - The rest (moisture and moisture) 100 ALIGN! 100 ALIGN!

(4) as in Example 4, wherein the TAED is replaced by NOBS

Ί9

Example 9

The following high density detergent formulations P and Q containing bleach were prepared according to the invention:

P Q Blown powder Zeolite A 15.0 15.0 Sulphate - 5.0 LAS 3.0 3.0 QAS - 1.5 DETPMP 0.4 0.4 CMC 0.4 0.4 MA / AA 4.0 2,0 Agglomerates LAS 5.0 5.0 TAS 2,0 2,0 Silicate 3.0 3.0 Zeolite A 8.0 8.0 Carbonate 8.0 8.0 Spray Perfume 0.3 0.3 45E7 2,0 2,0 25E3 2,0 - Dry additives Citrate 5.0 - Bicarbonate - 3.0 Carbonate 8.0 15.0 TAED (3) 6.0 2,0 PB1 14.0 7.0 Protease # 1.0 1.0 Lipolase 0.4 0.4 Termamyl 0.6 0.6

Carezym 0.6 0.6 Silicone antifoam 5.0 5.0 granule Sulphate - 3.0 The rest (moisture and moisture) 100.0 100.0 other Density (g / liter) 850 850

(4) as in Example 4

Example 10

According to the invention, the following detergent formulations R and S were prepared:

R WITH Agglomerate 4 5 AS 11, 0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA / AA 4.0 2,0 CMC 0.5 0.5 DETPMP 0.4 0.4 Metolóza 0.6 0.2 Spray 25E5 5.0 5.0 Perfume 0.5 0.5 Dry additives HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED (3) 5.0 7.0 Percarbonate 20.0 20.0 SRA 0.3 0.3 Protease # 1.4 1.4 Lipolase 0.4 0.4 Carezym 0.6 0, 6 Termamyl 0.6 0.6 Silicone antifoam 5.0 5.0 particle Brightener 1 0.2 0.2 Brightener 2 0.2 - Rest (humidity and others) 100 ALIGN! 100 ALIGN! Density (g / liter) 850 850

(4) as in Example 4

Claims (26)

PATENT CLAIMS A detergent composition comprising (a) a source of peroxide compounds, (b) a peroxyacid bleach precursor composition comprising i) an organic peroxyacid bleach precursor, ii) a hydrogen peroxide scavenger, said bleaching organic peroxyacid precursor and said hydrogen peroxide scavenger are in said composition in close physical proximity. 2. A detergent composition according to claim 1, wherein said organic peroxyacid bleach precursor is in a perfect blend in said composition. A detergent composition according to any one of claims 1 or 2, wherein said hydrogen peroxide scavenger is selected from compounds that react with hydrogen peroxide via a decomposition, neutralization or adsorption process or a combination thereof. A detergent composition according to any one of claims 1 to 3, wherein the hydrogen peroxide scavenger is selected from the group consisting of a heavy metal ion, a catalase enzyme, and a peroxydase enzyme. 5. A detergent composition according to any one of claims 1 to 4 wherein the hydrogen peroxide scavenger is a heavy metal ion selected from the elements found in the third and fourth rows of the third to the twelfth columns of the periodic table. A detergent composition according to either claim 4 or claim 5 wherein said heavy metal ion is selected from the group consisting of Fe, Cu, and Mn and mixtures thereof. The detergent composition according to any of claims 4 to 6, wherein said heavy metal ion is in an amount of less than 5% by weight of the bleach precursor composition, preferably less than 1%, more preferably less than 0.1%. The detergent composition of any one of claims 1 to 4, wherein the hydrogen peroxide scavenger is a catalase type enzyme selected from the group consisting of Terminox ^R and Fermicolase ^R. A detergent composition according to any one of claims 1 to 4, wherein the hydrogen peroxide scavenger is a peroxidase-type enzyme selected from the group consisting of horseradish peroxidase, ligninase and haloperoxidase. The detergent composition of any of claims 8 or 9, wherein said enzyme is present in an amount of less than 5% by weight of the bleach precursor composition. The detergent composition of any one of claims 4 to 7, wherein said heavy metal ion is carried by a mineral material containing at least 200 ppm of said heavy metal ion. 12. A detergent composition according to claim 11 wherein said material is a non-dimensional, phyllosilicate mineral material. A detergent composition according to any one of claim 11 or 12, characterized in that said mineral material is clay. A detergent composition according to any one of claims 11 to 14 13, characterized in that said mineral material is smectic clay. A detergent composition according to any one of claims 1 to 14, wherein said precursor is present in an amount greater than 3% by weight. a detergent composition. A detergent composition according to any one of claims 1 to 15, wherein said bleach precursor is selected from those containing one or more N- or O-acyl groups. 17. A detergent composition according to claim 16 wherein said bleach precursor is Ν, Ν-Ν ', Ν' tetraacetylethylenediamine. A detergent composition according to any one of claims 1 to 17, wherein said bleach precursor composition is an agglomerate which is further bound with a binder. 19. The detergent composition of claim 18 wherein said bleach precursor agglomerate is further provided with a coating material. 20. A detergent composition according to claim 19 wherein said coating material is selected from the group consisting of polyacrylic acid, cellulose acetate, copolymeric polycarboxylic acid, and monomeric aliphatic acid, and mixtures thereof. 21. A detergent composition according to any one of claims 1 to 20 wherein said active oxygen source is hydrogen peroxide, preferably an inorganic perhydrate bleaching composition. 22. A detergent composition according to claim 21 wherein said perhydrate bleach is sodium perborate or sodium percarbonate. 23. A detergent composition according to any one of claims 1 to 22 comprising a surfactant and a heavy metal ion sequestrant selected from the group consisting of organic phosphates, nitrilotriacetic acid and polyaminocarboxylic acids. 24. The detergent composition of claim 23 wherein said heavy metal ion sequestrant is ethylenediamine disuccinate (EDDS). 25. A detergent composition according to any one of claims 23 or 24 wherein said heavy metal ion masking agent is present in the composition as a separate composition from said peroxyacid bleaching composition. A method for preparing a detergent composition as defined in any one of claims 1 to 25, comprising the following steps: (a) preparing a peroxyacid bleach precursor agglomerate by mixing an organic peroxyacid bleach precursor compound with a hydrogen peroxide scavenger and adding a binder; b) treating said agglomerates with a coating material, (c) drying the coated agglomerates; and d) introducing said dry agglomerates into a detergent composition comprising a source of peroxide compounds.