DE60015716T2 - Laundry additive bag - Google Patents

Abstract

The present invention relates to laundry additive sachets. The sachets comprise at least two compartments and may comprise further compartments. At least one of the compartments comprises a liquid laundry additive composition.

Description

TECHNICAL TERRITORY

The The present invention relates to the field of laundry additives, which is designed for use in conjunction with a conventional detergent are. Such laundry additives are usually designed to the performance of the traditional Detergent to the amplifier. The present laundry additives are in the form of a water-soluble Bag provided at least two chambers.

GENERAL STATUS OF THE TECHNOLOGY

Laundry Additive Products are well known in the art. Such products are in general has been used to enhance the performance of the conventional, primary To increase detergent, mainly by providing additional Bleaching performance. conventional Washing additives are in the form of powders, liquids or gels. however, have been recently also added additives in the form of tablets on the market. Tablets proved to be Consumers as attractive, as a more accurate dosage is possible and a wasteful overdose or underdosing is reduced. In addition, such single-dose products for consumers attractive as a spill or less likely. However, the applicants have found out that although such tablets are preferred by consumers Nevertheless, there is a desire for a product in which the Users are not in direct contact with the ingredients of the composition comes.

It It is therefore an object of the present invention to provide a laundry additive composition in unit dose, where the user is not in direct contact with the ingredients of the composition comes.

These Task is through a bag with laundry additive, comprising a liquid Washing additive composition, dissolved.

EP O132726 describes a bag comprising a water-permeable outer bag and a water-soluble inner bag containing a liquid detergent composition.

One special problem of using a liquid composition over one particulate Composition for filling the bag is that ingredients, especially aggressive ingredients, such as Bleach, the materials that make up the bag, either dissolve or damage, what a premature one resolution of the bag and release of the liquid laundry additive composition. Furthermore can some liquid Ingredients simply through the wall of the bag leak, so the composition runs out of the bag and the laundry additive composition at the time of use no longer corresponds to the correct dose.

It It is also an object of the present invention to provide a laundry additive product provide more than one advantage. This task is solved by that different ingredients are used to differentiate the To achieve advantages. However, it has been found that these ingredients not always compatible with each other are. Indeed it happens in some cases to a reaction of the ingredients with each other, so at least one of the ingredients is completely used up before use by the user becomes. In such cases Of course, the performance of the laundry additive is adversely affected.

It It is therefore an object of the present invention to provide a laundry additive in the form of a bag, comprising at least two chambers and comprising at least one liquid Composition, provide.

SUMMARY THE INVENTION

According to the present Invention provides a bag of laundry additive comprising at least two different compositions, the first and second Composition characterized by the presence of at least one Ingredient differ, the bag is two or more water-soluble Film or film produced chambers comprises and wherein the second composition comprises a liquid composition comprising a particulate one Bleach, is.

To A second aspect of the present invention is a method for treating tissues with a bag according to the invention with laundry additives in conjunction with a conventional detergent provided in the presence of water.

To Another aspect of the present invention is the use a bag according to the invention provided as a laundry additive. In addition, the use will a bag according to the invention provided to wash and / or soften tissue. Furthermore the use of a bag according to the invention is provided, to wash and / or ironing to facilitate.

DETAILED DESCRIPTION OF THE INVENTION Bag of laundry additive

The present invention relates to a bag of laundry additive, comprising one or more liquid Compositions which are described in more detail below. The bag comprises at least two chambers and consists of a water-soluble Film or foil material.

Liquid or particulate Bags comprising compositions are discussed in the prior art. However, the bags were typically either insoluble, so they could be removed at the end of the wash, or were not sufficiently soluble in water. The most common Bags discussed in the prior art are made of polyvinyl alcohol (PVA). However, bags made of PVA are sensitive to bleaching agents, so that the bag is due to use by the user of the effect of bleach on the PVA would degrade and burst if the bag having a composition, especially a liquid composition, comprising a bleach, filled would become. Applicants have addressed this problem by using particulate bleach in a liquid matrix use.

The Applicants have also addressed the known problem that PVA bags Gelled on contact with water. This gelation phenomenon occurs on when the outside surface of the PVA bag in water dissolves, but, instead of spreading in the surrounding water, forms a gel, which surrounds the bag and so further dissolving the Bag prevents. this leads to to prevent the bag from dissolving completely, leaving residues of the bag Bag remain on the tissues. Applicants have found that by using a bag, for example, by use a hydrophobically modified cellulosic polymer and most preferred made of hydroxypropylmethylcellulose (HPMC), which with PVA related problems can be circumvented. HPMC is not only more stable across from Bleaching, but also does not cause the gelling problem of PVA, and for these reasons it is preferred to make the bag by means of HPMC.

bag can prepared according to the methods known from the prior art become. In particular, the bags are made by first inserting a Piece of film / foil suitable size is cut. Then the film is folded to the required number and size of the chambers to form, and the edges then sealed using any suitable technique, such as welding.

Laundry Additive Composition

Of the As described above, the bag comprises at least two chambers. At least one of the chambers is, at least to some extent Degree, with at least one liquid Washing additive composition filled. The other chamber is with another liquid Composition or alternatively filled a particulate composition. Actually the chambers, at least to some extent, with different Filled compositions. With the term "different Composition "is meant that the first and / or second composition at least does not contain an ingredient that is not in the other composition is available.

In the embodiment, in which the bag comprises a third or yet another chamber, can they Chambers at least to some extent with a third or third degree be filled with yet another composition, different from each other the other compositions, for example the first or second composition, if a third composition exist.

In a preferred embodiment the first composition is a liquid or particulate, preferably a particular Composition comprising ingredients selected from the group consisting of Washing additive ingredients are listed.

The second composition comprises a bleaching agent different from the if applicable in the first composition existing differs and in liquid Form is present. Bleaching agents are described in more detail below wherein the preferred bleaching agent is for use in However, the second composition of this embodiment is a particulate peracid. In a more preferred embodiment is the peracid selected from the series of preformed monoperoxycarboxylic acids, described in more detail below are described. In a more preferred embodiment is the preformed peracid Phthaloylamidoperoxicapronsäure, also called PAP. The preformed peracid is in particulate form is used and is then suspended in a liquid matrix. The liquid Matrix, if present, is essentially non-aqueous, which means that it does not contain so much water that it causes a dissolution of the material, from which the bag consists comes. Applicants have found that the preferred ingredients for suspending PAP (suspending agent) solvent are the material that makes up the bag over time neither dissolve still damage. More preferably, the suspending agent is a long-chain, weak polar solvent. With long chain are solvents by a carbon chain having more than 6 carbon atoms and with weakly polar is a solvent with a dielectric constant meant by under 40. Preferred solvents include C12-14 paraffin and more preferably C12-14 isoparaffin. The advantage of the present embodiment is the major improvement in removing bleachable soils, which offers the washing additive.

In an alternative and equally preferred embodiment the second composition is the same as that described above, but the first composition is a fabric softening composition, comprising an ingredient that softens tissue and also to it leads, that the fabrics iron easier to let. The first composition of this embodiment may be liquid but is preferably present in particulate form. The softening Ingredient may be present in an amount of from 20% to 80% by weight of the first composition. The remaining ingredients can selected from any of the ingredients of the laundry additive.

Equally is provided that the above embodiment be changed can that of the performance-imparting ingredient in the first Composition is not a softening ingredient, but for example one enzyme or several enzymes, especially Carezyme, an organic Polymer compound, a soil dissolving Polymer, a dye transfer inhibitor, a brightener and mixtures thereof.

In a further alternative embodiment it is also preferable to have a bag with a laundry additive of the same To produce a composition structure as described in the first embodiment above; in the first, second or first and second compositions an additional Element that is not a softening ingredient such as described in the previous paragraph, can be added.

The Inventive liquid composition when used to suspension of a particulate component Other structuring ingredients include the matrix to stabilize. A preferred structuring agent is one Combination of sodium alkylbenzenesulfonate (LAS) and sodium sulfate, the dehydrated was used to form a crystalline structure.

Tissue, those with the compositions according to the invention, comprising a softening ingredient, are treated not only softer, but also easier to iron. The advantage of the lighter ironing you do not just realize that the tissues have less wrinkles, but also because the folds can be removed more easily, for example on ironing.

ingredients of the washing additive

The used compositions contain a variety of different ingredients, including Builders, surfactants, enzymes, bleaches, alkalinity sources, Colorants, fragrance, lime soap dispersants, organic polymer compounds, including polymeric dye transfer inhibitor, Crystal formation inhibitors, heavy metal ion sequestrants, metal ion salts, Enzyme stabilizers, corrosion inhibitors, foam suppressants, Solvent, Fabric softening agents, optical brighteners and hydrotropes.

Builder

The compositions of the invention preferably contain a builder, typically present in an amount of from 1 to 80% by weight, preferably from 10 to 70% by weight, and most preferably from 20 to 60% by weight, based on the composition of active detergent ingredients.

water-soluble Builder

suitable water-soluble Builders include the water-soluble ones monomeric polycarboxylates or their acid forms, homopolymers or copolymers polycarboxylic or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl radicals, which are separated by not more than two carbon atoms include, carbonates, bicarbonates, borates, phosphates and each Mixture of the above substances.

The Carboxylate or polycarboxylate builders may be of the monomeric or oligomeric type Type, although monomeric polycarboxylates for cost and performance reasons in Are generally preferred.

suitable Carboxylates having a carboxyl group include the water-soluble ones Salts of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates having two carboxy groups the water-soluble Salts of succinic acid, malonic, (Ethylenedioxy) ketobutyric acid, maleic acid, Diglycolic acid, tartaric acid, tartronic acid and fumaric acid as well as the ether carboxylates and the sulfinyl carboxylates. polycarboxylates with three carboxy groups include in particular water-soluble citrates, Aconitrates and citraconates and succinate derivatives such as the carboxymethyloxysuccinates, described in British Patent No. 1,379,241, lactoxysuccinates, described in British Patent No. 1,389,732, and aminosuccinates, described in NL-A-7205873, and the oxypolycarboxylate materials, such as 2-oxa-1,1,3-propane tricarboxylates described in the British Patent No. 1,387,447.

polycarboxylates with four carboxy groups include oxydisuccinates disclosed in U.S. Pat British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates with sulfo substituents include the sulfosuccinate derivatives disclosed in the British Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolyzed citrates described in U.S. Pat British Patent No. 1,439,000.

alicyclic and heterocyclic polycarboxylates include cyclopentane cis, cis, cis tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran tetracarboxylates, 1,2,3,4,5,6-hexane hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols, such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.

The preferred polycarboxylates of the above are hydroxycarboxylates with up to three carboxy groups per molecule, especially citrates.

The acids, of which the monomeric or oligomeric polycarboxylate chelating agents are derived, or Mixtures thereof with their salts, eg. As citric acid or Citrate / citric acid mixtures are also considered useful Builder components viewed.

borate builders and builders of borate-forming materials useful in detergent storage. or washing conditions borate can also be used However, under washing conditions below 50 ° C, especially below 40 ° C, not prefers.

Examples for carbonate builders are alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate, and mixtures thereof with ultrafine calcium carbonate as published in DE-A-2,321,001, on November 15, 1973, disclosed.

strongly preferred builders for use in the present invention are water-soluble Phosphate builder. Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, Sodium and potassium orthophosphate, sodium polymeta / phosphate in which the degree of polymerization ranges from 6 to 21, and salts phytic acid.

specific Examples of water-soluble Phosphate builders are the alkali metal tripolyphosphates, sodium, Potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, Sodium and potassium orthophosphate, sodium polymeta / phosphate in which the degree of polymerization ranges from 6 to 21, and salts phytic acid

Partially soluble or insoluble builder compound

The compositions according to the invention, especially those in particulate form, may comprise a partially soluble or insoluble builder. Examples of partially water-soluble builders include the crystalline layered silicates as disclosed in EP-A-0164514, DE-A-3417649 and DE-A-3742043. The crystalline sodium layer silicates of the general formula are preferred NaMSi _x O _{2 + 1} .yH ₂ O wherein M is sodium or hydrogen, x is a number ranging from 1.9 to 4, and y is a number from 0 to 20. Crystalline layered sodium silicates of this type preferably have a two-dimensional sheet structure, such as the so-called δ-layer structure, as in EP 0 164514 and EP 0 293640 described. Processes for the preparation of crystalline layered silicates of this type are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2.

The most preferred crystalline layered sodium silicate compound has the formula δ-Na ₂ Si ₂ O ₅ , known as NaSKS-6 (trade name), marketed by Hoechst AG.

The Crystalline layered sodium silicate material is in granular detergent compositions preferably as particulate Fabric in inninger mixture with a solid, water-soluble, ionizable material as described in PCT Patent Application No. WO92 / 18594 described. The solid, water-soluble ionizable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof, with citric acid being preferred.

Examples of largely water-insoluble builders include the sodium aluminosilicates. Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ]. xH ₂ O, where z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline, being 10 % to 28%, more preferably between 18% and 22% of water in bound form.

The Aluminosilicate zeolites can Naturally occurring materials, but are preferably synthetic Origin. Synthetic crystalline aluminosilicate ion exchange materials are available under the name zeolite A, zeolite B, zeolite P, zeolite X, Zeolite HS and mixtures thereof.

One preferred method of synthesis of aluminosilicate zeolites is that of Schoeman et al. described (published in Zeolite (1994) 14 (2), 110-116), in which the author describes a method of preparing colloidal aluminosilicate zeolites describes. The colloidal aluminosilicate zeolite particles should preferably be such that no more than 5% of the particles have a Size over 1μm in diameter and not more than 5% of the particles are less than 0.05 μm in diameter to have. Preferably, the aluminosilicate zeolite particles have a average diameter between 0.01 μm and 1 μm, more preferably between 0.05 μm and 0.9 μm, most preferably between 0.1 μm and 0.6 μm.

Zeolite A has the formula Na ₁₂ [AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .xH ₂ O where x ranges from 20 to 30, in particular 27. Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .276H ₂ O. Zeolite MAP as disclosed in EP-B-384,070 is herein a preferred zeolite builder.

preferred Aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When used as a component of a detergent composition provide colloidal aluminosilicate zeolites, especially colloidal zeolite A, better builder performance in terms of better stain removal. A better builder performance will also be diminished in terms of one Fabric encrustation and better preservation of the whiteness of the fabric observed Problems that are likely with detergent compositions with bad Builders related.

A surprising finding is that mixed aluminosilicate zeolite detergent compositions comprising colloidal zeolite A and colloidal zeolite Y over commercially available zeolite A same weight to provide the same performance in the sequestration of calcium ions. Another surprising finding is that the above-described mixed aluminosilicate zeolite detergent compositions provide better performance in sequestering magnesium ions over commercially available zeolite A of the same weight.

surfactant

suitable Surfactants are selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants and mixtures thereof. The surfactant is typical in an amount of from 0.2 to 30% by weight, more preferably from 0.5 to 10 wt .-%, most preferably from 1 to 5 wt .-%, based on the composition of the active detergent ingredients.

A Typical list of anionic, nonionic, ampholytic and zwitterionic Classes and types of these surfactants are described in U.S. Patent 3,929,678, issued to Laughlin and Heuring on December 30, 1975. A List of suitable cationic surfactants is disclosed in U.S. Patent 4,259,217, issued to Murphy on March 31st 1981, listed. A list of surfactants typically found in detergent compositions is contained in, for example, EP-A-0414 549 and the PCT applications No. WO 93/08876 and WO 93/08874.

nonionic surfactant

in the Essentially any nonionic surfactant that is suitable for washing purposes suitable to be incorporated into the compositions. preferred not restrictive Classes of suitable nonionic surfactants are listed below.

nonionic Surfactant from ethoxylated alcohol

The Alkylethoxylate condensation products of aliphatic alcohols with From 1 to 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can be either straight or branched, primary or secondarily be and contain usually 6 to 22 carbon atoms. Particularly preferred the condensation products of alcohols with an alkyl group 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole Alcohol.

Surfactant out end-capped alkyl alkoxylate

A suitable surfactant of endcapped alkyl alkoxylate are the epoxy-capped, poly (oxyalkylated) alcohols represented by the formula: R ₁ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ₂ ] (I) wherein R _{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms; R _{2 is} a linear or branched aliphatic hydrocarbon radical having 2 to 26 carbon atoms; x is an integer having an average of 0.5 to 1.5, more preferably 1; and y is an integer having a value of at least 15, more preferably at least 20.

Preferably, the surfactant of formula I has at least 10 carbon atoms in the terminal epoxide unit [CH ₂ CH (OH) R ₂ ]. Suitable surfactants of formula I of the invention are POLY-TERGENT ^© SLF-18B nonionic surfactants, Olin Corporation, for example, as described in WO 94/22800, published October 13, 1994, Olin Corporation.

Ether-capped poly (oxyalkylated) alcohols

Preferred surfactants for use herein include ether-capped poly (oxyalkylated) alcohols having the formula: R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² wherein R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms; R ^{3 is} H or a linear aliphatic hydrocarbon radical of 1 to 4 carbon atoms; x is an integer with an average between 1 and 30, where if x 2 or greater, R ^{3 may be the} same or different and k and j are integers having an average of 1 to 12, and more preferably 1 to 5.

R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with 8 to 18 carbon atoms being most preferred. H or a linear aliphatic hydrocarbon radical having 1 to 2 carbon atoms is most preferred for R ³ . Preferably, x is an integer having an average of 1 to 20, more preferably 6 to 15.

As described above, in the preferred embodiments, R ^{3 may be the} same or different when x is greater than two. That is, R ³ may vary between any of the alkyleneoxy units as described above. For example, R3 may be selected to form ethylene oxide (EO) or propylene oxide (PO) when x is 3, and may be in the order (EO) (PO) (EO), (EO) (EO) (PO); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO) vary. Of course, the integer number three is chosen here only as an example, and the variation may be much larger and x may take on a much higher integer value, and may include, for example, numerous (EO) units and a much smaller number of (PO) units be.

Especially Preferred surfactants as described above include those with a low cloud point from below 20 ° C. These surfactants have a low cloud point can then used in conjunction with a high cloud point surfactant, as below for superior Grease cleaning benefits is described.

The most preferred ether-capped poly (oxyalkylated) alcohol surfactants are those in which k is 1 and j is 1 such that the surfactants have the following formulas: R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² wherein R ¹ , R ² and R ^{3 are} as defined above and x is an integer having an average of 1 to 30, preferably 1 to 20 and more preferably 6 to 18. Most preferred are surfactants wherein R ¹ and R ^{2 are} in the range of 9 to 14, R ^{3 is} H to form ethyleneoxy, and x is in the range of 6 to 15.

The ether-capped, poly (oxyalkylated) alcohol surfactants include three general components, namely a linear or branched alcohol, an alkylene oxide and a Alkyl ether end cap. The alkyl ether end cap and the alcohol are used as a hydrophobic, oil-soluble Section of the molecule, while the alkylene oxide group forms the hydrophilic, water-soluble portion of the molecule.

These Surfactants have significant compared to conventional surfactants Improvements in their stain removal properties and film forming Properties and in the removal of grease spills, when used in conjunction with high cloud point surfactants.

Generally expressed can the ether-capped invention poly (oxyalkylated) alcohol surfactants are prepared by a Aliphatic alcohol is reacted with an epoxide to form a Ether, which is then reacted with a base to a to form second epoxide. The second epoxide is then mixed with a reacted alkoxylated alcohol to the inventive novel To form connections. Examples of methods of preparation the ether-capped, poly (oxyalkylated) alcohol surfactants are below described:

Nonionic surfactant ethoxylated / propoxylated fatty alcohol

The ethoxylated C ₆ -C ₁₈ fatty alcohols and the mixed ethoxylated / propoxylated C ₆ -C ₁₈ fatty alcohols are suitable surfactants for use herein, particularly when they are water-soluble. Preferably, the ethoxylated fatty alcohols are the C ₁₀ -C ₁₈ ethoxylated fatty alcohols having a degree of ethoxylation of from 3 to 50, most preferably the ethoxylated C ₁₂ -C ₁₈ fatty alcohols having a degree of ethoxylation of from 3 to 40. Preferably, the mixed ethoxylated / propoxylated Fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10.

Nonionic EO / PO condensates with propylenegl

The condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of 1500 to 1800 and is water-insoluble. Examples of compounds of this type include certain of the commercially available Pluronic ^™ surfactants marketed by BASF.

Nonionic EO condensation products with propylene oxide / ethylenediamine adducts

The condensation products of ethylene oxide with the product of the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic portion of these products consists of the reaction product of ethylene diamine and excess propylene oxide and generally has a molecular weight of 2500 to 3000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic ^™ compounds marketed by BASF.

anionic surfactant

in the Essentially, each is suitable for Purification purpose suitable anionic surfactant. These include salts (including for example, sodium, potassium, ammonium and substituted ammonium salts, such as Mono-, di- and triethanolamine salts) of the anionic sulphate, sulphonate, Carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are prefers.

Other anionic surfactants include the isethionates, such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids in or derived from tallow oil.

anionic sulphate

Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C ₅ -C ₁₇ acyl-N- (C ₁ -C ₄ alkyl) and -N- ( C ₁ -C ₂ hydroxyalkyl) glucamine sulfates and sulfates of alkyl polysaccharides, such as the sulfates of alkyl polyglucoside (wherein the nonionic unsulfated compounds are described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary C ₁₀ -C ₁₈ alkyl sulfates, more preferably the branched chain C ₁₁ -C ₁₅ alkyl sulfates and the straight chain C ₁₂ -C ₁₄ alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C ₁₀ -C ₁₈ alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C ₁₁ -C _18, most preferably a C ₁₁ -C ₁₅ alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably of 1 to 5 moles of ethylene oxide per molecule.

In In a particularly preferred aspect of the invention are mixtures the preferred alkyl sulfate and Alkylethoxysulfattenside used. Such mixtures are disclosed in PCT Patent Application No. WO 93/18124 disclosed.

anionic sulfonate

Anionic sulfonate surfactants suitable for use herein include the salts of linear C ₅ -C ₂₀ alkyl benzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids. Alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixture thereof.

anionic carboxylate

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

Suitable alkyl ethoxy carboxylates include those with the formula RO (CH ₂ CH ₂ 0) _x CH ₂ C00 ^- M ⁺ wherein R is a C ₆ - to C ₁₈ alkyl group, x is in the range of 0 to 10 and the ethoxylate distribution is such the amount of material by weight is less than 20% when x is 0 and M is a cation. Suitable alkylpolyethoxypolycarboxylate surfactants include those having the formula RO (CHR ₁ -CHR ₂ -O) -R ₃ , wherein R is a C ₆ to C ₁₈ alkyl group, x is 1 to 25, R ₁ and R _{2 are} selected from the group consisting of hydrogen, a methyl acid residue, a succinic acid residue, a hydroxysuccinic acid residue, and mixtures thereof, and R _{3 is} selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbons of 1 to 8 carbon atoms, and mixtures thereof.

suitable Soap surfactants include the secondary soap surfactants which have a Carboxy unit in combination with a secondary carbon included. Preferred secondary Soap surfactants for use herein are water-soluble Representative selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain Soaps can also as a foam suppressant be included.

Alkali

Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R ¹ ) CH ₂ COOM, wherein R is a linear or branched C ₅ -C ₁₇ alkyl or alkenyl group, R ^{1 is} a C ₁ -C ₄ alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and Oleylmethylsarcosinate in the form of their sodium salts.

amphoteric surfactant

suitable amphoteric surfactants for this purpose Use include the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include the compounds of the formula R ₃ (OR ₄ ) _x N ⁰ (R ⁵ ) ₂ wherein R _{3 is} selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkylphenyl group of 8 to 26 carbon atoms or mixtures thereof; R _{4 is} an alkylene or hydroxyallyl group having 2 to 3 carbon atoms or mixture thereof; x is 0 to 5, preferably 0 to 3; and each R ^{5 is} an alkyl or hydroxyalkyl group of 1 to 3 or a polyethylene oxide group of 1 to 3 ethylene oxide groups. Preferred are C ₁₀ -C ₁₈ alkyldimethylamine oxide, and C _10-18 -Acylamidoalkyldimethylaminoxid.

One suitable example of an alkylaphodicarboxylic acid is Miranol (TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.

zwitterionic surfactant

The Detergent compositions herein may also contain zwitterionic surfactants contain. These surfactants can in the broadest sense as derivatives of secondary and tertiary amines, Derivatives of heterocyclic secondary and tertiary Amines or derivatives quaternary Ammonium compounds, quaternary Phosphonium or tertiary Sulfonium compounds are described. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for this purpose Use.

Suitable betaines are those compounds of the formula R (R ') ₂ N ⁺ R ² COO ^- wherein R is a C ₆ -C ₁₈ hydrocarbyl group, each R _{1 is} typically a C ₁ -C ₃ alkyl and R ^{2 is} a C ₁ -C ₅ -hydrocarbyl group. Preferred betaines are C _12-18 dimethyl ammonium hexanoate and the C _10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

cationic surfactant

In Cationic ester surfactants used in this invention are preferred water-dispersible compounds having surfactant properties, comprising at least one ester (i.e., -COO -) linkage and at least one cationic loaded group. Other suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in US Pat. Nos. 4,282,842, 4,239,660 and 4260529 discloses.

Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C ₆ -C ₁₆ , preferably C ₆ -C _10, N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are represented by methyl, hydroxyethyl or hydroxypropyl groups are substituted.

Softener ingredients

The Softener ingredients according to the invention can from all known ingredients that make a tissue softening Have effect selected be.

to Providing the plasticizing properties of ready to use Compositions used clay minerals can be as expandable, three-layered Clays are described, d. H. Aluminosilicates and magnesium silicates with an ion exchange ability of at least 50 meq / 100 g of clay. The description of clays term "expandable" refers to the ability the toner layer structures swell on contact with water or to be expanded. The three-layered, Expandable clays are those materials that are geological are classified as smectites.

There are two classes of smectite-type clays; in the first class, aluminum oxide is present in the silicate crystal lattice; in the second smectite class, magnesium oxide is present in the silicate crystal lattice. The general formulas of these smectites are Al ₂ (Si ₂ O ₅ ) ₂ (OH) ₂ and Mg ₃ (Si ₂ O ₅ ) (OH) ₂ for the alumina type and magnesium oxide type clays, respectively. It should be noted that the amount of hydration water in the above formulas may vary depending on the processing of the clay. This is immaterial to the use of the smectite clays in the present invention because the expanding properties of the hydrated clays are determined by the structure of the silicate lattice. Further, in the crystal lattice of smectites, atom substitutions by iron and magnesium may occur, while metal cations such as Na ⁺ , Ca ⁺⁺ and H ⁺ may be present along with the water of hydration to ensure electrical neutrality. Except as noted below, such cation substitutions are immaterial to the use of the clays herein because the desirable physical properties of the clays are not significantly altered thereby.

The useful herein Three-layer, expandable aluminosilicates are further characterized by a dioctahedral crystal lattice, while the expandable, three-layered magnesium silicates a trioctahedral Have crystal lattice.

As noted hereinbefore, the clays used in the compositions of the present invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, magnesium ions, and the like. It is common to differentiate clays from the predominantly or exclusively absorbed cation. For example, a sodium earth soil is one in which sodium is predominantly absorbed as the cation. Such absorbed cations may participate in exchange reactions with cations present in aqueous solutions. A typical exchange reaction involving a smectite type alumina is expressed by the following equation. Smectite Clay (Na) + NH ₄ OH → Smectite Clay (NH ₄ ) + NaOH.

There in the preceding equilibrium reaction, a weight equivalent of an ammonium ion is a weight equivalent Replaced sodium, it is common the cation exchange ability (sometimes referred to as "base exchange capacity") in milliequivalents per 100 g of alumina (meq./100 g). The cation exchange ability Of clays can be measured in several ways, for example followed by electrodialysis, by exchange with ammonium ions by titration or by a methylene blue method, all completely in Grimshaw, "The Chemistry and Physics of Clays ", Pp. 264-265, Interscience (1971) are. The cation exchange ability of a clay mineral is related to factors such as swelling properties the clay, the charge of the clay, which in turn at least partially determined by the lattice structure, and the like in context. The ion exchange ability of clays is very high varies and is in the range of about 2 meq / 100 g for kaolinite to about 150 meq / 100g and above for certain Clays of montmorillonite types. Illite clays have an ion exchange ability in the lower area, d. H. by about 26 meq / 100g for an average illite clay.

Illite and kaolin clay soils, with their relatively weak ion exchange capacity, are preferably not used as clays in the ready-to-use compositions. In fact, such illite and kaolin-clay soils are an essential component of clay soils and, as mentioned above, are derived from ready-to-use fabric surface compositions removed. However, smectites, such as nontonite, having an ion exchange capacity of about 70 meq / 100g, and montmorillonite having an ion exchange capacity greater than 70 meq / 100g, have found utility in the ready-to-use compositions in that they are deposited on fabrics to the desired levels to provide plasticizing benefits. Accordingly, clay minerals useful herein can be characterized as expandable, three-layer smectite type clays having an ion exchange capacity of at least about 50 meq / 100 g.

Without To be bound to a certain theory, it seems that the advantageous softening (and possibly color-inhibiting) Benefits of the ready-to-use compositions and the physical Properties and ion exchange properties of those used herein Clay can be attributed. This is to say that it has been shown in experiments that non-expandable clays, like the kaolinites and the illites, each containing clay classes an ion exchange ability of less than 50 meq / 100g are not the beneficial aspects of clays used in the ready-to-use compositions have.

The smectite clays used in the compositions herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite and vermiculite. The clays herein are available under various trade names, for example Thixogel # 1 ^® and Gelwhite GP ^® from Georgia Kaolin Co., Elizabeth, New Jersey, USA; Volclay BC ^® and Volclay # 325 ^®, from American Colloid Co., Skokie, Illinois, USA; Black Hills Bentonite BH450 ^®, from International Minerals and Chemicals; and Veegum Pro and Veegum F, by RT Vanderbilt. It should be noted that smectite-type minerals, which are available under the above trade names, may include mixtures of various single-unit minerals. Such mixtures of smectite minerals are suitable for use herein.

While any smectite-type clay having a cation exchange capacity of at least about 50 meq / 100 g is useful herein, certain clays are preferred. For example, Gelwhite GP ^® is an extremely white form of smectite clay and is therefore preferred when formulating white, granular detergent compositions. Volclay BC ^®, a clay mineral of the smectite type with at least 3% iron (expressed as Fe ₂ O ₃₎ in the crystal lattice and a very high ion exchange capacity, is one of the most effective and efficient clays for use in detergent compositions and preferably from the standpoint of product performance terms.

suitable Clay minerals for this purpose Can use based on the fact that smectite has a true 14Å x-ray diffraction pattern. This characteristic pattern provides in combination with a in the aforementioned Fashion performed Exchange capacity measurement a basis for the selection of certain smectite-type minerals for use in the granular detergent compositions disclosed herein.

The Alumina is preferably mainly in the form of granules before, wherein at least 50%, preferably at least 75% and still more preferably at least 90% in the form of granules having a size of at least 0.1 mm up to 1.8 mm, preferably up to 1.18 mm, preferably from 0.15 mm to 0.85 mm. Preferably, the amount is clay in the granules at least 50% by weight, more preferably at least 70 wt .-% and most preferably at least 90 wt .-% of Granules.

Smectite clays U.S. Patent Nos. 3,862,058; 3,948,790; 4,062,647. The European Patent Nos. EP-A-299,575 and EP-A-313,146 in the name of Procter and Gamble Company describe suitable organic polymeric flocculants made of clay.

Other suitable softening ingredients are long chain polymers and copolymers derived from monomers such as ethylene oxide, Acrylamide, acrylic acid, Dimethylaminoethyl methacrylate, vinyl alcohol, vinylpyrrolidone and Ethylenimid. Preference is given to polymers of ethylene oxide, acrylamide and acrylic acid. These polymers have an average molecular weight in the Range from 100,000 to 10 million, more preferably from 150,000 to 5 million. The average molecular weight of a polymer can easily by gel permeation chromatography against standards of polyethylene oxide with narrow molecular weight distributions become. The most preferred polymers are polyethylene oxides.

Other suitable softening ingredients include cationic fabric softeners which may also be incorporated into the compositions of the present invention suitable for use in laundering processes. Suitable cationic fabric softening agents include the water run-soluble tertiary amines or dilange-chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.

enzymes

Where present, the enzymes are selected from the group consisting from cellulases, hemicellulases, peroxidases, proteases, glucoamylases, en, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, Keratanases, reductases, oxidases, phenol oxidases, lipoxygenases, Ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, Arabinosidases, hyaluronidase, chondroitinases laccase or mixtures from that.

preferred Enzymes include protease, amylase, lipase, peroxidases, cutinase and / or cellulose in association with one or more plant cell wall degrading enzymes.

The cellulases suitable according to the invention comprise cellulases from bacteria or fungi. Preferably, they have a pH optimum between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al., J61078384, and WO96 / 02653, which disclose cellulases from fungi made from Humicola insolens, Trichoderma, Thielavia, and Sporotrichum, respectively. EP 739 982 describes cellulases isolated from a novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2,075,028; GB-A-2.095.275; DE-OS-2,247,832 and WO95 / 26398.

Examples Such cellulases are cellulases derived from a strain of Humicola insolens (Huinicola grisea var. thermoidea), especially the Humicola strain DSM 1800, are manufactured. Other suitable cellulases are cellulases from Humicola insolens with a molecular weight of 50 KDa, one isoelectric point of 5.5 and with 415 amino acids; and a 43kD endoglucanase from Humicola insolens, DSM 1800, with cellulase activity; a preferred one Endoglucanase ingredient has the amino acid sequence found in the PCT Patent Application No. WO 91/17243. Equally suitable Cellulases are the EGIII cellulases of Trichoderma longibrachiatum, described in WO94 / 21801, Genencor, published September 29, 1994. Particularly suitable cellulases are the cellulases with color care benefits. Examples of such cellulases are cellulases described in EP-A-495257, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are particularly useful. See also WO91 / 17244 and WO91 / 21801. Other suitable cellulases for the Fabric care and / or with cleaning properties are described in WO96 / 34092, WO96 / 17994 and WO95 / 24471.

The Cellulases are normal in the detergent compositions in an amount of 0.0001 to 2 wt .-% of active enzyme based on containing the detergent composition.

peroxidase can in combination with oxygen sources, for example percarbonate, Perborate, persulfate, hydrogen peroxide, etc., for "bleaching in solution, "that is, to prevent the transmission of dyes or pigments that are made while washing from substrates be removed on other substrates in the washing solution used become. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and Haloperoxidase, such as chloro- and bromoperoxidase. Peroxidase Detergent compositions are, for example, international in the PCT Application WO 89/099813, WO89 / 09813 and EP-A-5407847 filed on 6th November 1991, disclosed. Also suitable is the enzyme laccase.

preferred amplifier are substituted phenthiazine and phenoxasine-10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoaazine propionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted Syringates (C3-C5 substituted alkylsyringates) and phenols. sodium or perborate are preferred sources of hydrogen peroxide.

The Cellulases and / or peroxidases are in the detergent compositions normally in an amount of from 0.0001 to 2% by weight of active enzyme based on the detergent composition.

Other preferred enzymes that may be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which have a positive immunological cross-reaction with the antibody against the lipase produced by the microorganism Pseudomonas fluorescent IAM 1057 show. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the trade name Lipase P "Amano", hereinafter referred to as "Ainano-P". Other suitable commercial lipases include Amano-CES, lipases from Chromobacter viscosum, e.g. Chromobacter viscosum var. Lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, Chromobacter viscosum lipases from US Biochemical Corp., USA, and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. Particularly suitable lipases are lipases such as M1 Lipase ^R and Lipomax ^R (Gist-Brocades) and Lipolase ^R and Lipolase Ultra ^R (Novo), which have been found to be very effective when used in combination with the compositions of the invention. Also suitable are the lipolytic enzymes described in EP 258,068 , WO 92/05249 and WO 95/22615 to Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 to Unilever.

Also suitable are cutinases [EC 3.1.1.50], which as a special type lipase can be considered, namely as Lipases that do not interfacial activation require. The addition of cutinases to detergent compositions has been described, for example, in WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).

The Lipases and / or cutinases are in the detergent composition normally in an amount of 0.0001 to 2% by weight of active enzyme based on the detergent composition.

Suitable examples of proteases are the subtilisins obtained from certain strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). One suitable protease with maximum activity IMPH-range of 8 to 12 is obtained from a strain of Bacillus, developed and mentioned as ESPERASE ^® by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE ^®, DURAZYM ^® and SAVINASE ^® from Novo and MAXATASE ^®, MAXACAL ^®, PROPERASE® ^® and MAXAPEM ^® (protein engineered Maxacal after) from Gist-Brocades.

proteolytic Enzymes also include modified bacterial serine proteases, such as those in EP-A-251446, (in particular pages 17, 24 and 98) on April 28, 1987, and hereafter referred to as "Protease B", and in the European Patent Application 199,404, Venegas, published October 29, 1986, which is a modified bacterial proteolytic serine enzyme refers to herein "protease A "is called. What is suitable herein is "protease C is called, which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine Replaced valine at position 104, serine asparagine at position 123 replaced alanine threonine at position 274. Protease C is published in WO 91/06637 on May 16, 1991. Genetically modified variants, in particular protease C are also included herein.

A Particularly preferred protease, termed "protease D", is a carbonyl hydrolase variant with a non-naturally occurring amino acid sequence, which consists of a Precursor carbonyl by substituting several amino acid residues with another amino acid in a position of carbonyl hydrolase corresponding to position +76, is derived, preferably in combination with one or multiple amino acid residue positions, which correspond to those selected from the group consisting from +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and / or +274 according to the numbering of subtilisin from Bacillus amyloliquefaciens, as in WO95 / 10591 and in the patent application by C. Ghosh et al., "Whitening Compositions Comprising Protease Enzymes "with U.S. Serial No. 08 / 322,677, filed on October 13, 1994.

Also suitable according to the invention are proteases, described in the patent applications EP 251 446 and WO 91/06637, protease BLAP ^® described in WO91 / 02792 and alia variants described in WO 95/23221.

Similarly, a protease from Bacillus sp. NCIMB 40338, described in WO 93/18140 A to Novo, with activity in the upper pH range possible. Enzymatic detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. If desired, a protease with reduced adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant detergent-type protease-like protease useful herein is described in WO 94/25583 to Novo. Other suitable proteases are in EP 516 200 described by Unilever.

Other preferred protease enzymes include protease enzymes which a Carbonylhydrolasen variant with a non-naturally occurring amino acid sequence which are obtained by substituting several amino acid residues of a precursor carbonyl hydrolase through other amino acids is derived, with the majority of those in the precursor enzyme substituted amino acid residues Position +210 in combination with one or more of the following radicals corresponds to: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the numbered position corresponds to the naturally occurring one Subtilisin from Bacillus amyloliquefaciens or equivalent amino acid residues in other carbonyl hydrolases or subtilisin (such as Bacillus lentus Subtilisin). Preferred enzymes of this type include the with position changes at +210, +76, +103, +104, +156 and +166.

The proteolytic enzymes are in the detergent compositions of the invention in an amount of 0.0001 to 2 wt .-%, preferably from 0.001 to 0.2 wt .-%, more preferably from 0.005 to 0.1 wt .-% pure enzyme included on the weight of the composition.

Amylases (α and / or β) may be included to remove carbohydrate-based stains. WO94 / 02597, Novo Nordisk A / S, published February 3, 1994, describes cleaning compositions in which amylase mutants are present. See also WO95 / 10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-Amylases are known in the art and include those described in US Pat. No. 5,003,257; EP 252,666 ; WO / 91/00353; FR 2,676,456; EP 285,123 ; EP 525,610 ; EP 368,341 ; and British Patent No. 1,296,839 (Novo). Other suitable amylases are stability-enhancing amylases described in WO94 / 18314, published August 18, 1994, and WO96 / 05295, Genencor, published February 22, 1996, and amylase variants with additional modification in the direct parent compound, available from Novo Nordisk A / S, disclosed in WO 95/10603, published in April 95. Also suitable are amylases described in EP 277 216 WO95 / 26397 and WO96 / 23873 (all to Novo Nordisk).

Examples of commercial α-amylases products are Purafect OxAm ^® from Genencor and Termamyl ^®, Ban ^®, Fungamyl ^® and Duramyl ^®, Natalase ^® all available from Novo Nordisk A / S Denmark WO95 / 26397 describes other suitable amylases: α-amylases characterized that its specific activity in a temperature range from 25 ° C to 55 ° C and at a pH in the range of 8 to 10, at least 25% higher than the specific activity of Termamyl ^®, measured in the Phadebas ^{® α-Amylaseaktivitätsassay.} Suitable variants of the abovementioned enzymes are those described in WO96 / 23873 (Novo Nordisk). Other amylolytic enzymes having improved properties in terms of activity level and the combination of thermal stability and a higher level of activity are described in WO95 / 35382.

preferred Close amylase enzymes those described in WO95 / 26397 and in the co-pending application of Novo Nordisk, PCT / DK96 / 00056, described.

The amylolytic enzymes are in the detergent compositions of the invention in an amount of 0.0001 to 2% by weight, preferably 0.00018 to 0.06 wt.%, more preferably from 0.00024 to 0.048 wt.% pure Enzyme based on the weight of the composition.

In a particularly preferred embodiment include the compositions of the invention Amylase enzymes, especially those in WO95 / 26397 and the same pending Registration of Novo Nordisk PCT / DK96 / 00056 in combination with a complementary Amylase described.

By "complementary" is meant the addition of one or more amylases suitable for laundering Examples of complementary amylases (α and / or β) are described below: WO94 / 02597 and WO95 / 10603, Novo Nordisk A / S, describe cleaning compositions containing amylase mutants Other amylases known for use in cleaning compositions include α- and β-amylases α-amylases are known in the art and include those described in U.S. Patent Nos. 5,003,257; EP 252,666 ; WO / 91/00353; FR 2,676,456; EP 285,123 ; EP 525,610 ; EP 368,341 ; and British Patent No. 1,296,839 (Novo). Other suitable amylases are stability-enhancing amylases described in WO94 / 18314 and WO96 / 05295, Genencor, and amylase variants with additional modification in the direct parent compound, available from Novo Nordisk A / S, disclosed in WO 95/10603. Also suitable are amylases described in EP 277 216 (Novo Nordisk). Examples of commercial α-amylases products are Purafect Ox Am ^® from Genencor and Termamyl ^®, Ban ^®, Fungamyl ^® and Duramyl ^®, all available from Novo Nordisk A / S Denmark. WO95 / 26397 describes other suitable amylases: α-amyla characterized in that their specific activity in a temperature range of 25 ° C to 55 ° C and at a pH in the range of 8 to 10 at least 25% higher than the specific activity of Termamyl ^® , measured in Phadebas ^® α -Amylaseaktivitätsassay. Suitable variants of the abovementioned enzymes are those described in WO96123873 (Novo Nordisk). Other amylolytic enzymes having improved properties in terms of activity level and the combination of thermal stability and a higher level of activity are described in WO95 / 35382. Preferred complementary amylases for the present invention are the amylases sold under the tradename Purafect Ox Am ^R and described in WO 94/18314, WO 96/05295 and sold by Genencor; Termamyl ^®, Fungamyl.RTM ^®, Ban ^® Natalase ^® and Duramyl ^®, all available from Novo Nordisk A / S and Maxamyl ^® by Gist-Brocades.

The complementary Amylase is in the detergent composition of the invention generally in an amount of 0.0001 to 2 wt .-%, preferably from 0.00018 to 0.06 wt.%, more preferably from 0.00024 to 0.048 Wt .-% pure enzyme based on the weight of the composition contain. Preferably, a weight ratio of the pure enzyme is the specific amylase to the complementary amylase between 9: 1 and 1: 9, more preferably 4: 1 and 1: 4, and most preferably between 2: 1 and 1: 2.

The mentioned above Enzymes can have any suitable origin, such as plants, animals, Bacteria, fungi and yeasts. They can also be more mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.) origin be. It can be purified or non-purified forms of these enzymes are used. Are included by definition also mutants of the native enzymes. Mutants can be produced, for example, by protein and / or gene engineering, obtain chemical and / or physical modifications of native enzymes become. To common practice belongs also the expression of the enzyme in a host organism in which the genetic material for the Preparation of the enzyme was cloned.

The Enzymes are normally in the detergent composition in one Amount of 0.0001 to 2 wt .-% of active enzyme by weight the detergent composition. The enzymes can be considered as separate individual ingredients (prills, granules, stabilized Liquids, etc., which contain an enzyme) or as mixtures of two or several enzymes (eg cogranules) are added.

Other suitable detergent ingredients that may be added are Enzyme oxidation scavengers in EP-A-553607, filed January 31, 1992 are. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A number of enzyme materials and adjuvants for their incorporation into synthetic detergent compositions are also described in WO 93/07263 A and WO 93/07260 A, Genencor International, WO 89/08694 A, Novo, and in US Pat US 3,553,139, 5 , January 1971, to McCarty et al. Enzymes are also in US 4,101,457 , Place et al., July 18, 1978, and in US 4,507,219 , Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such preparations are disclosed in U.S. Pat US 4,261,868 , Hora et al., Apr. 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyrrstabilisierungstechniken are in US 3,600,319, 17 , August 1971, Gedge et al., In EP 199,405 and EP 200,586, 29 , October 1986, Venegas, discloses and explains. For example, enzyme stabilization systems are also available in US 3,519,570 described. A useful Bacillus, sp. AC13, which provides proteases, xylanases and cellulases, is described in WO 94/01532 A to Novo.

bleach

suitable Bleaching agents include chlorine and oxygen releasing bleaches, preferably oxygen-releasing bleaches which are a hydrogen peroxide source and an organic peroxyacid bleach precursor compound contain. The preparation of the organic peroxyacid proceeds via a in situ reaction of the precursor with a hydrogen peroxide source. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In a preferred Aspect contains the composition is a preformed organic peroxyacid in one liquid Matrix as a suspended solid as described above. Also conceivable are compositions which are a mixture of a hydrogen peroxide source and an organic peroxyacid precursor in Combination with a preformed organic peroxyacid contained.

inorganic Perhydrate bleaches

Particulate compositions preferably contain a source of hydrogen peroxide as an oxygen releasing bleach. Preferred sources of hydrogen peroxide include inorganic perhydrate salts.

The inorganic perhydrate salts are usually in the form of the sodium salt in an amount of from 1% to 40% by weight, more preferably from 2 wt% to 30 wt%, and most preferably from 5 wt% to 25 wt .-% of the compositions.

Examples Inorganic perhydrate salts include perborate, percarbonate, perphosphate, Persulfate and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts is in preferred embodiments such granular However, compositions a coated form of the material used, which better storage stability of the perhydrate salt in the granular Product offers.

Sodium perborate may be in the form of the monohydrate of nominal formula NaBO ₂ H ₂ O ₂ or of the tetrahydrate, NaBO ₂ H ₂ O ₂ .3H ₂ O.

Alkali metal percarbonates, in particular sodium percarbonate, are preferred perhydrates for inclusion in compositions according to the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid. Sodium percarbonate, a hydrogen peroxide addition compound, tends to release the hydrogen peroxide quite rapidly upon dissolution, which may increase the tendency for locally high levels of bleach to form. The percarbonate is most preferably incorporated into such compositions in a coated form which provides stability within the product.

A suitable coating material which provides stability within the product comprises the mixed salt of a water-soluble alkali metal sulfate and carbonate. Such coatings, together with coating methods, have already been described in GB-1,466,799 issued to Interox on Mar. 9, 1977. The weight ratio of the mixed salt / percarbonate coating material is in the range of from 1: 200 to 1: 4, more preferably from 1:99 to 1: 9, and most preferably from 1:49 to 1:19. Preferably, the mixed salt is sodium sulfate and sodium carbonate having the general formula Na ₂ SO ₄ .n.Na ₂ CO ₃ wherein n is between 0.1 to 3, n is preferably 0.3 to 1.0, and n is most preferably 0.2 to Is 0.5.

Another suitable coating material which provides stability within the product comprises sodium silicate having a SiO ₂ : Na ₂ O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1 and / or sodium metasilicate, preferably used in an amount of from 2 to 10% by weight, (usually from 3 to 5% by weight) of SiO ₂ based on the weight of the inorganic perhydrate salt. The coating can also contain magnesium silicate. Coatings containing silicate and borate salts or boric acid or other inorganic salts are also suitable.

Peroxyacid bleach precursor

worin L eine Abgangsgruppe ist und X im Wesentlichen jede Funktionalität annimmt, sodass die durch Perhydrolyse hergestellte Peroxysäure folgende Struktur besitzt: Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to yield a peroxyacid. Peroxyacid bleach precursors can generally be represented as

where L is a leaving group and X assumes essentially any functionality such that the peroxyacid produced by perhydrolysis has the structure:

The peroxyacid bleach precursor compounds are preferably present in an amount between 0.5 and 20% by weight, more preferably between 1 and 10% by weight, most preferably from 1.5 to 5% by weight of the compositions.

suitable Peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, their precursor selected from many classes could be. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of suitable Materials in these classes are disclosed in GB-A-1586789. Suitable esters are in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

leaving group

The Leaving group, hereafter called L group, must be sufficiently reactive be so that the perhydrolysis reaction within the optimal period can expire (eg within a wash cycle). Is L, however too reactive, this activator is for use in one Bleaching composition difficult to stabilize.

und Mischungen davon, wobei R¹ eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R³ eine Alkylkette mit 1 bis 8 Kohlenstoffatomen ist, R⁴ H oder R³ ist, R⁵ eine Alkenylkette mit 1 bis 8 Kohlenstoffatomen ist und Y H oder eine lösungsvermittelnde Gruppe ist. Jedes R¹, R³ und R⁴ kann durch im Wesentlichen jede funktionelle Gruppe substituiert werden, einschließlich beispielsweise durch Alkyl-, Hydroxy-, Alkoxy-, Halogen-, Amin-, Nitrosyl-, Amid- und Ammonium- oder Alkylammoniumgruppen.Preferred L groups are selected from the group consisting of:

and mixtures thereof, wherein R ^{1 is} an alkyl, aryl or alkaryl group of 1 to 14 carbon atoms, R ^{3 is} an alkyl chain of 1 to 8 carbon atoms, R ^{4 is} H or R ³ , R ^{5 is} an alkenyl chain of 1 to 8 carbon atoms is and is YH or a solubilizing group. Each of R ¹ , R ³ and R ⁴ may be substituted by substantially any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

The preferred solubilizing groups are -SO ₃ ^- M ⁺ , CO ₂ ^- M ⁺ , -SO ₄ ^- M ⁺ , -N + (R ³ ) ₄ X- and O-N (R ³ ) ₃ and most preferably -SO ₃ ^- M ⁺ and -CO ₂ ^- M ⁺ wherein R ³ is an alkyl chain having 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, Me ethyl sulfate or an acetate anion.

Perbenzoic acid precursor

Provide perbenzoic acid precursors in perhydrolysis, perbenzoic acid.

suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyloxybenzenesulfonates, including for example, benzoyloxybenzenesulfonate:

Ac = COCH₃; Bz = BenzoylAlso suitable are the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, including, for example:

Ac = COCH ₃ ; Bz = benzoyl

Perbenzoic acid precursor compounds of the imide type include N-benzoylsuccinimide, tetrabenzoylethylenediamine and the N-benzoyl-substituted ureas. Suitable perbenzoic acid precursors of Imidazole type include N-benzoylimidazole and N-benzoylbenzimidazole and other suitable N-acyl group-containing perbenzoic acid precursors N-benzoyl pyrrolidone, Dibenzyltaurine and benzoylpyroglutamic acid.

Other Perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides and the Connection with the formula

Phthalsäureanliydrid is another perbenzoic acid precursor compound useful herein:

worin n 0 bis 8, vorzugsweise 0 bis 2 ist, und R⁶ eine Benzoylgruppe ist.Suitable N-acylated lactamperbenzoic acid precursors have the formula:

wherein n is 0 to 8, preferably 0 to 2, and R ^{6 is} a benzoyl group.

Perbenzoic acid derivative precursors

Perbenzoic acid derivative precursor provide perbenzoic acids substituted in perhydrolysis.

suitable substituted perbenzoic acid derivative precursors any of the perbenzoic precursors disclosed herein, wherein the benzoyl group by essentially any non-positively charged (i.e. non-cationic) functional group, including, for example by alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and Amide groups.

worin R₁ eine Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R² eine Arylen- oder eine Alkarylengruppe mit 1 bis 14 Kohlenstoffatomen ist, R⁵ H oder eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 10 Kohlenstoffatomen ist und L im Wesentlichen jede Abgangsgruppe ist. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R¹ kann Aryl, substituiertes Aryl oder Alkylaryl mit Verzweigungen, Substitutionen oder beidem sein und kann synthetischer Herkunft oder natürlicher Herkunft sein, einschließlich beispielsweise Talgfett. Analoge Strukturvariationen sind für R² zulässig. Die Substitution kann Alkyl-, Aryl-, Halogen-, Stickstoff-, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen umfassen. R⁵ ist vorzugsweise H oder Methyl. R¹ und R⁵ sollten nicht mehr als insgesamt 18 Kohlenstoffatome enthalten. Amidsubstituierte Bleichmittel-Aktivatorverbindungen dieses Typs sind in EP-A-0170386 beschrieben.A preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulas:

wherein R _{1 is} an aryl or alkaryl group having 1 to 14 carbon atoms, R ^{2 is} an arylene or an alkarylene group having 1 to 14 carbon atoms, R ^{5 is} H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms, and L is essentially any leaving group. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains 4 to 8 carbon atoms. R ¹ may be aryl, substituted aryl, or alkylaryl with branches, substitutions, or both, and may be of synthetic or natural origin, including, for example, tallow fat. Analogous structure variations are allowed for R ² . The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably H 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-0170386.

cationic Peroxyacid precursor

cationic Peroxyacid precursor compounds result in perhydrolysis cationic peroxyacids.

typically, cationic peroxyacid precursors are formed, by the peroxyacid part a suitable peroxyacid precursor compound by a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group, is substituted. Cationic peroxyacid precursors are typically as a salt with a suitable anion, such as a halide ion or a methylsulfate, present in the composition.

The such cationically substituted peroxyacid precursor compound may be a precursor compound from perbenzoic acid or a substituted derivative thereof as hereinbefore described. Alternatively, the peroxyacid precursor compound may be a precursor compound from alkyl percarboxylic acid or an amide-substituted alkyl peroxyacid precursor as described below be.

Cationic peroxyacid precursors are disclosed in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; GB 1,382,594 ; EP 475,512, 458,396 and 284.292 ; and in JP 87-318,332.

suitable cationic peroxyacid precursors any ammonium or alkylammonium-substituted alkyl or benzoyloxybenzenesulfonate, N-acylated caprolactams and monobenzoyl tetraacetyl glucose benzoyl peroxides.

A preferred cationically substituted benzoyloxybenzenesulfonate is 4- (trimethylammonium um) methyl derivative of benzoyloxybenzenesulfonate:

One preferred cationically substituted alkyloxybenzenesulfonate the formula:

preferred cationic peroxyacid precursors of Class of N-acylated caprolactams include the trialkylammoniummethylenebenzoylcaprolactams, in particular trimethylaminonium methylene benzoylcaprolactam:

wobei n 0 bis 12, insbesondere 1 bis 5 ist.Other preferred cationic peroxyacid precursors of the class of N-acylated caprolactams include the triallyl ammonium methylene caprolactams:

where n is 0 to 12, in particular 1 to 5.

One Another preferred cationic peroxyacid precursor is 2- (N, N, N-trimethylammonium) ethyl-sodium-4-sulfophenyl carbonate chloride.

Alkyl bleach precursor

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

Preferred imidype alkyl percarboxylic acid precursor compounds include the N, N, N ¹ N ¹ tetraacetylated alkylenediamines wherein the alkylene group contains from 1 to 6 carbon atoms, especially those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include Sodium 3,5,5-trimethyl hexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Amide substituted alkyl peroxyacid precursors

worin R¹ eine Alkylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R² eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen ist, R⁵ H oder eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen ist und L im Wesentlichen jede Abgangsgruppe ist. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R¹ kann ein geradkettiges oder verzweigtes Alkyl mit Verzweigungen, Substitutionen oder beidem sein und kann synthetischer Herkunft oder natürlicher Herkunft sein, einschließlich beispielsweise Talgfett. Analoge Strukturvariationen sind für R² zulässig. Die Substitution kann Alkyl-, Halogen-, Stickstoff-, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen umfassen. R⁵ ist vorzugsweise H oder Methyl. R¹ und R⁵ sollten nicht mehr als insgesamt 18 Kohlenstoffatome enthalten. Amidsubstituierte Bleichmittel-Aktivatorverbindungen dieses Typs sind in EP-A-0170386 beschrieben.Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those having the following general formulas:

wherein R ^{1 is} an alkyl group having 1 to 14 carbon atoms, R ^{2 is} an alkylene group having 1 to 14 carbon atoms, R ^{5 is} H or an alkyl group having 1 to 10 carbon atoms, and L is substantially each leaving group. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains 4 to 8 carbon atoms. R ¹ may be a straight chain or branched alkyl with branches, substitutions or both, and may be of synthetic or natural origin including, for example, tallow fat. Analogous structure variations are allowed for R ² . The substitution may include alkyl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably H 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-0170386.

organic Benzoxazine peroxyacid precursor

einschließlich der substituierten Benzoxazine des Typs

worin R₁ H, Alkyl, Alkaryl, Aryl, Arylalkyl ist und worin R², R³, R⁴ und R⁵ dieselben oder unterschiedliche Substituenten sein können, ausgewählt aus H, Halogen-, Alkyl-, Alkenyl-, Aryl-, Hydroxyl- Alkoxyl-, Amino-, Alkylamino-, COOR₆- (worin R₆ H oder eine Alkylgruppe ist) und Carbonylfunktionen.Also suitable are benzoxazine-type precursor compounds as disclosed, for example, in EP-A-332,294 and EP-A-482,807, especially those having the formula:

including the substituted benzoxazines of the type

wherein R _{1 is} H, alkyl, alkaryl, aryl, arylalkyl and wherein R ² , R ³ , R ⁴ and R ^{5 may be the} same or different substituents selected from H, halo, alkyl, alkenyl, aryl, hydroxyl Alkoxyl, amino, alkylamino, COOR ₆ - (wherein R _{6 is} H or an alkyl group) and carbonyl functions.

One particularly preferred precursor of the benzoxazine type is:

Preformed organic peroxy

The organic peroxyacid bleach system can additionally or alternatively to an organic peroxyacid bleach precursor compound, contain a preformed organic peroxyacid, typically in an amount of 0.5 to 25% by weight, more preferably 1 to 10% by weight the composition.

worin R¹ eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R² eine Alkylen-, Arylen- oder eine Alkarylengruppe mit 1 bis 14 Kohlenstoffatomen ist, R⁵ H oder eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 10 Kohlenstoffatomen ist. R¹ enthält vorzugsweise 6 bis 12 Kohlenstoffatome. R² enthält vorzugsweise 4 bis 8 Kohlenstoffatome. R¹ kann ein geradkettiges oder verzweigtes Alkyl, substituiertes Aryl oder Alkylaryl mit Verzweigungen, Substitutionen oder beidem sein und kann synthetischer Herkunft oder natürlicher Herkunft sein, einschließlich beispielsweise Talgfett. Analoge Strukturvariationen sind für R² zulässig. Die Substitution kann Alkyl-, Aryl-, Halogen-, Stickstoff-, Schwefel- und andere typische Substituentengruppen oder organische Verbindungen umfassen. R⁵ ist vorzugsweise H oder Methyl. R¹ und R⁵ sollten nicht mehr als insgesamt 18 Kohlenstoffatome enthalten. Amidsubstituierte organische Peroxysäureverbindungen dieses Typs sind in EP-A-01703 86 beschrieben.A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulas:

wherein R ^{1 is} an alkyl, aryl or alkaryl group of 1 to 14 carbon atoms, R ^{2 is} an alkylene, arylene or alkarylene group of 1 to 14 carbon atoms, R ^{5 is} H or an alkyl, aryl or alkaryl group of 1 to 10 carbon atoms. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains 4 to 8 carbon atoms. R ¹ may be a straight chain or branched alkyl, substituted aryl or alkylaryl with branches, substitutions or both, and may be of synthetic or natural origin including, for example, tallow fat. Analogous structure variations are allowed for R ² . The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not contain more than a total of 18 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and Diperoxyhexadecanedioc. Dibenzoyl peroxide is a preferred organic peroxyacid herein. mono- and diperazelaic acid, Mono- and diperbrassylic acid are also suitable herein.

Preformed and on the subject Use of suitable monoperoxycarboxylic acids (hereinafter referred to as peracid) are mono-acids, which means that the peracid contains a peroxy group. Preferably, the peracid is in solid form.

In a preferred embodiment of the present invention, the peracid has the general formula XRC (O) OOH wherein R is a linear or branched alkyl chain having at least 1 carbon atom and X is hydrogen or a substituent group selected from the group consisting of alkyl, especially alkyl chains having 1 to 24 carbon atoms, aryl, halogen, ester, ether, amine, amide, substituted Phthalic acid amino groups, imide, hydroxide, sulfide, sulfate, sulfonate, carboxylic acid groups, heterocyclic groups, nitrate, aldehyde, phosphonate, phosphonic acid groups or mixtures thereof.

Especially Preferably, the R group comprises up to 24 carbon atoms. alternative the R group can be a branched alkyl chain comprising one or more several side chains, be the substituent groups selected from the group consisting of aryl, halogen, ester, ether, amine, amide, substituted phthalic acid amino groups, Imide, hydroxide, sulfide, sulfate, sulfonate, carboxylic acid groups, heterocyclic groups, nitrate, aldehyde, ketone or mixtures of which includes.

worin R C1-20 ist und worin A, B, C und D unabhängig voneinander entweder Wasserstoff oder Substituentengruppen sind, die einzeln ausgewählt sind aus der Gruppe, bestehend aus Alkyl, Hydroxyl, Nitro, Halogen, Amin, Ammonium, Cyanid, Carbonsäuregruppen, Sulfat, Sulfonat, Aldehyd oder Mischungen davon.In a preferred peracid, the X group of the above general formula is a phthalimido group. Particularly preferred peracids are therefore those having the general formula:

wherein R is C1-20 and wherein A, B, C and D are independently either hydrogen or substituent groups individually selected from the group consisting of alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyanide, carboxylic acid groups, sulfate , Sulfonate, aldehyde or mixtures thereof.

In a preferred aspect of the present invention, R is an alkyl group of 3 to 12 carbons atoms, more preferably having 5 to 9 carbon atoms. Preferred substituent groups A, B, C and D are linear or branched alkyl groups having 1 to 5 carbon atoms, but more preferably is hydrogen.

preferred peracids are selected from the group consisting of phthaloylamidoperoxyhexanoic acid, phthaloylamidoperoxyheptanoic acid, phthaloylamidoperoxyoctanoic acid, phthaloylamidoperoxynonanoic acid, phthaloylamidoperoxydecanoic acid and Mixtures thereof.

In a particularly preferred aspect of the present invention, the formula of the peracid is such that RC _{5 is} H ₁₀ , ie, phthaloylamidoperoxyhexanoic acid or PAP. This peracid is preferably used as a substantially water-insoluble solid or wet cake and is available under the tradename Euroco from Ausimont.

The peracid is preferably in an amount of 0.1 to 30 wt .-%, more preferably from 0.5 to 18% by weight and most preferably from 1 to 12% by weight the composition used.

Metal-containing bleach catalyst

The compositions described herein, the bleach detergent component can contain about that In addition, a metal-containing bleach catalyst as a preferred Component included. Preferably, the metal-containing bleach catalyst a bleach catalyst which is a transition metal contains, still more preferably a manganese or cobalt-containing bleach catalyst.

The Compositions of the invention can an effective amount of a bleach catalyst. The term "effective Quantity "is defined as one Amount of in the inventive compositions or while the use of transition metal bleach catalyst according to the processes of the invention, which is sufficient to at least partial oxidation of the Material oxidized by the composition or process is to effect, no matter what comparative conditions or conditions of use ".

Preferably can the compositions of the invention of 1 ppb (0.0000001%), more preferably 100 ppb (0.00001%), still more preferably 500 ppb (0.00005%), even more preferably 1 ppb (0.0001 %) to 99.9%, more preferably to 50%, even more preferably to 5% and even more preferably up to 500 ppb (0.05%) by weight of the composition of a metal bleach catalyst, as described below.

One suitable type of bleach catalyst is a catalyst comprising a heavy metal cation with a fixed catalytic bleaching activity, such as copper, Iron cations, a supporting one Metal cation with low catalytic bleaching activity or even no catalytic bleaching activity, such as zinc or aluminum cations, and a sequestering agent having fixed stability constants with respect to the catalytic and supporting metal cations, in particular ethylenediaminetetraacetic acid, Ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts from that. Such catalysts are disclosed in U.S. Patent 4,430,243.

Preferred types of bleach catalysts include the manganese-based complexes disclosed in U.S. Patent 5,246,621 and U.S. Patent 5,244,594. Preferred examples of these catalysts include Mn ^IV ₂ (μO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (PF ₆ ) ₂ , Mn ^III ₂ (μO) ₁ (μ-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4,7-triazacyclononane) 4- (ClO ₄ ) ₂ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ - (1,4,7-trimethyl-1,4,7-triazacyclononane) 2- (ClO ₄ ) ₃ , and mixtures thereof. Others are disclosed in European Patent Application Publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane , 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

The bleach catalysts suitable for the compositions herein may also be selected according to their suitability for the present invention. For examples of suitable bleach catalysts, see U.S. Patent 4,246,612 and U.S. Patent 5,227,084. See also U.S. Patent 5,194,416, which teaches mononuclear manganese (IV) complexes, such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ - (PF ₆ ).

Yet another type of bleach catalyst, as disclosed in U.S. Patent 5,114,606, is a water-soluble complex of manganese (III) and / or (IV) and a ligand which is a non-carboxylic acid polyhydroxy compound having at least three consecutive C-OH groups , Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose and mixtures of it.

worin R¹, R², R³ und R⁴ jeweils aus H, substituierten Alkyl- und Arylgruppen ausgewählt sein können, sodass jedes R¹ – N = C – R² und R³ – C = N – R⁴ einen fünf- oder sechsgliedrigen Ring bildet. Der Ring kann weitersubstituiert sein. Bist ein Brückenglied, ausgewählt aus O, S. CR⁵R⁶, NR⁷ und C=O, worin R⁵, R⁶ und R⁷ jeweils H, eine Alkyl- oder Arylgruppe sein können, einschließlich substituierter oder nicht substituierter Gruppen. Bevorzugte Liganden umfassen Pyridin-, Pyridazin-, Pyrimidin-, Pyrazin-, Imidazol-, Pyrazol- und Triazolringe. Wahlweise können die Ringe durch Substituenten, wie Alkyl, Aryl, Alkoxy, Halogenid und Nitro, substituiert sein. Besonders bevorzugt ist der Ligand 2,2'-Bispyridylamin. Bevorzugte Bleichkatalysatoren umfassen Co-, Cu-, Mn-,Fe-Bispyridyhnethan- und Bispyridylaminkomplexe. Starkbevorzugte Katalysatoren umfassen Co(2,2'- Bispyridylamin)Cl₂, Di(isothiocyanat)bispyridylamin-Cobalt(II),Trisdipyridylamin-Cobalt(II)perchlorat, Co(2,2-Bispyridylamin)₂O₂ClO₄, Bis-(2,2'-bispyridylamin)Kupfer(II)perchlorat, Tris(di-2-pyridylainin)-Eisen(II)perchlorat und Mischungen davon.U.S. Patent 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe or Cu, and a non-macrocyclic ligand. The ligands have the formula:

wherein R ¹ , R ² , R ³ and R ^{4 may} each be selected from H, substituted alkyl and aryl groups such that each R ¹ - N = C - R ² and R ³ - C = N - R ^{4 is} a five- or ^three -membered group forms six-membered ring. The ring may be further substituted. A bridge member selected from O, S. CR ⁵ R ⁶ , NR ⁷ and C = O, wherein R ⁵ , R ⁶ and R ^{7 may} each be H, an alkyl or aryl group, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, the rings may be substituted by substituents such as alkyl, aryl, alkoxy, halide and nitro. More preferably, the ligand is 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe bispyridymethane, and bispyridylamine complexes. Highly preferred catalysts include Co (2,2'-bispyridylamine) Cl ₂ , di (isothiocyanate) bispyridylamine cobalt (II), trisdipyridylamine cobalt (II) perchlorate, Co (2,2-bispyridylamine) ₂ O ₂ ClO ₄ , bis- (2,2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof.

Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate ligands, including N ₄ Mn ^III (uO) ₂ Mn ^IV N ₄₎ ⁺ and [Bipy ₂ Mn ^III (uO) ₂ Mn ^IV bipy ₂ ] - (ClO ₄ ) ₃ .

While the Structures of the bleach-catalyzing invention Manganese complexes not clarified It can be speculated that they hydrated chelates or others Include coordination complexes resulting from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation are formed. Also, the oxidation state of manganese cation in this catalytic Procedure is not known with certainty and could be the (+ II), (+ III), (+ IV) or (+ V) valence state. Since there are six possible points of attachment which gives ligands to the manganese cation may reasonably be speculated be that multinuclear species and / or "cage" structures are present in the aqueous bleaching medium can. In whatever form the effective Mn ligand species are present, They work in a way that is catalytic in nature with stubborn Stains, such as tea, ketchup, coffee, wine, juice and the like, one to provide better bleaching performance.

Other bleach catalysts are described, for example, in European Patent Application, Publ. 408,131 (cobalt complex catalysts), in European Patent Applications, Publ. 384,503 and 306,089 (metalloporphyrin catalysts), US 4,728,455 (Manganese catalyst / multidentate ligand catalyst), US 4,711,748 and European Patent Application, Publication No. 224,952, (alumosilicate-absorbed manganese catalyst), US 4,601,845 (Aluminosilicate support with manganese and zinc or magnesium salt), US 4,626,373 (Manganese / ligand catalyst), US 4,119,557 (Iron (III) complex catalyst), German Patent 2,054,019 (cobalt chelating catalyst), CA 866,191 (transition metal-containing salts), US 4,430,243 (Chelating agent with manganese cations and non-catalytic metal cations) and US 4,728,455 (Manganese gluconate catalysts).

Other preferred examples include cobalt (III) catalysts having the formula: Co [(NH ₃ ) _n M ' _m B' _b T ' _t Q _q P _p ] Y _y wherein cobalt has the oxidation state +3; n is an integer from 0 to 5 (preferably 4 or 5, most preferably 5); M 'represents a monodentate ligand; m is an integer of 0 to 5 (preferably 1 or 2, most preferably 1); B 'represents a bidentate ligand; b is an integer of 0 to 2; T 'represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y represents one or more suitably selected counter anions present in the number y, where y is an integer from 1 to 3 (preferably 2 to 3, most preferably 2 when Y is a charged state anion -1) to obtain a balanced charge salt, preferred Ys are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate and combinations thereof; and further wherein at least one of the coordination sites on the cobalt is unstable under detergent application conditions and the others Coordination sites stabilize the cobalt under washing conditions such that the reduction potential for cobalt (III) to cobalt (II) is less than 0.4 volts (preferably less than 0.2 volts) under alkaline conditions compared to a standard hydrogen electrode.

Preferred cobalt catalysts of this type have the formula: [Co (NH ₃ ) _n (M ') _m ] Y _y wherein n is an integer of 3 to 5 (preferably 4 or 5, most preferably 5); M 'is an unstable coordination unit, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2, most preferably 1); m + n = 6; and Y is a suitably selected counter anion present in the number y, where y is an integer from 1 to 3 (preferably 2 to 3, most preferably 2, when Y is a charged state anion) to get a salt with balanced charge.

The preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co (NH ₃ ) ₅ Cl] Y _y and especially [Co (NH ₃ ) ₅ Cl] Cl ₂ .

More preferred are the compositions of the present invention utilizing cobalt (III) bleach catalysts having the formula: [Co (NH ₃ ) _n (M) _m (B) _b ] T _y wherein cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M represents one or more ligands which are unilaterally coordinated to the cobalt; m is 0, 1 or 2 (preferably 1); B is a ligand which is bilaterally coordinated to the cobalt; b is 0 or 1 (preferably 0), and if b = 0, then m + n = 6, and if b = 1, then m = 0 and n = 4; and T is one or more suitably selected counter anions present in a number y, where y is an integer, to obtain a balanced charge salt (preferably, y is 1 to 3, most preferably 2, when T is an anion with charge state is -1); and wherein the constant of the rate of basic hydrolysis of the catalyst is further below 0.23 M ^-1 s ^-1 (25 ° C).

Preferred T are selected from the group consisting of chloride, iodide, I ₃ -, formate, nitrate, nitrite, sulfate, sulfate, citrate, acetate, carbonate, bromide, PF ₆ -, BF ₄ -, B (Ph) ₄ - , Phosphate, phosphate, silicate, tosylate, methanesulfonate, and combinations thereof. Alternatively, T may be protonated if there is more than one anionic group in T, for example, HPO ₄ ^2- , HCO ₃ -, H ₂ PO ₄ -, etc.

Of Further, T can be selected be from the group consisting of non-traditional, inorganic Anions, such as anionic surfactants (eg, linear alkylbenzenesulfonates (LAS), alkyl sulfates (AS), alkyl ethoxy sulfonates (AES), etc.) and / or anionic polymers (e.g., polyacrylates, polymethacrylates, etc.).

The M moieties include, but are not limited to, for example, F ^-, SO ₄ ^-2, NCS ^-, SCN ^-, S ₂ O ₃ ^-2, NH _3, PO ₄ ^3-, and carboxylates (which preferably monocarboxylates, wherein but more than one carboxylate may be present in the moiety as long as the binding to the cobalt per moiety occurs only via one carboxylate, the other carboxylate in the M moiety may be protonated or in its salt form). Alternatively, M may be protonated if more than one anionic group is present in M (eg, HPO ₄ ^2- , HCO ₃ -, H ₂ PO ₄ -, HOC (O) CH ₂ C (O) O-, etc.). ). Preferred M groups are substituted and unsubstituted C ₁ -C ₃₀ carboxylic acids having the formula: RC (O) O wherein R is preferably selected. is selected from the group consisting of hydrogen and unsubstituted and substituted C ₁ -C ₃₀ (preferably C ₁ -C ₁₈ ) alkyl, unsubstituted and substituted C ₆ -C ₃₀ (preferably C ₆ -C ₁₈ ) aryl and unsubstituted and substituted C ₃ -C ₃₀ (preferably C ₅ -C ₁₈ ) heteroaryl, wherein the substituents are selected from the group consisting of -NR ' ₃ , -NR' ₄ ⁺ , -C (O) OR ', - OR ', -C (O) NR' ₂ , wherein R 'is selected from the group consisting of hydrogen and C ₁ -C ₆ moieties. Thus substituted Rs thus include the moieties - (CH ₂ ) _n OH and - (CH ₂ ) _n NR ' ₄ ⁺ wherein n is an integer from 1 to 16, preferably from 2 to 10, and most preferably from 2 to 5 ,

Most preferred M are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C ₄ -C ₁₂ alkyl and benzyl. The most preferred R is methyl. Preferred carboxylic acid M groups include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic acids , Aspartic acid, fumaric acid, lauric acid, linoleic acid, lactic acid, malic acid, and especially acetic acid.

The B groups include carbonate, di- and higher carboxylates (eg, oxalate, Malonate, malate, succinate, maleate), picolinic acid and alpha and beta amino acids (e.g. Glycine, alanine, beta-alanine, phenylalanine).

Cobalt bleach catalysts useful herein are known and are described, for example, together with their base hydrolysis rates in ML Tobe, "Base Hydrolysis of Transition-Metal Complexes." Adv. Inorg., Bioinorg., Mech., (1983), 2, pages 1-94. For example, Table 1 on page 17 provides the base hydrolysis rates (designated as k _OH ) for cobalt pentaamine catalysts coupled with oxalate (k _OH = 2.5 x 10 ^-4 M ^-1 s ^-1 (25 ° C)), NCS ^- (k _OH = 5.0 x 10 ^-4 M ^-1 s ^-1 (25 ° C)), formate (k _OH = 5.8 x 10 ^-4 M ^-1 s ^-1 (25 ° C)) and acetate (k _OH = 9.6 x 10 ^-4 M ^-1 s ^-1 are (25 ° C)) complexed. the ammeisten preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co (NH _{3) 5} OAc] T _y, wherein OAc an acetate and especially cobalt pentaamine acetate chloride, [Co (NH ₃ ) ₅ OAc] Cl ₂ , and [Co (NH ₃ ) ₅ OAc] (OAc) ₂ ; [Co (NH ₃ ) ₅ OAc] (PF ₆ ) ₂ ; [Co (NH ₃ ) ₅ OAc] (SO ₄ ); [Co (NH ₃ ) ₅ OAc] (BF ₄ ) ₂ ; and [Co (NH ₃ ) ₅ OAc] (NO ₃ ) ₂ (herein "PAC").

These Cobalt catalysts can be easily prepared by known methods, such as in the previous article by Tobe and the references cited there, in U.S. Patent 4,810,410, to Diakun et al, issued March 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic compounds, W.L. Jolly (Prentice Hall, 1970), pp. 461-3; Inorg. Chem, 18, 1497-1502 (1979); Inorg. Chem, 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. 3, 173-176 (1960); and in Journal of Physical Chemistry, 56, 22-25 (1952); and taught in the synthesis examples provided below become.

For receiving in the detergent compositions according to the invention suitable cobalt catalysts can disclosed in U.S. Patent Nos. 5,559,261, 5,581,005 and 5,597,936 Synthetic routes are produced.

• i) ein Übergangsmetall ausgewählt aus der Gruppe, bestehend aus Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III) und Ru(IV), vorzugsweise Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III), Fe(IV), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI) und Mischungen davon;
• ii) einen makropolycyclischen Liganden mit Querbrücken, der von vier oder fünf Donoratomen an dasselbe Übergangsmetall koordiniert wird, wobei der Ligand umfasst:
• a) einen organischen makrocyclischen Ring, enthaltend vier oder mehr Donoratome (vorzugsweise sind mindestens 3, noch bevorzugter mindestens 4 dieser Donoratome N), die voneinander durch kovalente Bindungen an 2 oder 3 Nichtdonoratome getrennt sind, wobei zwei bis fünf (vorzugsweise drei bis vier, noch bevorzugter vier) dieser Donoratome an dasselbe Übergangsmetallatom in dem Komplex koordiniert sind;
• b) eine Kette mit Querbrücken, die mindestens 2 nicht benachbarte Donoratome des organischen, makrocyclischen Rings kovalent verbindet, wobei die kovalent verbundenden, nicht benachbarten Donoratome Brückenkopf-Donoratome sind, die an dasselbe Übergangsmetall in dem Komplex koordiniert sind, und worin die Kette mit den Querbrücken 2 bis etwa 10 Atome umfasst (vorzugsweise ist die Kette mit Querbrücken ausgewählt aus 2, 3 oder 4 Nichtdonoratomen und 4–6 Nichtdonoratomen mit einem weiteren Donoratom) und
• iii) wahlweise einen oder mehrere nicht makropolycyclische Liganden, vorzugsweise ausgewählt aus der Gruppe, bestehend aus H₂O, ROH, NR₃, RCN, OH^–, OOH^–, RS^–, RO^–, RCOO^–, OCN, SCN, N₃ ^–, CN^–, F^–, Cl^–, Br^– , I^–, O2^–, NO₃ ^–, NO₂ ^–, SO₄ ^2-, SO₃ ^2-, PO₄ ^3-, organischen Phosphaten, organischen Phosphonaten, organischen Sulfaten, organischen Sulfonaten und aromatischen N-Donoren, wie Pyridinen, Pyrazinen, Pyrazolen, Imidazolen, Benzimidazolen, Pyrimidinen, Triazolen und Thiazolen, wobei R H, wahlweise substituiertes Alkyl, wahlweise substituiertes Aryl ist.

Other suitable bleach catalysts include transition metal bleach catalysts, comprising:

• i) a transition metal selected from the group consisting of Mn (II), Mn (III), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV), Co (I) , Co (II), Co (III), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III) , Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV) , W (V), W (VI), Pd (II), Ru (II), Ru (III) and Ru (IV), preferably Mn (II), Mn (III), Mn (IV), Fe (II ), Fe (III), Fe (IV), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI) and mixtures thereof;
• ii) a cross-bridged macropolycyclic ligand coordinated to the same transition metal by four or five donor atoms, said ligand comprising:
• a) an organic macrocyclic ring containing four or more donor atoms (preferably at least 3, more preferably at least 4 of these donor atoms are N) separated from each other by covalent bonds to 2 or 3 non-donor atoms, with two to five (preferably three to four, more preferably four) of these donor atoms are coordinated to the same transition metal atom in the complex;
• b) a cross-bridged chain covalently linking at least two non-adjacent donor atoms of the organic macrocyclic ring, wherein the covalently bonded, non-adjacent donor atoms are bridgehead donor atoms coordinated to the same transition metal in the complex, and wherein the chain is substituted with the Crossbridges 2 to about 10 atoms (preferably, the cross-bridged chain is selected from 2, 3 or 4 non-donor atoms and 4-6 non-donor atoms with another donor atom) and
• iii) optionally one or more non-macropolycyclic ligands, preferably selected from the group consisting of H ₂ O, ROH, NR _3, RCN, OH ^-, OOH ^-, RS ^-, RO ^-, RCOO ^-, OCN, SCN, N ₃ ^-, CN ^-, F ^-, Cl ^-, Br ^-, I ^-, O 2 ^-, NO ₃ ^-, NO ₂ ^-, SO ₄ ^2-, SO ₃ ^2-, PO ₄ ^3-, organic phosphates, organic phosphonates, organic, Sulfates, organic sulfonates and aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, wherein R is H, optionally substituted alkyl, optionally substituted aryl.

b) einem makropolycyclischen Liganden mit Querbrücken der Formel (II) mit einer Dentizität von 5 oder 6:

c) dem makropolycyclischen Liganden mit Querbrücken der Formel (III) mit einer Dentizität von 6 oder 7:

worin jede E-Einheit die Gruppierung mit folgender Formel darstellt: (CR_n)_a-X-(CR_n)_a' worin X ausgewählt ist aus der Gruppe, bestehend aus Sauerstoff, Schwefel, -NR-, Phosphor, oder X eine kovalente Bindung darstellt, worin E folgende Formel hat: (CR_n)_a-(CR_n)_a' für jede E-Einheit die Summe von a + a' unabhängig von 1 bis 5 ausgewählt ist; jede G-Einheit eine (CR_n)_b-Gruppierung ist; jede R-Einheit unabhängig ausgewählt ist aus H, Alkyl, Alkenyl, Alkynyl, Aryl, Alkylaryl und Heteroaryl, oder zwei oder mehr R-Einheiten kovalent verknüpft sind, um einen aromatischen, heteroaromatischen Ring oder einen Cycloalkyl- oder Heterocycloalkylring zu bilden; jede D-Einheit ein Donoratom ist, das unabhängig ausgewählt ist aus der Gruppe, bestehend aus Stickstoff, Sauerstoff, Schwefel und Phosphor, und mindestens zwei Atome, die D-Einheiten umfassen, Brückenkopf-Donoratome sind, die an das Übergangsmetall koordiniert sind; B-Einheiten ein Kohlenstoffatom, eine D-Einheit oder ein Cycloalkylring oder ein heterocyclischer Ring sind; jedes n eine ganze Zahl ist, die unabhängig ausgewählt ist aus 1 und 2, was die Valenz der Kohlenstoffatome, an welche die R-Einheiten kovalent gebunden sind, vervollständigt; jedes n' eine ganze Zahl ist, die unabhängig ausgewählt ist aus 0 und 1, was die Valenz des D-Donoratoms, an das die R-Gruppierungen kovalent gebunden sind, vervollständigt; jedes n" eine ganze Zahl ist, die unabhängig von 0, 1 und 2 ausgewählt ist, was die Valenz der B-Atome, an welche die R-Gruppierungen kovalent gebunden sind, vervollständigt; jedes a und jedes a' eine ganze Zahl sind, die unabhängig von 0 bis 5 ausgewählt sind, wobei die Summe aller a + a'-Werte in dem Liganden der Formel (I) im Bereich von etwa 8 bis etwa 12 liegt; die Summe aller a + a'-Werte in dem Liganden der Formel (II) im Bereich von etwa 10 bis etwa 15 liegt und die Summe aller a + a'- Werte in dem Liganden der Formel (III) im Bereich von etwa 12 bis etwa 18 liegt; jedes b eine ganze Zahl ist, die unabhängig von 0 bis 9 ausgewählt ist, oder in jeder der obigen Formeln eine oder mehrere der (CR_n)_b-Gruppierungen, die jedes beliebige der D-Atome kovalent mit dem B-Atom verbinden, fehlt, solange mindestens zwei (CR_n)_b zwei der D-Donoratome kovalent an das B-Atom in der Formel binden und die Summe aller b-Indizes im Bereich von etwa 2 bis etwa 5 liegt.The preferred cross-bridged macropolycyclic ligands are selected from the group consisting of consisting of:
a) a cross-bridged macropolycyclic ligand of formula (I) having a denticity of 4 or 5:

b) a cross-bridged macropolycyclic ligand of formula (II) having a denticity of 5 or 6:

c) the cross-bridged macropolycyclic ligand of formula (III) having a denticity of 6 or 7:

wherein each E unit represents the grouping with the formula: (CR _n ) _a -X- (CR _n ) _{a '} wherein X is selected from the group consisting of oxygen, sulfur, -NR-, phosphorus, or X is a covalent bond, wherein E has the formula: (CR _n ) _a - (CR _n ) _{a '} for each E unit, the sum of a + a 'is selected independently of 1 to 5; each G unit is a (CR _n ) _b grouping; each R moiety is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl and heteroaryl, or two or more R moieties are covalently linked to form an aromatic, heteroaromatic ring or a cycloalkyl or heterocycloalkyl ring; each D unit is a donor atom independently selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, and at least two atoms comprising D units are bridgehead donor atoms coordinated to the transition metal; B units are a carbon atom, a D unit or a cycloalkyl ring or a heterocyclic ring; each n is an integer independently selected from 1 and 2, which completes the valency of the carbon atoms to which the R moieties are covalently bonded; each n 'is an integer independently selected from 0 and 1, which completes the valency of the D donor atom to which the R moieties are covalently bonded; each n "is an integer selected independently of 0, 1 and 2, which completes the valency of the B atoms to which the R moieties are covalently attached, each a and each a 'is an integer, which are independently selected from 0 to 5, the sum of all a + a 'values in the ligand of formula (I) being in the range of about 8 to about 12; the sum of all a + a' values in the ligand of Formula (II) ranges from about 10 to about 15 and the sum of all a + a 'values in the ligand of formula (III) ranges from about 12 to about 18; each b is an integer that is independent is selected from 0 to 9, or in each of the above formulas, one or more of the (CR _n ) _b moieties covalently linking any of the D atoms to the B atom is absent as long as at least two (CR _n ) _b two of the D donor atoms covalently bond to the B atom in the formula and the sum of all b indices ranges from about 2 to about 5.

A Further description of the bleaching catalysts of the invention is in WO 98/39406 A1 on September 11, 1998, WO 98/39098 A1, published September 11, 1998 1998, and WO 98/39335 A1 on September 11, 1998.

The Nomenclature herein to describe the transition metal bleach catalyst is the same nomenclature style used in the above References is used. The chemical names of one or however, more of the ligands described herein may be derived from the according to the rules of the International Union of Pure and Applied Chemistry (IUPAC) assigned name. For example, has one for the For the purposes of the present invention, preferred ligand, 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane, the IUPAC name 4,11-dimethyl-1,4,8,11-tetraazabicyclo [6.6.2] hexadecane. Another preferred ligand is 5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane.

Metal bleach catalysts useful in the compositions of the invention may generally comprise known compounds when consistent with the definition of the invention, and, more preferably, any of a wide variety of novel compounds expressly designed for current use in laundry detergents are. Suitable bleach catalysts for use in the compositions herein further include, for example:
Manganese (II) Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Diaqua-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) hexafluorophosphate;
Aquahydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) hxafluorphosphat;
Diaqua-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecanmangan (II) hexafluorophosphate;
Diaqua-5,12-dimethy-1-1,5,8,12-tetraazabicyclo [6.6.2] hexidecanmangan (II) tetrafluoroborate;
Diaqua-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecanmangan (II) tetrafluoroborate;
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) hexafluorophosphate;
Manganese (II) Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexdecan;
Iron (II) Dichloro-5,12-ditnethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Iron (II) dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Copper (II) Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Copper (II) Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Cobalt (II) Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Cobalr (II) Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Manganese (II) Dichloro-5,12-dimethyl-4-phenyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Manganese (II) Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Manganese (II) Dichloro-5,12-dimethyl-2,11-diphenyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-4,10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Manganese (II) Dichloro-2,4,5,9,11,12-hexamethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexidecan,
Manganese (II) Dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) dichloro-2,2,4,5,9,11,11,12-octamethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-3,3,5,10,10,12-hexamethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-3,5,10,12-tetram44ethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-3-butyl-5,10,12-trimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) Dichloro-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Iron (II) Dichloro-1,5,8,12-tetra arabi cyclo [6.6.2] hexadecane;
Iron (II) Dichloro-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Manganese (II) aqua-chloro-2- (2-hydroxyphenyl -) - 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) aqua-chloro-10- (2-hydroxybenzyl) -4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Manganese (II) -chloro-2- (2-hydroxybenzyl) -5-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) chloro-10- (2-hydroxybenzyl) -4-methyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Chloro-5-methyl-12- (2-picolyl) -1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) chloride;
Chloro-4-methyl-10- (2-picolyl) -1,4,7,10-tetraazabicyclo [5.5.2] tetradecanmangan (II) chloride;
Manganese (III) Dichloro-5- (2-sulfato) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) aqua-chloro-5- (2-sulfato) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II) aqua-chloro-5- (3-sulfonopropyl) -12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Dichloro-5- (trimethylammoniumpropyl) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) chloride;
Manganese (II) Dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo [8.5.2] heptadecane;
Manganese (II) Dichloro-14,20-dimethyl-1,10,14,20-tetraazatricyclo [8.6.6] docosa-3 (8), 4,6-triene;
Manganese (II) Dichloro-4,11-dimethyl-1,4,7,11-tetraazabicyclo [6.5.2] pentadecane;
Manganese (II) Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [7.6.2] heptadecane;
Manganese (II) Dichloro-5,13-dimethyl-1,5,9,13-tetraazabicyclo [7.7.2] heptadecane;
Manganese (II) Dichloro-3,10-bis (butylcarboxy) -5,12-dimethy) -1,5,8,12-tetraazabicyclo [6.6.2] hexidecan;
Manganese (II) -diaqua-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Chloro-20-methyl-1,9,20,24,25-pentaazatetracyclo [7.7.7.1 ^3,7 .1 ^11,15 .] Pentacosa-3,5,7 (24), 11,13,15 (25) -hexaen manganese (II) hexafluorophosphate;
Trifluoromethanesulfone-20-methyl-1,9,20,24,25-pentaazatetracyclo [7.7.7.1 ^3,7 .1 ^11,15 .] Pentacosa-3,5,7 (24), 11,13,15 (25) -hexaenmangan trifluoromethanesulfonate (II);
Trifluoromethanesulfone-20-methyl-1,9,20,24,25-pentaazatetracyclo [7.7.7.1 ^3,7 .1 ^11,15 .] Pentacosa-3,5,7 (24), 11,13,15 (25) -hexaeneisen trifluoromethanesulfonate (II);
Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo [6.6.5] nonadecanmangan (II) hexifluorphosphat;
Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo [5.5.5] heptadecanmangan (II) hexafluorophosphate;
Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo [6.6.5] nonadecanmangan (II) chloride;
Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo [5.5.5] heptadecanmangan (II) chloride;
Manganese (II) dichloro-5,12,15,16-tetramethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane and
Manganese (II) -chloro 5-ethyl-12- (2'-oxybenzyl) -1,5,8,12-tetraazabicyclo [6.6.2] hexadecane.

Further suitable complexes used as transition-metal bleach catalysts can be used not only include monometallic, mononuclear species such as those herein shown above, but also bimetallic or trimetallic Species or cluster species. Monometallic, mononuclear complexes are preferred. As defined herein, a monometallic transition metal bleach catalyst only one transition metal atom per mole of the Kommplexes. A monometallic, mononuclear complex is one in which every donor atom of the essential macrocyclic Ligands to the same transition metal atom is bound, that is, that the essential ligand does not bridge two or more transition metal atoms.

worin X unabhängig koordinierender oder überbrückender Art ist, wofür H₂O, O₂ ^2-, O^2-, ^–OH, HO₂ ^–, SH^–, S^2–, >SO, Cl^–, SCN^–, N₃ ^–, N^3–, RSO₃ ^–, RCOO^–, NH₂ ^– und NR₃ nicht einschränkende Beispiele sind, worin R H, Alkyl, Aryl ist, das jeweils wahlweise substituiert ist, und R ¹COO ist, worin R¹ eine Alkyl-, Aryleinheit ist, die jeweils wahlweise substituiert sein kann;
L ein Ligand ist, der ein organisches Molekül mit einer Anzahl von Stickstoffatomen ist, die über alle oder einige der Stickstoffatome an die Manganzentren koordiniert sind;
z die Ladung des Komplexes angibt und eine ganze Zahl ist, die einen positiven oder negativen Wert haben kann;
Y ein einwertiges oder mehrwertiges Gegenion ist, das Ladungsneutralität vermittelt, was auf der Ladung z des Komplexes beruht; und q z/Y ist.Further examples of manganese transition metal complexes are the manganese (III) and manganese (IV) complexes having the general formula:

wherein X is independently a coordinating or bridging type, is what H ₂ O, O ₂ ^2-, O ^{2-, -} OH, HO ₂ ^-, SH ^-, S ^2-,> SO, Cl ^-, SCN ^-, N ₃ ^-, N ^3, RSO ₃ ^-, RCOO ^-, NH ₂ ^- and NR ₃ are non-limiting examples, wherein R is H, alkyl, aryl, each being optionally substituted, and R ¹ COO, wherein R ¹ is an alkyl, aryl moiety each of which may optionally be substituted;
L is a ligand which is an organic molecule having a number of nitrogen atoms coordinated to all or some of the nitrogen atoms to the manganese centers;
z indicates the charge of the complex and is an integer that may have a positive or negative value;
Y is a monovalent or polyvalent counterion that mediates charge neutrality, based on the charge z of the complex; and qz / Y is.

Among these manganese complexes are those in which the coordinating or bridging group X is either CH ₃ COO ^-, O ^2-, or mixtures thereof, preferably when said manganese atom has an oxidation state (IV) and X is O ^2-. Preferred ligands are those which contain at least three nitrogen atoms and which are coordinated via three nitrogen atoms to one of the manganese centers and are preferably macrocyclic in nature.

worin t eine ganze Zahl mit dem Wert 2 oder 3 ist; s eine ganze Zahl mit dem Wert 3 oder 4 ist; q eine ganze Zahl mit dem Wert 0 oder 1 ist, R¹ und R² jeweils unabhängig ausgewählt sind aus Wasserstoff, Alkyl, Aryl, das jeweils wahlweise substituiert sein kann; R³ unabhängigerweise ausgewählt ist aus Wasserstoff, Alkyl, Aryl, das jeweils wahlweise substituiert sein kann.Preferred ligands have the formula:

where t is an integer of 2 or 3; s is an integer of 3 or 4; q is an integer of 0 or 1, R ¹ and R ^{2 are} each independently selected from hydrogen, alkyl, aryl, each of which may optionally be substituted; R ^{3 is} independently selected from hydrogen, alkyl, aryl, each of which may optionally be substituted.

Non-limiting examples of preferred ligands are 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN) and 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me ₄ -TACN ).

The choice of counterion Y to provide charge neutrality is not critical to the activity of the complex. Non-limiting examples of the counterion include chloride, sulfate, nitrate, methyl sulfate, surfactant ions such as long chain alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, tosylate, trifluoromethyl sulfonate, perchlorate, BPh ₄ ^- , PF ₆ ^-, and mixtures thereof.

Examples of manganese complexes of this type include: i) [(Me ₃ -TACN) Mn ^IV (mO) ₃ Mn ^IV (Me ₃ -TACN)] ²⁺ (PF ₆ ^- ) ₂ ; ii) [(Me ₄ -TACN) Mn ^IV (mO) ₃ Mn ^IV (Me ₄ -TACN)] ²⁺ (PF ₆ ^- ) ₂ ; iii) [(Me ₃ -TACN) Mn ^III (mO) (m-OAc) ₂ Mn ^III (Me ₃ -TACN)] ²⁺ (PF ₆ ^- ) ₂ ; iv) [(Me ₄ -TACN) Mn ^III (mO) (m-OAc) ₂ Mn ^III (Me ₃ -TACN)] ²⁺ (PF ₆ ^- ) ₂ ; Other manganese complex catalysts are the mononuclear complexes of the formula: [LMn ^IV (OR) ₃ ] Y wherein manganese, Mn, has the +4 oxidation state; R is a C ₁ -C ₂₀ radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl, and residual combinations thereof; at least two R groups may also be linked together to form a bridging unit between two oxygens coordinated to the manganese; L is a ligand selected from a C ₃ -C ₆₀ residue with min at least 3 nitrogen atoms coordinated to the manganese; and Y is an oxidatively stable counterion depending on the charge of the complex.

Non-limiting examples of the preferred complexes are those in which L is 1,4,7-trimethyl-1,4,7-triazacyclononane and 2 is methyl-1,4,7-trimethyl-1,4,7-triazacyclononane and RC ₁ - Is alkyl.

worin t 2 ist; s 3 ist; R¹, R² und R³ unabhängig ausgewählt sind aus Wasserstoff, C₁-C₆-Alkyl, Aryl, das jeweils wahlweise substituiert sein kann.Further examples of mononuclear manganese complex catalysts having a bleaching effect in the absence of a hydrogen peroxide source or other peroxygen bleaching agent include those having the formula: [LM _n X _p ] ^Z Y _q wherein manganese can be present in one of the oxidation states II, III or IV; each X independently represents a coordinating species with the exception of RO ^- , such as Cl ^- , Br ^- , I ^- , F ^- , NCS ^- , N ₃ ^- , I ₃ ^- , NH ₃ , RCOO ^- , RSO ₃ ^- , RSO ₄ ^- in which R is alkyl or aryl which may be optionally substituted, OH ^-, O ₂ ^2-, HO ₂ ^-, H ₂ O, SH, CN ^-, OCN ^-, S ₄ ^2-, and mixtures thereof; p is an integer of 1 to 3; z indicates the charge of the complex and is an integer that may be positive, zero or negative; Y is a counterion whose choice depends on the charge z of the complex; q = z / Y; and L is a ligand having the formula:

wherein t is 2; s is 3; R ¹ , R ² and R ^{3 are} independently selected from hydrogen, C ₁ -C ₆ alkyl, aryl, each of which may optionally be substituted.

„Bcyclam" (5,12-Dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecan) wird hergestellt nach J. Amer. Chem. Soc., (1990), 112, 8604.A particularly useful metal bleach catalyst is [Mn (Bcyclam) C12]:

"Bcyclam" (5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane) is prepared according to J. Amer. Chem. Soc., (1990), 112, 8604.

The Bleach catalysts herein can along with additional Materials are processed to reduce the influence of color, if so for the aesthetics of the product desired or in enzyme-containing particles as exemplified below as shown, or the compositions can be prepared to contain catalyst "speckles".

Organic polymer compound

organic Polymer compounds can be added as preferred ingredients of the composition according to the invention. With organic polymer compound is essentially any polymeric organic Connection meant, usually in detergent compositions with dispersants, agents for Prevention of re-deposition of residues, dirt repellent agents or other washing properties is present.

The organic polymer compound is in the detergent compositions the invention typically in an amount of 0.1 to 30 wt .-% present, more preferably from 0.5 to 15% by weight, most preferably from 1 to 10% by weight of the compositions.

Examples of organic polymer compounds include the water-soluble organic homo- or co-polymeric polycarboxylic acids, modified polycarboxylates or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are 2,000-10,000 molecular weight polyacrylates and their copolymers with any other suitable monomer unit, including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acids or their salts, maleic anhydride, acrylamide , Alkylene, vinyl methyl ether, styrene and any desired of it. Preferred are the copolymers of acrylic acid and maleic anhydride having a molecular weight of 5,000 to 100,000, more preferably 20,000 to 100,000.

preferred commercially available acrylic acid-containing Polymers with a molecular weight below 15,000 include those listed below the trade name Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 sold by BASF GmbH and under the trade name Acusol 45N, 480N, 460N sold by Rohm and Haas.

Preferred acrylic acid-containing copolymers include those which comprise as monomer units: a) from 90% to 10%, preferably from 80% to 20%, by weight of acrylic acid or its salts, and b) from 10% to 90% Wt .-%, preferably 20 wt .-% to 80 wt .-% of a substituted acrylic monomer or its salts having the general formula - [CR ₂ -CR ₁ (CO-OR ₃ )] - wherein at least one of the substituents R ₁ , R ₂ or R ₃ , preferably R ₁ or R ₂ , is an alkyl or hydroxyalkyl group of 1 to 4 carbons, R ₁ or R ₂ may be hydrogen and R ₃ may be hydrogen or an alkali metal salt. Most preferred is a substituted acrylic monomer wherein R _{1 is} methyl, R _{2 is} hydrogen (ie, a methacrylic acid monomer).

The most preferred copolymer of this type has a molecular weight from 3500 and contains 60 Wt .-% to 80 wt .-% acrylic acid and 40% to 20% by weight of methacrylic acid.

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

Other optional polymers can Polyvinyl alcohols and acetates, both modified and unmodified, cellulosic and modified cellulosic compounds, polyoxyethylenes, Polyoxypropylenes and copolymers thereof, both modified and unmodified, terephthalate esters of ethylene or propylene glycol or mixtures thereof with polyoxyalkylene units.

suitable Examples are in U.S. Patent Nos. 5,591,703, 5,597,789 and 4,490,271 disclosed.

soil

Suitable polymeric soil release agents include soil release agents comprising: (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments having a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments having a degree of polymerization of from 2 to 10, wherein the hydrophilic segment does not include oxypropylene unit unless it is attached to adjacent moieties at each end by ether linkages; or (iii) a mixture of oxyalkylene moieties comprising oxyethylene and 1 to 30 oxypropylene moieties, the hydrophilic segments preferably comprising at least 25% oxyethylene moieties, and more preferably especially for those ingredients having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobic constituents comprising (i) C ₃ -alkyl-terephthalate segments, wherein, when the hydrophobic constituents also include oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C ₃ oxyalkylene terephthalate units is 2: 1 or less, (ii) C ₄ -C ₆ -alkylene or C ₄ -C ₆ -oxyalkylene segments or mixtures thereof, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) C ₁ -C ₄ - Alkyl ether or C ₄ -Hydroxyalkylethersubstituenten or mixtures thereof, wherein the substituents in the form of C ₁ -C ₄ alkyl ether or C ₄ - hydroxyalkyl ether cellulose derivatives or mixtures thereof, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a) (i) have a degree of polymerization above 200, although higher levels may be used, preferably from 3 to 150, more preferably from 6 to 100. Suitable hydrophobic C ₄ -C ₆ oxyalkylene segments include, but are not limited to on, end caps of polymeric soil release agents, such as MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O-, wherein M is sodium and n is an integer of 4-6 as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 Gosselink, revealed.

Polymeric soil release agents useful herein also include cellulosic derivatives such as cellulosic hydroxyether polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxycellulose ethers such as METHOCEL (Dow). Cellulosic soil repellent agents for this purpose also include those selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyalkyl cellulose; See U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.

Soil release agents characterized by hydrophobic poly (vinyl ester) portions include graft copolymers of poly (vinyl ester), for example, C ₁ -C ₆ vinyl esters, preferably poly (vinyl acetate), on polyalkylene oxide backbones, such as the polyethylene oxide backbones , grafted on. See European Patent Application 0 219 048, published April 22, 1987, by Kud et al.

One another suitable soil release agent is a random copolymer blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The Molecular weight of these polymeric soil release agents is in the Range from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976, and U.S. Patent 3,893,929 to Basadur on July 8, 1975.

One another suitable polymeric soil release agent is a polyester with repeating units of ethylene terephthalate units, containing 10-15 % By weight of ethylene terephthalate units together with: 90-80% by weight of polyoxyethylene terephthalate units derived from a polyoxyethylene glycol having an average molecular weight of 300-5,000.

One Another suitable soil release polymer is a sulfonated product a substantially linear ester oligomer comprising an oligomeric Ester backbone of recurring terephthaloyl and oxyalkyleneoxy units and terminal moieties, which are covalently bound to the main chain. These dirt repellent agents in U.S. Patent 4,968,451 issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink, fully described. Other suitable polymeric soil release agents include the terephthalate polyesters from U.S. Patent 4,711,730 issued December 8, 1987 to Gosselink et al, the anionic, end-capped, oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the oligomeric block polyester compounds from U.S. Patent 4,702,857 issued October 27, 1987 to Gosselink. Other polymeric soil release agents also include the soil release agents from U.S. Patent 4,877,896 issued October 31, 1989 to Maldonado et al, which anionic, especially sulfoarolyl, end-capped Terephthalate ester disclosed.

One Another soil release agent is an oligomer with recurring Units of terephthaloyl units, sulfoisoterephthaloyl units, Oxyethyleneoxy and oxy-1,2-propylene units. The recurring units form the main chain of the oligomer and are preferably modified Isethionate end caps completed. A particularly preferred soil release agent of this type comprises a sulfoisophthaloyl unit, 5 terephthaloyl units, Oxyethyleneoxy and oxy-1,2-propyleneoxy units in the ratio 1.7 to 1.8 and two end-cap units of sodium 2- (2-hydroxyethoxy) ethanesulfonate.

Heavy metal ion sequestrant

The Compositions of the invention can as an optional ingredient, a heavy metal ion sequestrant contain. With heavy metal ion sequestrant is herein incorporated Component meant to mask (chelate) heavy metal ions. These ingredients can also have calcium and magnesium chelate forming properties, but preferably show selectivity to the binding of heavy metal ions, like iron, manganese and copper.

Heavy metal ion sequestrant are generally in an amount of 0.005 wt .-% to 20 wt .-% present, preferably from 0.1% to 10% by weight, more preferably from 0.25% to 7.5%, most preferably 0.5% by weight to 5% by weight of the compositions.

Heavy metal ion sequestrant, which are acidic by nature, with, for example, phosphonic acid or Carboxylic acid functionalities, can either in their acid form or as a complex / salt with a suitable counter cation, such as an alkali or alkali metal ion, an ammonium or a substituted Ammonium ion or any mixture thereof. Preferably each salt / complex is water-soluble. The molar ratio of Countercation to the heavy metal ion sequestrant is preferred at least 1: 1.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above-mentioned types are diethylenetriaminepenta- (methylenephosphonate), ethylenediaminetri (methylenephosphonate), hexamethylenediamine tetra (methy lenphosphonat) and hydroxyethylene-1,1-diphosphonate.

Other suitable heavy metal ion sequestrants for this purpose Uses include nitrilotriacetic acid and polyaminocarboxylic acids, such as ethylenediaminetetraacetic, ethylenetriaminepentaacetic, ethylenediamine, ethylenediaminediglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salt from that.

Especially preferred are ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted Ammonium salts thereof or mixtures thereof. Preferred EDDS compounds are the free acid form and sodium or magnesium salts or complexes thereof.

Organodiphosphonic acid, in whose chemical structure contains no nitrogen. This definition therefore concludes the organo-aminophosphonates, which, however, in compositions of the invention as components of heavy metal ion sequestrants could be.

The organodiphosphonic acid is preferably a C ₁ -C ₄ diphosphonic acid, more preferably a C ₂ diphosphonic acid such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP), and may be in partially or fully ionized form , especially as a salt or complex.

water-soluble sulfate salt

The Compositions optionally contain a water-soluble Sulfate salt. Optionally, the water-soluble sulfate salt is in one Amount of 0.1 wt% to 40 wt%, more preferably 1 wt% to 30% by weight, most preferably from 5% to 25% by weight of the compositions contain.

The water-soluble Sulfate salt can be essentially any salt of sulfate be with any countercation. Preferred salts are selected from the sulfates of the alkali and alkaline earth metals, in particular sodium sulfate.

Alkali metal silicate

An alkali metal silicate is a preferred component of the compositions of the invention. A preferred alkali metal silicate is a sodium silicate having a SiO ₂ : Na ₂ O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, and most preferably 2.0. Sodium silicate is preferably present in an amount of less than 20 weight percent, preferably from 1 weight percent to 15 weight percent, most preferably from 3 weight percent to 12 weight percent SiO 2. The ₂ alkali metal silicate may be in the form of the anhydrous salt or a hydrated salt.

Alkali metal silicate may also be included as part of an alkalinity system to be available.

The alkalinity system preferably also contains sodium metasilicate which is present in an amount of at least 0.4 weight percent SiO ₂ . Sodium metasilicate has a nominal SiO ₂ : Na ₂ O ratio of 1.0. The weight ratio of the sodium silicate to the sodium metasilicate, measured as SiO ₂ , is preferably 50: 1 to 5: 4, more preferably 15: 1 to 2: 1, most preferably 10: 1 to 5: 2.

colorants

Of the Term "colorant" as used herein stands for Any substance that has light in certain wavelengths from the visible light spectrum absorbed. Such colorants when added to a detergent composition the effect that they have the visible color and therefore the appearance change the detergent composition. Colorants can, for example be either dyes or pigments. Preferably, the colorants stable in the composition in which they are contained. In a Therefore, the colorant is preferably the high pH composition stable in base and in a low pH composition the colorant is preferably acid-stable.

The first and / or second and / or further composition may contain a colorant, a mixture of colorants, colored particles, or a mixture of colored particles, such that the different phases have a different optical appearance. Preferably, either the first or the second phase comprises a colorant. If both the first and the second phase and / or further phases Colorants, it is preferred that the colorants have a different visual appearance.

enzyme Stabilizing system

Here in preferred enzyme-containing compositions may be from 0.001% to 10% by weight, preferably 0.005 wt% to 8 wt%, most preferably 0.01 Wt .-% to 6 wt .-% of an enzyme-stabilizing system. The enzyme stabilization system can be any stabilization system which is compatible with the detergent enzyme. Such stabilizing Systems can Calcium ions, boric acid, propylene glycol, short-chain carboxylic acid, Boronic acid, Chlorine bleach scavengers and mixtures thereof. Such stabilizing systems can also reversible enzyme inhibitors, such as reversible protease inhibitors, include.

Foam suppression systems

The Detergent tablets according to the invention preferably comprise a suds suppressing system when in use are formulated in washing machine washing compositions, which in one Amount of 0.01% by weight to 15% by weight, preferably 0.05% by weight up to 10% by weight, most preferably from 0.1% by weight to 5% by weight the composition is present.

suitable Foam suppression systems for this purpose Can use essentially comprise all known foam-suppressing compounds, including for example, foam-suppressing Silicone compounds, foam-suppressing 2-alkyl and Alcanolverbindungen. Preferred foam suppression systems and foam-suppressing Compounds are disclosed in PCT Application No. WO93 / 08876 and EP-A-705 324 discloses.

Polymeric dye transfer inhibiting medium

The Compositions herein can be used Furthermore 0.01% by weight to 10% by weight, preferably 0.05% by weight to 0.5% by weight polymeric dye transfer inhibiting Means include.

The polymeric dye transfer inhibiting Means are preferably selected of polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations from that.

Optical brightener

The suitable for use in laundry processes herein Compositions also optionally contain from 0.005% to 5% by weight. certain types of hydrophilic optical brightener.

worin R₁ ausgewählt ist aus Anilin, N-2-Bis-hydroxyethyl und NH-2-Hydroxyethyl, R₂ ausgewählt ist aus N-2-Bis-hydroxyethyl-, N-2-Hydroxyethyl-N-methylamino, Morphilin, Chlor und Amino und M ein salzbildendes Kation, wie Natrium oder Kalium, ist.Hydrophilic optical brighteners useful herein include those having the structural formula:

wherein R _{1 is} selected from aniline, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, R _{2 is} selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholine, chlorine and Amino and M is a salt-forming cation, such as sodium or potassium.

In the above formula, when R _{1 is} aniline, R _{2 is} N-2-bis-hydroxyethyl, and M is a cation, such as sodium, then the brightener is 4,4'-bis - [(4-anilino-6- (N-2-bis-hydroxyethyl -) - s -triazin-2-yl) amino] -2,2'-stilbene disulfonic acid and disodium salt. This particular brightener species is sold under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

In the above formula, when R _{1 is} aniline, R _{2 is} N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, then the brightener is 4,4'-bis - [(4-aniline -6- (N-2-hydroxyethyl-N-methylamino) -s-tria zin-2-yl) amino] 2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is sold under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

In the above formula, when R _{1 is} aniline, R _{2 is} morphilin, and M is a cation such as sodium, then the brightener is 4,4'-bis - [(4-anilino-6-morphilino-s-triazine-2 yl) amino] 2,2'-stilbene disulfonic Natriuinsalz. This particular brightener species is sold under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Other preferred optical brighteners are those known as brighteners 49 and distributed by Ciba-Geigy.

Other optional ingredients

Other optional ingredients for inclusion in the compositions of the invention include fragrances and bulking salts, with sodium sulfate a preferred filling salt is.

pH of the compositions

The Compositions of the invention are preferably not formulated to be inappropriate high pH, preferably having a pH of 7.0 to 12.5, more preferably from 7.5 to 11.8 and most preferred from 8.0 to 11.5, measured as a 1% solution in distilled water.

Examples

The The present example provides the detergent additive bags described herein again and should not be limiting be.

Claims (11)

A laundry additive bag comprising at least two various compositions, wherein the first and second Composition by the presence of at least one ingredient differ, wherein the bag comprises two or more chambers, made of water-soluble Film or film material are produced and wherein the second Composition comprising a particulate bleach, liquid composition is. The wash additive bag of claim 1, wherein the Bag includes three or more chambers. Wash additive bag according to one of the preceding Claims, the water-soluble Film or sheet material is hydroxypropylmethylcellulose. A laundry additive bag according to claim 2, comprising at least three compositions, wherein the first, second and third composition by the presence of at least one Ingredient differ. A laundry additive bag according to claim 2 or 4, wherein The first, second and third composition are so different differ that in a composition at least one ingredient that is not present in the other two compositions is included. Wash additive bag according to one of the preceding Claims, wherein the first composition is an ingredient selected from a softening ingredient, enzyme, an organic, polymeric Compound, a soil release agent, a dye transfer inhibitor, a brightener and mixtures thereof. Wash additive bag according to one of the preceding Claims, wherein the second composition comprises a bleaching agent containing a preformed monoperoxycarboxylic acid, preferably phthaloylamidoperoxyhexanoic acid. Method of treating tissues with a laundry additive bag according to one of the preceding claims in conjunction with a usual Detergent in the presence of water. Use of a bag according to any one of claims 1 to 7 as a laundry additive. Use of a bag according to any one of claims 1 to 7, to wash and / or soften fabric. Use of a bag according to any one of claims 1 to 7 to wash and / or ironing too facilitate.