MXPA00002808A - Cleaning compositions - Google Patents

Abstract

The invention relates to bleaching compositions and cleaning compositions comprising the bleaching compositions, containing a specific photo-bleaching agent and a bleaching agent capable of providing a peroxyacid bleaching compound. The compositions are particularly useful in laundry and dish washing processes to provide enhanced photo-bleaching performance, fabric whiteness appearance and overall cleaning.

Description

CLEANING COMPOSITIONS TECHNICAL FIELD The invention relates to bleaching compositions and cleaning compositions comprising bleaching compositions, which contain a specific photobleaching agent and a bleaching agent capable of providing a peroxyacid bleaching compound. The compositions are particularly useful in laundry and dishwashing processes to provide photobleaching performance, appearance of whiteness to fabrics and improved general cleanliness.

BACKGROUND OF THE INVENTION In the art, several compounds are known which, after being exposed to light, can be photoactivated, becoming an active species for additional chemical or photochemical reactions. Two general examples thereof are the photobleaching compounds porphyrin and phthalocyanine. These non-metallated compounds, and especially when combined with an appropriate cation, can undergo a series of reactions, starting with a photochemical reaction step which transforms the compound into an excited state. The excited state of the molecule can react with spots to whiten them or alternatively after subsequent steps of reaction along with molecular oxygen can produce "active oxygen". Active oxygen includes "singlet oxygen" or superoxide molecules. The superoxide can subsequently be converted to hydrogen peroxide. The "singlet oxygen", superoxide or hydrogen peroxide, formed in this series of reactions, are oxidizing species that can react with stains to whiten them chemically to a colorless state and normally soluble in water, which results in what is known as bleaching. photochemical Examples of porphyrins or porphyrin-type compounds include hematoporphyrin, chlorophyll, chlorin, oxychlorin, pheophorbide, pyropheophorbide, benzoporphyrins, tetra-arylporphyrin, zinc tetraphenylporphyrin, expanded porphyrins obtained from tripyrrimetimethane. Examples of phthalocyanines and naphthalocyanines include phthalocyanines and naphthalocyanines of zinc, aluminum, indium, silicon and gallium, the most common being zinc and aluminum phthalocyanines. Other examples of photobleaching agents are dyes of the xanthene family such as rose bengal, eosin and fluorescein. Additional examples of photobleaches include metachromic dyes such as thionin, methylene blue, benzo [a] phenoxyazinium (Nile Blue A) and benzo [a] phenothiazinium. A limitation to the use of some of these more water-soluble photobleaners may be their low surface activity. One of the problems associated with the use of phthalocyanine photoblank compounds, naphthalocyanines and porphyrin arises from the fact that these are not soluble in water, particularly when the parent rings are substituted only with hydrogen. A task for the formulators of photobleaching compounds and cleaning products has been to prepare photobleaching agents that are soluble in water. In an effort to achieve this, several patent documents refer to photobleaching with phthalocyanine derivatives, which have various solubilizing substituents, such as EP-1 19746, EP-379312, EP-553608, EP-596187 and EP-692947. These documents describe selected substituent units that are hydrophilic and which bind to the photosensitive ring units to increase the solubility or photochemical properties of the molecule. In general, three or more substituents are necessary to obtain the required solubility. However, a problem with the introduction of (high numbers of) substituent groups is that the photoblanking properties of the ring system are frequently affected. For example, a change that increases solubility could reduce the quantum efficiency of the molecule. This can cause the derivative compound not to have sufficient photobleaching properties. First, this can lead to less oxygen formation in the singlet and thus less bleaching. Secondly, the absorption spectrum can change, leading to undesirable coloring of the photobleaching compounds during use, which is a particular problem when used in the photobleaching of fabrics.

. The preparation of photobleaching agent derivatives is known in the art. However, the preparation of these photobleaching agents derivatives proceeds with low yields which introduces impurities and increases costs. These impurities can also introduce undesirable coloration which produces staining, particularly when used on fabrics. Another important limitation for using most photobleaching compounds known in the art is that they are highly colored materials (having an absorption in the range of 600-800 nanometers). For example, high concentrations of these compounds in fabrics will lead to staining of the fabric. Therefore, it should be avoided that photobleaching compounds are deposited in high quantities on the fabric during washing. In addition, the accumulation of these compounds on the surface of the fabric should be avoided. Even another limitation of most photobleaching compounds known in the art is that the introduction of solubilizing groups tends to destabilize the compounds in such a way that they tend to decompose once exposed to light, in particular sunlight, which it deactivates as photobleaching compounds, thus leading to a lower bleaching performance. Moreover, it is frequently required that in the cleaning compositions containing the photobleaching compounds, additional bleaching agents be present. However, these bleaching agents can also cause the decomposition and inactivation of photobleaching agents. Therefore, there is a need for improved photobleaching compounds which are water soluble, which have optimal photobleaching properties and which overcome the problems of decomposition and accumulation. Currently the inventors have discovered improved photobleaching agents for use in cleaning compositions. The photobleaching agent is formed by integrating a photobleaching compound (which is soluble in water or slightly soluble in water), with a specific polymeric compound, soluble in water. The inventors have discovered that in this way a photobleaching agent is obtained which has an improved water solubility and which has improved surfactancy. Without wishing to be limited by theory, the improvement in photobleaching results from photobleaching agents that have an improved affinity towards the soils present in the fabrics for washing. Therefore, more specific and more effective bleaching of these soils is achieved. In addition, the photobleaching agents included in this invention can provide more efficient photobleaching performance because they are more stable when exposed to light or bleach. Thus, for a given amount of photobleaching agent deposited on a surface, a greater amount of singlet oxygen or other bleaching species can be generated before the photobleach decomposes. In addition, the photobleaching agent has an absorption spectrum that results in a desired color, in particular a blue color, of the agent and the fabric containing the agent. Moreover, the inventors have discovered that the photobleaching agent migrates uniformly towards the surface of the fabric. In this way, high amounts of photobleaching can be avoided in one place, which leads to staining. The inventors have also discovered that the agent accumulates to a lesser degree in the fabric in subsequent washes. The staining of the fabric by means of highly colored inactive agents is also avoided, because the photobleaching agent of the invention can be prepared without the introduction of impurities. Additionally, the photobleaching agent can provide a desired shade on the fabric, which leads to a better appearance of the fabric. Currently the inventors have discovered that detergents containing these novel photobleaching agents and a bleaching agent capable of providing a peroxyacid bleaching species, have, surprisingly, improved bleaching performance. It has been found that the efficiency of the peroxy acid-containing bleaching agent or that which provides peroxyacid is improved when novel photobleaching agents are present. It is believed that this is caused by the generation, by means of the photobleaching agent, of peroxide radicals instead of singlet oxygen under the influence of sunlight. It is believed that peroxide radicals provide improved bleaching performance. Improved performance and efficiency results in improved cleaning of stains that can be bleached and an appearance of improved whiteness of the fabrics and, alternatively, allows the formulation of cleaning compositions with a reduced level of bleaching agent or photobleaching agent. .

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a bleaching composition comprising: (a) from 0.5 ppm by weight of a photobleaching agent, comprising a polymeric component and a photobleaching component, integrated one with the other. (b) from 0.1% by weight of a bleaching agent that is capable of providing a peroxyacid compound. The bleaching composition is preferably present in a cleaning composition, preferably a dishwashing detergent or even more preferred laundry detergent.

DETAILED DESCRIPTION OF THE INVENTION Photobleaching Agent The photobleaching agent of the invention comprises one or more specific polymeric components and one or more photobleaching components integrated with one another, as described in the present invention. "Integrated to each other" when used in the present invention refers to the integration between the components of the agent, which can be achieved by a process comprising the steps of a) forming a molten material or a solution, comprising a compound photo-bleach and a polymeric compound; b) in an additional step, form and separate the photobleaching agent. This could mean that the photobleaching agent component is adsorbed on or absorbed in the polymer component, or that the polymeric component and the photobleaching agent component form an associative complex structure or coacervate complex structure. The weight ratio of the polymeric component to the photobleaching component in the photobleaching agent is from 1: 1 to 1, 000: 1, preferably from 5: 1 to 1, 000: 1, more preferred from 20: 1 to 100: 1, even more preferred from 20: 1 to 60: 1. The photobleaching agent of the invention preferably contains from 50% to 99.9% by weight, more preferred from 90% to 99.9% by weight, even more preferred from 92% to 99% by weight, and even more preferred from 95% to 98% by weight. % by weight of the polymer component. The photobleaching agent of the invention preferably contains from 0.1% to 50% by weight, more preferred from 0.1% to 10% by weight, even more preferred from 1% to 8% by weight, and even more preferred from 2% to 5% by weight. % by weight of the photobleaching component. When the agent is used in fabrics, higher levels of the photobleaching component may be preferred when a hue effect is desirable on the fabrics. It may be preferred that the photobleaching agent be coated or encapsulated. Preferred coating or encapsulating agents are for example starch, sucrose, glycerin, waxes and oils, or preferably mixtures thereof. Usually, the coating or encapsulating material is present in a weight ratio to the photobleaching agent of 2: 1 to 15: 1, preferably about 8: 1 to 12: 1. The bleaching composition of the present invention contains the photobleaching agent at a level of at least 0.5 ppm by weight. Typically, the photobleaching agent is incorporated in a bleaching composition, or in the cleaning compositions comprising the bleaching composition, at a level from about 0.75 ppm to 3% by weight, preferably from 0.1 ppm to 1% by weight, even more preferred from 5.0 ppm to 0.5% by weight and especially preferred from around 15 ppm to 300 ppm or even up to 150 ppm. In the solid cleaning compositions of the present invention, it may be preferred that the photobleaching agent be present as a separate particulate material. Preferably as a particulate material added in dry or dry blended. It may be preferred that the photobleaching agent be premixed with the anionic surfactants of the present invention or with other additional ingredients of the compositions, as described later in the present invention. The photobleaching agent can also be sprayed onto the particulate material contained in the solid cleaning composition of the present invention.

Polymeric Compounds The polymeric compound to be integrated with a photobleaching compound to form the polymeric component of the photobleaching agent of the invention, preferably comprises polymerized monomeric units containing di-polar aprotic groups. Preferably, at least 50%, more preferred. at least 75%, still more preferred at least 90%, still more preferred at least 95% of the polymerized monomer units contain a di-polar, aprotic group. The polymeric compounds of the invention can be homopolymers, which comprise a base structure having a type of polymerized monomer units, or copolymers comprising a base structure having different polymerized monomer units. The polymeric compounds preferably have a number average molecular weight from 500 to 1,000,000; most preferred from 1,000 to 100,000; even more preferred from 2,000 to 80,000, still more preferred from 5,000 to 60,000. Highly preferred monomer units include vinylamides such as N-vinylpyrrolidone and N-vinylacetamide as well as vinylheterocycles such as N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine and 4-vinylpyridine N-oxide. These monomeric units containing aprotic, dipolar group are particularly effective to solubilize the photobleaching component. Co-monomers can be used to confer additional properties to the polymer such as charge, hydrophobic character and hydrophilicity. Suitable comonomers include acrylic acid or methacrylic acid, its salts and esters including methyl, ethyl, hydroxyethyl, propyl, hydroxypropyl, butyl, ethylhexyl, decyl, lauric, i-bornylic, cetyl, palmityl, phenoxyethyl, stearyl acrylate. Also included are diethylaminoethylacrylate, dimethylaminoethylacrylate, dimethylaminopropylacrylate and the choline esters of acrylic acid or methacrylic acid. Also included is acrylamide or methacrylamide and its various N-substituted derivatives including N-methylolacrylamide, N, N-dimethylaminopropylacrylamide, N, N, N-trimethylammoniopropylacrylamide, N, N-diethylaminopropylacrylamide, N-tert-butylacrylamide, N -tert-octylacrylamide, N-undecylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid. Also included are vinyl esters such as vinylacetate, vinylpropionate, vinyl laurate, neo-octanoic vinyl ester, neo-nonanoic acid vinyl ester, neo-decanoic acid vinyl ester.

Also included are other vinyl monomers such as styrene, vinyltoluene, α-methylstyrene. Also included are unsaturated acids such as crotonic acid, maleic acid, fumaric acid, itaconic acid or their respective anhydrides or esters. The most preferred polymeric compounds according to this invention are polyvinylimidazole (PVI), or a copolymer of polyvinylpyrrolidone and polyvinylimidazole (PVPVI), more preferred polyvinylpyrrolidone (PVP). Preferably, these highly preferred polymeric compounds have an average molecular weight of from 20,000 to 60,000. In addition, mixtures of two or more polymeric compounds, described in the present invention can be used to integrate them with a photobleaching compound to form the polymeric component of the photobleaching agent of the invention.

Photobleaching Compound The photobleaching compound to be integrated with a polymeric compound to form the photobleaching component of the photobleaching agent of the invention can be any compound known in the art that can undergo a reaction of a series of reactions, starting with a photochemical reaction step together with molecular oxygen to form "active oxygen" molecules. Active oxygen includes "singlet oxygen" or superoxide molecules. The superoxide can subsequently be converted to hydrogen peroxide. The "oxygen in singlet", superoxide or hydrogen peroxide, formed in this series of reactions, are oxidizing species that can react with stains to whiten them chemically to a colorless state and normally soluble in water, which results in what is known as photochemical bleaching. Photobleaching compounds are compounds having a porphyrin or porphyrin structure. Porphyrin and porphyrin, in the literature, are used as synonyms, but conventionally porphine means the simplest porphyrin without any substituent; in which porphyrin is a sub-class of porphine. References made to porffin in this application will include porphyrin. The porphine structures preferably contain a metal element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferred Ge, Si or Ga, or even more preferred Al, very preferred Zn . It may be preferred that the photobleaching compound or component is substituted with substituents that are selected from the group consisting of alkyl groups such as the methyl, ethyl, propyl, t-butyl groups and aromatic ring systems such as the pyridyl, N-oxide pyridyl, naphthyl and anthracyl. The photobleaching compound or component may have solubilizing groups as substituents, however, for the present invention it is preferred that the photobleaching component or component has only 2 or less solubilizing groups, Even more preferred the compound, or photobleaching component does not have solubilizing substituent groups, or more preferred is not substituted. Highly preferred photobleaching compounds are compounds having a phthalocyanine structure, which preferably has the metal elements or cations described above. The metal phthalocyanines and their derivatives have the structure indicated in formula 1 and / or formula 2, in which the positions of the atoms of the phthalocyanine structure are numbered in the conventional manner. The phthalocynins may be substituted, for example the phthalocynin structures which are substituted at one or more of the positions of the atoms 1-4, 6, 8-1 1, 13, 15-18, 20, 22-25, 27 of Formula 1 and / or Formula 2. However, the highly preferred transition metal phthalocyanine is an unsubstituted phthalocyanine. For oxidation states of the element or metal cation greater than (II), the symbol X4 of formula 2 represents an anion, preferably OH- or Ci- when the oxidation state is (III).

Bleaching agent The bleaching composition of the present invention contains from 0.1% by weight of a bleaching agent capable of providing a peroxy acid-based bleach. Preferably, the bleaching composition contains from 0.5% to 50% by weight of the bleaching agent, more preferred from 1% to 25%, or even from 1.5% to 10%. The bleaching composition is preferably comprised in a cleaning composition, preferably a laundry or dishwashing detergent composition, such that the bleaching agent is present at a level from 0.1% to 25% by weight, preferably from 0.5 % up to 20% or even from 1% up to 15% by weight of the cleaning composition. The bleaching composition may comprise any of the additional ingredients as described in the present invention. It may be preferred that the bleaching composition contains the bleaching agent intimately mixed with a carrier material or a coating material or mixtures thereof. Preferably, the bleaching agent comprises a preformed or even more preferred peroxy acid compound, a peroxy acid-based bleach precursor, capable of providing a peroxyacid compound. Preferably, the bleaching composition comprises a peroxyacid precursor and a source of hydrogen peroxide. The production of the peroxyacid occurs in an in situ reaction of the precursor with a source of hydrogen peroxide. Compositions containing mixtures of a source of hydrogen peroxide and an inorganic peroxyacid precursor in combination with a preformed organic peroxyacid are also contemplated. It may be preferred that the bleaching composition comprises more than one peroxyacid compound, preferably precursors, preferably at least one peroxyacid compound or preferably peroxyacid precursor that provides a peroxyacid compound containing at least 7 carbon atoms and therefore less a peroxyacid compound or, preferably, a peroxyacid precursor that provides a peroxyacid compound containing from 2 to 6 carbon atoms.

Peroxyacid-based bleach precursor Peroxyacid-based bleach precursors are compounds that can react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Peroxyacid precursors can generally be represented as: O ll X-C- L wherein L is a leaving group and X is essentially any functionality, such that in perhydrolysis, the structure of the peroxyacid produced is: O I! X-C- OOH Suitable peroxy acid-based bleach precursor compounds typically contain one or more N-acyl or O-acyl groups, whose precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1 147871, 2143231 and EP-A-0170386.

Outgoing groups The outgoing group, hereinafter referred to as group L, must be reactive enough for the perhydrolysis reaction to occur within the optimum time frame (eg, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize to be used in a bleaching composition. The preferred L groups are selected from the group consisting of: R3 Y -O- CH = C- CH = CH2 - O-CH = C- CH = CH- R3 O Y II I? -O-C = CHR4 • and -N- S- CH- R4 l II R3 O and mixtures thereof, in which R ^ is an alkyl, aryl or alkaryl group containing 1 to 14 carbon atoms, R3 is an alkyl chain that contains 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a group solubilizer. Any of R1, R3 and R4 can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups. The preferred solubilizing groups are -S? 3"M +, -C? 2" M +, - S? 4"M +, -N + (R3) 4? - and O-N (R3) and most preferably -S? 3" M + and -C? 2"M +, wherein R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, more sodium and potassium being preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Precursors of bleach based on alkylpercarboxylic acid The precursors of bleach based on alkylpercarboxylic acid form percarboxylic acids in perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylcarboxylic acid bleach precursors of the imide type include the N-NN-N-tetraacetylated alkylene diamines in which the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. The TAED is preferably not present in the agglomerated particulate material of the present invention, but is preferably present in the detergent composition, which contains the particulate material. Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Amide-substituted alkylperoxy acid precursors Amide-substituted alkylperoxy acid precursor compounds are suitable herein, including those having the following general formulas: R1- C- N- R2- C- L R1- N- C- R2- C- L II I? II l? II OR R5 OR R5 Q O where R "! is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and R§ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group; R1 can be straight or branched chain alkyl, aryl or substituted alkylaryl which contains branching, substitution or both and which can be obtained from any synthetic sources or natural sources including for example tallow fat. Analogous structural variations are allowed for R2. R2 may include alkyl, aryl, in which said R2 may also contain halogen, nitrogen, sulfur and other substituent groups or typical organic compounds. R5 is preferably H or methyl. R1 and R5 preferably should not contain more than 18 carbon atoms in total. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386. Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds which are selected from (6-octanamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and the highly preferred (6-nonanamido-caproyl) oxybenzenesulfonate and mixtures thereof as described in EP-A-0170386.

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

Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids in perhydrolysis. Typically, the cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion. The peroxyacid precursor compound which will be so cationically substituted may be a perbenzoic acid precursor compound or a substituted derivative thereof as described hereinabove. Alternatively, the peroxyacid precursor compound may be a precursor alkylcarcarboxylic acid compound or an amide substituted alkylperoxyacid precursor as described hereinafter. Cationic peroxyacid precursors are described in the U.S. Patents. Nos. 4,904,406; 4,751, 015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; R.U. 1, 382.594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Examples of preferred cationic peroxyacid precursors are described in United Kingdom patent application No. 9407944.9 and in the patent applications of E.U.A. Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the substituted ammonium or alkylammonium alkyl or benzoyloxybenzenesulfonates, the N-acylated caprolactams and the benzoylperoxides of monobenzoyltetraacetyl glucose. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkylammonium methylenebenzoylcaprolactams and trialkylammonium methylenealkylcaprolactams.

Organic peroxyacid precursors of the benzoxazine type Also suitable are the benzoxazine type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: wherein R-j is H, alkyl, alkaryl, aryl or arylalkyl.

Preformed organic peroxyacid A preferred class of organic peroxyacid compounds are the amine substituted compounds of the following general formulas: R '- wherein R "! is an alkyl, aryl or alkaryl group having from 1 to 14 carbon atoms, R ^ is an alkylene, arylene and alkarylene group containing from 1 to 14 carbon atoms, and R§ is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386. Other organic peroxyacids include the diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, acid diperoxytetradecanedioic acid and diperoxyhexadecandioic acid Mono- and diperazelaic acid, mono- and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid are also suitable in the present invention.

Sources of Hydrogen Peroxide The inorganic perhydrate salts are a preferred source of hydrogen peroxide for use in the bleaching compositions of the invention or the cleaning compositions comprising the bleaching composition. These salts are normally incorporated in the form of the alkali metal salt, preferably the sodium salt, at a level of 1% to 40% by weight, most preferably 2% to 30% by weight and more preferably 5% to 25% by weight. % by weight of the bleaching or cleaning compositions. Examples of inorganic perhydrate salts include perborate, percarbonate, perfosphate, persulfate and persilicate. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt. They can be included as the crystalline solid without additional protection. However, for certain perhydrate salts the preferred embodiments of said granulated compositions use a coated form of the material which provides a better storage stability for the perhydrate salt in the granulated product. Suitable coatings comprise inorganic salts such as the alkali metal salts of silicate, carbonate or borate, or mixtures thereof, or organic materials such as waxes, oils or fatty soaps. Sodium perborate is a preferred perhydrate salt and may be in the form of the monohydrate of the nominal formula NaB 2 H 2 o 2 or the tetrahydrate Na B 2 H 2 2-3 2-3 H 2. The alkali metal percarbonates, particularly sodium percarbonate, are the preferred perhydrates in the present invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C? 3.3H2? 2, and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions of the present invention. The sources of hydrogen peroxide may be coated, preferably with inorganic salts, acids or organic salts, silicates or mixtures thereof.

Additional ingredients The bleaching compositions according to the invention or the cleaning compositions of the present invention may also contain additional ingredients. The precise nature of these additional ingredients and the levels of incorporation thereof will depend on the physical form of the compositions and the precise nature of the washing operation for which it will be used. The compositions preferably contain one or more additional components selected from surfactants, detergency builders, sequestrants, bleaches, bleach precursors, bleach catalysts, polymeric organic compounds, enzymes, suds suppressors, lime soap dispersants, soil suspending and anti-redeposition agents, soil release agents, perfumes and inhibitors of additional corrosion. Highly preferred in the compositions of the present invention may be chelating agents, capable of forming complexes with or binding to heavy metal ions. It has been found that chelating agents can further improve the solubility of bleaching agents. It is believed that this may be because the chelating agents form complexes with the heavy metal ions contained in the photobleaching agent. Any of the chelating agents described in the present invention may be appropriate in the compositions of the present invention.

The levels of the ingredients, when described in the present invention, are in percent (%) by weight of the cleaning composition, which contains the bleaching composition of the invention, unless otherwise indicated.

Surfactant The bleaching compositions or cleansing compositions preferably contain one or more surfactants which are selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants, and mixtures thereof. A typical list of anionic, nonionic, ampholytic and zwitterionic classes, as well as species of these surfactants, is given in the U.S. patent. No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (Vols. I and II, by Schwartz, Perry and Berch). A listing of suitable cationic surfactants is given in the U.S.A. No. 4,259,217, issued to Murphy on March 31, 1981. When present, the ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic Surfactant The compositions preferably comprise an anionic surfactant. Essentially any of the surfactants useful for detersive purposes may be comprised in the detergent composition. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred. Surfactant systems comprising a sulphonate and sulfate surfactant are highly preferred, preferably a linear or branched alkylbenzene sulfonate and alkyl ethoxy sulfates, such as those described herein, preferably combined with cationic surfactants as described herein invention. Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, methyl tauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C- | 2_Ci 8 monoesters), sulfosuccinate diesters (especially saturated and unsaturated C6-C-14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids, as well as hydrogenated rosin acids present in tallow oil or derivatives thereof.

. Sulphonic Anion Surfactant The anionic sulfate surfactants suitable for use in the present invention include the primary and secondary, linear and branched alkyl sulphates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, C5- acyl glucamin sulfates. Ci 7-N- (C 1 -C 4 alkyl) and -N- (C 1 -C 2 hydroxyalkyl), and alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (non-sulphonated nonionic compounds are described herein). The alkyl sulfate surfactants are preferably selected from the linear and branched primary C 10 -C 18 alkyl sulfates, most preferably the branched chain C 1 -C 15 alkyl sulfates and the straight chain C 12 -C 14 alkyl sulfates. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the alkyl sulfates of C- | Q-Ci 8 that have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. Most preferably, the alkyl ethoxy sulfate surfactant is an alkyl sulfate of C-H-C-J 8 mL and preferably of C-J-I -C-J S, which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and / or sulfonate surfactants and alkyl ethoxysulfate. Such mixtures have been described in PCT patent application No. WO 93/18124.

Sulfonate anionic surfactant The sulfonic anionic surfactants suitable for use in the present invention include the linear C5-C20 alkylbenzene sulphonate salts. alkyl esters sulfonates, primary or secondary Cβ-C22 alkan sulfonates, Cs-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any of mixtures thereof.

Carboxylate Anionic Surfactant The carboxylate anionic surfactants include the alkylethoxycarboxylates, the alkylpolyethoxy polycarboxylate surfactants and the soaps ("alkylcarboxyls"), especially certain secondary soaps as described herein. Suitable alkylethoxycarboxylates include those with the formula RO (CH2CH2?) XCH2COO_M + in which R is an alkyl group of Ce a C-J8. x varies from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material in which x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxy polycarboxylate surfactants include those having the formula RO- (CHR-? - CHR2-O) -R3 in which R is an alkyl group of CQ to CJ S- * is from 1 to 25, Rj and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. The preferred secondary soap surfactants for use in the present invention are the water-soluble members 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 be included as suds suppressors.

Alkali metal sarcosinate surfactant agent Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R1) CH2COOM, in which R is a linear or branched C5-C-17 alkyl or alkenyl group, R1 is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant Essentially any of the alkoxylated nonionic surfactants are suitable in the present invention. Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkylphenols, ethoxylated nonionic alcohols, ethoxylated / propoxylated nonionic fatty alcohols, nonionic condensates ethoxylate / propoxylate with propylene glycol and the nonionic ethoxylated condensation products with adducts of propylene oxide / ethylenediamine.

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

Non-ionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides suitable for use in the present invention are those having the structural formula R2CONR1Z, in which: R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl , 2-hydroxypropyl, ethoxy, propoxy, or a mixture thereof, preferably C 1 -C 4 alkyl, most preferably C 1 or C 2 alkyl, more preferably C 1 alkyl; (that is, methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C-19 alkyl or alkenyl, most preferably straight-chain C9-C-17 alkyl or alkenyl, more preferably C-1 alkyl or alkenyl. Straight chain C17 or a mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be obtained from a reducing sugar in a reductive amination reaction; most preferably Z is a glycityl.

Non-ionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula: R6CON (R7) 2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R ^ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and - (C2H4?) xH, wherein x is in the range of 1 to 3.

Nonionic Surfactant of Albuterol Polysaccharide The alkylpolysaccharides suitable for use in the present invention are described in US Pat. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, eg, a polyglucoside, a hydrophilic group containing from 1.3 to 10 units of saccharide. Preferred alkyl polyglycosides have the formula R2? (CnH2nO) t (glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glucosyl is preferably obtained from glucose.

Amphoteric Surfactant Amphoteric surfactants suitable for use in the present invention include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) xN ° (R5) 2, wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a group of polyethylene oxide containing from 1 to 3 ethylene oxide groups. Preferred are the alkyl dimethylamine oxide of CI Q-CI SY e 'acylamidoalkyldimethylamine oxide of Cj rj-C-18- A suitable example of an alkylamphecarboxylic acid is Miranol (MR) C2M Conc., Manufactured by Miranol, Inc., Dayton , NJ.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated in the detergent compositions according to the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are examples of zwitterionic surfactants that can be used herein. Suitable betaines are those compounds having the formula: R (R ') 2N + R COO- in which R is a hydrocarbyl group of C? -C- | 8 each R1 is typically C-1-C3 alkyl, and R2 is a C1-C5 hydrocarbon group. Preferred betaines are C12-C-18 dimethyl ammonium hexanoate betaines and CJ QC-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Surfactants are also suitable for use in the present invention. of betaine complexes.

Cationic Surfactants Cationic surfactants suitable for use in the detergent compositions of the present invention include the quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactant is a mono-based surfactant N-alkyl or alkenylammonium of CQ-C ^ \ beta, preferably C5-C-10. wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Also preferred are monoalkoxylated or bisalkoxylated amine surfactants. Another suitable group of cationic surfactants that can be used in the detergent compositions or components thereof in the present invention are cationic ester surfactants. Suitable cationic ester surfactants, including choline ester surfactants, have been described, for example, in US Pat. Nos. 42228042, 4239660 and 4260529.

Cationic surfactants based on monoalkoxylated amine In the present invention, the cationic surfactants based on monoalkoxylated amine preferably of the general formula I are highly preferred: wherein R1 is an alkyl or alkenyl portion containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, more preferred from about 6 to about 14 carbon atoms; R2 and R3 are each independently alkyl groups containing from 1 to about 3 carbon atoms, preferably methyl, more preferably both R2 and R3 are methyl groups; R 4 is selected from hydrogen (preferred), methyl and ethyl; X "is an anion such as chloride, bromide, methylsulfate, sulfate or the like to provide electrical neutrality, A is an alkoxy group, especially an ethoxy, propoxy or butoxy group, and p is from 0 to about 30, preferably 2 to about 15. , more preferred 2 to about 8. Preferably the group ApR4 in formula I has p = 1 and is a hydroxyalkyl group, having no more than 6 carbon atoms in which the -OH group is separated from the ammonium nitrogen atom quaternary by not more than 3 carbon atoms Particularly preferred groups ApR4 are -CH2CH2OH, -CH2CH2CH2OH, -CH2CH (CH3) OH and -CH (CH3) CH2OH, with -CH2CH2OH being particularly preferred.The preferred R1 groups are linear alkyl groups Linear groups R1 having from 8 to 14 carbon atoms are preferred.More other preferred monoalkoxylated amine cationic surfactants to be used in the present invention are those of the carbon atom. formula wherein R1 is C-io-C-iß hydrocarbyl and mixtures thereof, especially C? 0C alkyl, preferably C alquilo? 0 alkyl and C alquilo? alquilo alkyl; C-? 2, and X is any convenient anion to provide charge balance, preferably chloride or bromide. As indicated, compounds of the above type include those in which the ethoxy (CH2CH2O) (EO) units are replaced with butoxy, isopropoxy [CH (CH3) CH2O] and units (i-Pr) [CH2CH (CH3O)] or n-propoxy units (Pr), or mixtures of units EO and / or Pr and / or i-Pr. The levels of the monoalkoxylated amine-based cationic surfactants used in the detergent compositions of the invention preferably range from 0.1% to 20%, more preferred from 0.2% to 7%, more preferred still from 0.3% to 3.0% by weight of the cleaning composition.

Cationic surfactant based on bis-alkoxylated amine The cationic surfactant based on bis-alkoxylated amine preferably has the general formula II: wherein R1 is an alkyl or alkenyl portion containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, more preferred from about 10 to about 14 carbon atoms; R2 is an alkyl group containing from 1 to 3 carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl; X "is an anion such as chloride, bromide, methylsulfate, sulfate or the like, sufficient to provide electrical neutrality.A and A 'can vary independently and each is selected from C -? - C alkoxy, especially ethoxy, (i.e. -CH2CH2O-), propoxy, butoxy and mixtures thereof, p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferred still both p and q are 1. The highly preferred bis-alkoxylated amine based cationic surfactants for use in the present invention are of the formula wherein R 1 is C 0 -C 18 hydrocarbyl and mixtures thereof, preferably C 1, C 2 alkyl, Cu and mixtures thereof. X is any convenient anion to supply charge balance, preferably chloride. With reference to the general cationic structure of bis-alkoxylated amine indicated above, since in a preferred compound R1 is obtained from the alkyl fractions of C? 2-C fatty acids (coconut), R2 is methyl and ApR3 and A'qR4 they are each monoethoxy. Other cationic bis-alkoxylated amine based cationic surfactants useful in the present invention include compounds of the formula: wherein R1 is C10-C18 hydrocarbyl, preferably C10-Cu alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, preferably methyl and X is an anion, especially chloride or bromide. Other compounds of the above type include those in which the ethoxy (CH2CH2O) (EO) units are replaced with butoxy (Bu) isopropoxy units [CH (CH3) CH2O] and units (i-Pr) [CH2CH (CH3O)] or units n-propoxy (Pr), or mixtures of EO and / or Pr and / or i-Pr units.

Source of effervescence In particular, the solid compositions of the present invention may comprise a source of effervescence, preferably comprise an acid source, such that the source of acid is capable of reacting with an alkalinity system, in the presence of water for produce a gas. The acid source is preferably present at a level from 0. 1% to 50%, more preferred from 0.5% to 25%, even more preferred from 1% to 12%, preferably from 1% to 7%, and still more preferred from 2% to 5% by weight of the cleaning composition. It may be preferred that the source of acidity be present in the range of about 1% to about 3%, more preferred about 3% by weight of the cleaning composition. The acid source can be any suitable organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof. The acid source can be a mono-, bi- or triprotic acid. Preferred derivatives include a salt or ester of the acid. The source of acidity is preferably non-hygroscopic, which can improve storage stability. However, an acidic monohydrate source may be useful in the present invention. Organic acids and their derivatives are preferred. The acid is preferably soluble in water. Suitable acids include citric, melaic, maleic, glutaric, tartaric, succinic or adipic acids, monosodium phosphate, sodium bisulfate, boric acid, or a salt or ester thereof. Examples of alkaline species include carbonate, bicarbonate, hydroxide,. the various silicate, percarbonate, perborate, perfosphate, persulfate and persilicate anions. Such alkalinity species can be formed, for example, when the alkali salts selected from alkali metal or alkaline earth metal carbonate, bicarbonate, hydroxide or silicate, including stratified crystalline silicate salts and percarbonate salts, perborates, perfosfathates, persulfate and persilicate and any of the mixtures thereof are dissolved in water. Examples of carbonates are the alkaline earth metal and alkali metal carbonates, including sodium carbonate and sesquicarbonate and any of the mixtures thereof with ultra fine calcium carbonate such as those described in German Patent Application No. 2,321,001. published on November 15, 1973.

Water soluble detergent composition compound The compositions preferably contain a water soluble builder compound, typically present in the detergent compositions at a level of 1% to 80% by weight, preferably 10% to 70% by weight, more preferred from 20% to 60% by weight of the composition. Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, including citric acid or citrate salts, homo- or copolymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, borates, phosphates and mixtures of any of the foregoing. Suitable examples of water-soluble phosphate detergent builders are alkali metal tripolyphosphates, sodium pyrophosphate, potassium and ammonium and potassium and sodium ammonium pyrophosphate, sodium and potassium orthophosphate, and sodium polymetaphosphate, in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Meavating compound of partially soluble or insoluble detergency The compositions may contain a partially soluble or insoluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight, more preferably 20% by weight. % to 60% by weight of the composition. Examples of detergents largely soluble in water include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Naz [(Al? 2) z (Si? 2) and] -xH2? where z and y are at least 6; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, most preferably from 10 to 264. The aluminosilicate based materials are in hydrated form and preferably are crystalline, containing 10 % to 28%, most preferably from 18% to 22% of water in bound form. The aluminosilicate zeolites may be materials that occur in nature, but are preferably obtained in synthetic form. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na- | 2 [(AIO2)? 2 (S¡O2) i 2] xH2O where x is from 20 to 30, especially 27. Zeolite X has the formula: Another preferred aluminosilicate zeolite is the zeolite MAP builder. The zeolite MAP can be present at a level of 1% to 80%, most preferably 15% to 40% by weight of the compositions. The MAP zeolite is described in EP 384070A (Unilever). Another preferred builder may be a layered crystalline silicate based material, preferably of the formula Na2Si2O5, preferably as sold by Clariant under the trade name SKS-6, having an α, β, d configuration, or mixtures of said configuration. Preferably, the stratified crystalline silicate-based material is present at a level of from 0.1% to 10%, more preferred from 0.25% to 7.5% and more preferred even from 0.5% to 5% by weight of the compositions.

Heavy metal ion sequestrant The compositions preferably contain as an optional component a heavy metal ion sequestrant which acts to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelating ability, but preferably show selectivity for binding heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level from 0.005% to 20%, preferably from 0.1% to 10%, more preferred from 0.25% to 7.5% and more preferred still from 0.5% to 5% by weight of the compositions Heavy metal ion sequestrants suitable for use in the present invention include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethan-1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminpenta (methylene phosphonate), ethylenediamintri- (methylene phosphonate), hexamethylenediaminetetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate. Another heavy metal sequestrant suitable for use in the present invention includes nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminpentaacetic acid, ethylenediaminedisuccinic acid, ethylene diamine diglutharic acid, 2-hydroxypropylenediamine diuccinic acid or any of the salts thereof. Especially preferred is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. Other heavy metal ion sequestrants suitable for use in the present invention are described in EP-A-317,542, EP-A-399,133, EP-A-516,102, EP-A-509,382, EP-A-476,257, EP- A-510,331 and EP-A-528,859.

Enzymes The compositions may contain one or more enzymes. Additional preferred enzyme materials include commercially available enzymes. Said enzymes include the enzymes selected from lipases, cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases. , ß-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof. A preferred combination of additional enzymes in a composition according to the present invention comprises a mixture of applicable conventional enzymes such as lipase, protease, amylase, cutinase and / or cellulase, in conjunction with one or more plant cell wall degrading enzymes. Suitable enzymes are exemplified in the E: U: A: Nos. 3,519,570 and 3,533,139 patents. Suitable proteases are the subtilisins that are obtained from particular strains of B. subtilis and ß. licheniformis (subtilisin BPN and BPN ').

A suitable protease is obtained from a Bacillus strain, which has a maximum activity along the pH range of 8-12, developed and sold 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® by Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Maxacal manipulated protein) Gist-Brocades. The proteolytic enzymes also include modified bacterial serine proteases such as those described in European patent application Serial No. 87 303761.8, filed on April 28, 1987. (in particular pages 17,24 and 98), and which is called here "Protease B", and in the European patent application 199,404, Venegas, published on October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A" here. The one that is suitable here is called "Protease C", which is a variant of a Bacillus alkaline serine protease in which lysine replaces arginine in position 27, tyrosine replaces valine in position 104, serine replaces asparagine at position 123 and alanine replaces threonine at position 274. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published May 16, 1991. Jas is also included in the present invention genetically modified variants, particularly of protease C. A preferred protease called "Protease D" is a variant of carbonylhydrolase having an amino acid sequence that is not found in nature, and which is derived from a precursor carbonylhydrolase by substituting a different amino acid by a plurality of amino acid residues at a position in said carbonylhydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +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 the subtilisin from Bacillus amyloliquefaciens, as described in WO95 / 10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes", which has the EU serial number 08 / 322,677, filed October 13, 1994. Also suitable for the present invention are the proteases described in patent applications EP 251 446 and WO91 / 06637, and the BLAP® protease described in WO91 / 02792 and its variants described in WO95 / 23221. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other different enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & amp;; Gamble. A recombinant trypsin-like protease for detergents suitable in the present invention is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever. One or a mixture of proteolytic enzymes may be incorporated in the detergent compositions of the present invention, generally at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition. If present in the detergent compositions of the present invention, the lipolytic enzyme component is generally present at levels from 0.00005% up to 2% active enzyme by weight of the detergent composition, preferably from 0.001% to 1% by weight, more preferred from 0.0002% to 0.05% active enzyme by weight in the detergent composition. Suitable lipolytic enzymes for use in the present invention include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, such as those described in British Patent 1, 372, 034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas hisorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lysates include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipoliticum NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., Holland and lipases ex Pseudomonas gladioli. Particularly suitable lipases are lipases such as M1 Lipase ^ and Lipomax® (Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. Enzymes are also suitable (policies described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96700292 by Unilever. Cutinases are also suitable. 3.1.1.50] that can be considered as a special type of lipase, namely lipases that do not require interfacial activation.The addition of cutinases to detergent compositions has been described in e.g., WO-A-88/09367 (Genencor ), WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever) The LIPOLASE enzyme obtained from Humicola lanuginosa and commercially available from Novo (see also EPO 341, 947) is a preferred lipase for Another preferred lipase to be used in the present invention is lipolytic enzyme D96L which is a variant of the lipase obtained from Humicola lanuginosa, preferably the strain DSM 4106 of Humicola lanuginosa is used. variant of the lipolytic enzyme D96L is meant the lipase variant as described in the patent application WO 92/05249 in which the native lipase ex Humicola lanuginosa has the residue of aspartic acid (D) in position 96 changed to Leucine (L). In accordance with this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as D96L. To determine the activity of enzyme D96L, the LU test (analytical method, internal Novo Nordisk AF 95/6-GB 1991.02.07) can be used. A substrate for D) &L was prepared by emulsifying glycerin tributyrate (Merck) using gum arabic as an emulsifier. The lipase activity is tested using the pH stat method. The compositions may also contain one or a mixture of more than one amylase enzyme (a and / or β). WO94 / 02597, Novo Nordisk A / S published on February 3, 1994, describes cleaning compositions incorporating mutant amylases. See also WO95 / 10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in cleaning compositions include both α and β amylases. A-amylases are known in the art and include those described in the U.S.A. No. 5,003,257; EP 252,666; WO / 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and in the description of British Patent No. 1, 296,839 (Novo). Other suitable amylases are the stability amylases. improved described in WO94 / 18314, published on August 18, 1994 and WO96 / 05295, Genencor, published on February 22, 1996, as well as amylase variants having a further modification in the immediate parent available from Novo Nordisk A / S, described in WO 95/10603, published April 1995. Amylases described in EP 277 216, WO95 / 26397 and WO96 / 23873 (all by Novo Nordisk) are also suitable. Examples of commercial α-amylase 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-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® in a temperature range of 25 ° C to 55 ° C and a pH value in the range of 8 to 10, as measured by the Phadebas® α-amylase activity test. The variants of the above enzymes, described in WO96 / 23873 (Novo Nordisk), are suitable. Other preferred amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability, as well as a higher activity level are described in WO95 / 35382. The amylolytic enzymes, if present, are generally incorporated in the compositions at a level of 0.0001% to 2%, preferably 0.00018% to 0.06%, more preferred from 0.00024% to 0.048% pure enzyme by weight of the composition. The compositions of the invention can additionally incorporate one or more cellulase enzymes. Appropriate cellulases include both bacterial and fungal cellulases. Preferably, these will have an optimum pH of between 5 and 12, and an activity of more than 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are described in the U.S.A. No. 4,435,307, Barbesgoard et al, J61078384 and WO96 / 02653 which describe fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275; DE-OS-2,247,832 and WO95 / 26398. Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. Thermoidea, particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of approximately 50Kda, a isoelectric point of 5.5 and containing 415 amino acids, and a ~ 43kD endoglucanase obtained from Humicola insolens, DSM 1800, exhibiting cellulase activity, a preferred endoglucanase component having the amino acid sequence described in the PCT patent application No WO 91/17243 Cellulases also suitable are the cellulases EGlll of Trichoderma longibrachiatum described in WO94 / 21801, Genencor, published on September 29, 1994. Cellulases which are especially suitable are cellulases which have color care benefits. such cellulases are the cellulases described in European Patent Application No. 91202879.2, filed on November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO 91/17244 and WO91 / 21801. Other cellulases suitable for fabric care and / or cleaning properties are described in WO96 / 34092, WO96 / 17994 and WO95 / 24471. Peroxidase enzymes may also be incorporated into the compositions of the present invention. Peroxidases are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. These are used for "bleaching in solution", that is, to avoid the transfer of dyes or pigments removed from the substrates during the washing operations, to the other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in the PCT International Application WO89 / 099813, WO 89/09813 and in European Patent Application EP No. 91202882.6, filed November 6, 1991 and EP No. 96870013.8 , filed on February 20, 1996. The laccase enzyme is also suitable. Preferred improvers are fentiazine and phenoxasine, 10-phenothiazine propionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinpropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621). and substituted syringates (substituted C3-C5 alkylsalicylates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide. Said cellulases and / or peroxidases, if present, are normally incorporated in the composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Said additional enzymes, when present, are normally incorporated into the composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Additional enzymes can be added as separate individual ingredients (pellets, granulates, stabilized liquids, etc. containing an enzyme) or as mixtures of two or more enzymes (eg cogranulates).

Additional Organic Polymer Compound Additional organic polymeric compounds, not present in the photobleaching agent or integrated with the photobleaching component of the present invention, may be present in the compositions of the present invention. The term "organic polymeric compound" refers to any polymeric organic compound commonly used as dispersants, anti-redeposition agents and suspension of soils in detergent compositions, including any of the high molecular weight organic polymer compounds described as clay flocculating agents in the present invention. An organic polymeric compound as such is generally incorporated in the compositions at a level from 0.1% to 30%, preferably from 0.5% to 15%, most preferred from 1% to 10% by weight of the compositions. Suitable polymers are described in GB-A-1, 596,756. Examples of such salts are polyacrylic acid or polyacrylates of MW 1000-5000 and their copolymers with maleic anhydride, said copolymers having a molecular weight of 2,000 to 100,000, especially 40,000 to 80,000. Also suitable are polymaleate or polymaleic acid polymers and salts thereof. Polyamino compounds useful in the present invention include those obtained from aspartic acid including polyaspartic acid and such as those described in EP-A-305282, EP-A-305283 and EP-A-351629. Also suitable for incorporating into the compositions of the present invention are terpolymers containing selected monomeric units of maleic acid, acrylic acid, aspartic acid and vinyl alcohol or vinyl acetate, particularly those having an average molecular weight of 1,000 to 30,000 , preferably 3,000 to 10,000. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose and hydroxyethylcellulose. Additional and useful organic polymeric compounds are polyethylene glycols, particularly those with a molecular weight of 1000-10000, very particularly 2000 to 8000 and more preferably around 4000.

Cationic compounds for removal / anti-redeposition of dirt The compositions of the present invention may comprise water-soluble ethoxylated cationic amine compounds having removal / anti-redeposition properties of particulate dirt / clay soils. These cationic compounds are described in greater detail in EP-B-1 1 1965, EUA 4659802 and EUA 4664848. Particularly preferred compounds of these cationic compounds are the ethoxylated cationic monoamines, diamines or triamines. These compounds when present in the composition, generally are in an amount from 0.01% to 30% by weight, preferably from 0.05% to 10% by weight.

Foam suppressing system It may be preferred that the cleaning compositions require low foaming, and that therefore the incorporation of foam suppressors for the control thereof is desired. These are preferably in amounts of not more than 2.5% and more preferred in amounts not greater than 1.5% or even not greater than 0.5% by weight of the composition. The foam suppressor systems suitable for use in the present invention can comprise essentially any known antifoam compound, including, for example, silicone-based antifoam compounds and antifoam compounds based on 2-alkyl alkanol. The term antifoaming compound in the present invention refers to any compound or mixtures of compounds which act to depress the foaming or sudsing produced by a solution of a detergent composition, particularly when stirring that solution.

Polymeric dye transfer inhibiting agents The compositions of the present invention can also comprise from 0.01% up to 10%, preferably from 0.05% to 0.5% by weight of additional polymeric compounds, not contained in the photobleaching agent of the compositions of the invention, which act as dye transfer inhibiting agents. The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers can be cross-linked polymers.

. Optical brightener The compositions of the present invention also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful in the present invention include those having the structural formula: wherein R- ^ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula Rj is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is the disodium salt of acid 4,4, -bis [(4-anilino-6- ( N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and the disodium salt. This particular brightener species is marketed under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation. The Tinopal UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the above formula Rj is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [(4-an Flax-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenesulfonic acid. This particular brightener species is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula R ^ is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphino-s-triazin- 2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Polymeric agent for removing dirt The polymeric agents known to release soils, hereinafter "SRA", can optionally be used in the present compositions. If used, the SRAs will generally comprise from about 0.01% to 10.0%, typically about 0.1% a %, preferably from 0.2% to 3.0% by weight, of the compositions. Suitable SRAs include a sulphonated product of a substantially linear ester oligomer consisting of an oligomeric or polymeric ester base structure of terephthaloyl and oxyalkylenoxy repeating units and of sulfonated end portions obtained from allyl covalently attached to the base structure, for example as describes in the USA patent No. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other SRAs include polyesters of 1,2-propylene / polyoxyethylene terephthalate of non-ionic blocked ends of the U.S. patent. No. 4,71 1, 730, of December 8, 1987 to Gosselink and others, for example those produced by the transesterification / oligomerization of methyl ether of polyethylene glycol, DMT, PG and polyethylene glycol ("PEG"). Other examples of SRAs include: the oligomeric esters of anionic blocked ends partially and completely of the U.S. patent. No. 4,721, 580, of January 26, 1988 to Gosselink; the non-ionic blocked block polyester oligomeric compounds of the U.S.A. No. 4,702,857, dated October 27, 1987 to Gosselink; and the esters of terephthalate blocked at the anionic ends, especially sulfoaroyl of the patent E.U.A. No. 4,877,896 of October 31, 1989 to Maldonado Gosselink and others. SRAs also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see U.S. Pat. No. 3,959,230 to Hays of May 25, 1976 and the patent E.U.A. No. 3,893,929 to Basadur, July 8, 1975; cellulose derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see the patent E.U.A. No. 4,000,093, Dec. 28, 1976 to Nicol, et al., And methyl cellulosic esters having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity from about 80 to about 120 centipoises measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the commercial brands of the methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Other optional ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colorants and filler salts, including specks, with sodium sulfate being a preferred filler salt.

Detergent formulation with almost neutral wash pH Although cleaning compositions work well within a wide range of pH values (e.g., from about 5 to about 12), these are particularly appropriate when formulated to provide an almost wash pH neutral, that is, an initial pH from about 7.0 to about 10.5 at a concentration of from about 0.1 to about 2% by weight in water at 20 ° C. The formulations with almost neutral wash pH are better in terms of the stability of the enzyme and to prevent stains from fixing. In such formulations, the wash pH is preferably from about 7.0 to about 10.5, more preferred from about 8.0 to about 10.5, more preferred even from 8.0 to 9.0.

. Detergent formulations with preferred near-neutral wash pH are described in European Patent Application 83,200,668.6, filed May 16, 1983, J.H.M. Wertz and P: C: E: Goffinet. Such highly preferred compositions also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (for example less than about 20% by weight) of neutralizing agents, regulating agents, phase regulators, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, foam regulators, opacifiers, antioxidants, bactericides, dyes, perfumes and brighteners, such as those described in the EUA patent No. 4,285,841 to Barrat et al., Issued August 25, 1981 (incorporated by reference in the present invention).

Form of the compositions The bleaching compositions according to the invention and the cleaning compositions in the present invention can take a variety of physical forms including the granulated forms, in tablet form, in flakes, in tablets and in bars and in liquid form. The liquid forms can be aqueous or non-aqueous and can be in the form of a gel. The cleaning compositions can be pre-treatment compositions or they can be conventional laundry detergents. It may be preferred that the cleaning compositions are particularly granular detergent compositions, preferably so-called concentrated, adapted ones. to be added to a washing machine by means of a dispensing device placed in the drum of the machine with the load of dirty fabrics. Such granular detergent compositions or components thereof according to the present invention can be made through a variety of methods, including spray drying, dry mixing, extrusion, agglomeration and granulation. The bleaching compositions of the present invention can be added to the other components of the cleaning compositions as a dry aggregate material, mixed with the other components and agglomerated, exempt and / or spray dried. The bleaching agent and the photobleaching agent can be pre-mixed before being added to the other ingredients of the cleaning composition or bleaching composition.; The bleaching composition can also be pre-mixed with one or more of the additional ingredients of the cleaning composition, before the subsequent addition of the rest of the ingredients. The compositions may also be used in or in combination with additive whitening compositions, for example containing chlorine-based bleach. It could be preferred that the average particle size of the components of the granulated compositions according to the invention be such that no more than 15% of the particles are greater than 1.8 mm in diameter and no more than 15% of the particles are smaller of 0.25 mm in diameter. However, it may be preferred that the composition comprises particles with average particle size of at least 0.8 mm, preferably of at least 1.0 mm and more preferred from 1.0, or 1.5 to 2.5 mm. More preferred at least 95% of the particles will have such an average particle size. Such particles are preferably prepared by an extrusion process. The term "average particle size" as defined in the present invention is calculated by sieving a sample of the composition in a number of fractions (typically 5 fractions) in a series of sieves, preferably Tyler sieves. The weight of the fractions obtained in this way is plotted against the size of the opening of the screens. The average particle size is considered as the aperture size through which 50% by weight of the sample passes. The compact solid detergents can be manufactured using any suitable compaction process, such as tableting, block forming or extrusion, preferably tabletting.

Laundry Washing Method The machine laundry washing methods of the present invention typically comprise treating the laundry with an aqueous washing solution in a washing machine having dissolved or dispensed therein an effective amount of a washing detergent composition in the laundry. washing machine according to the invention. For an effective amount of the detergent composition it is tried to say from 10g to 300g of product dissolved or dispersed in a washing solution of a volume of 5 to 65 liters, which are typical doses of product and volumes of wash solution commonly used in conventional laundry washing methods. The dose is dependent on the particular conditions such as water hardness and dirtiness degree of the laundry. The detergent composition can be dispensed, for example, from a dispenser drawer of a washing machine or can be sprayed onto the laundry placed on the machine. In one aspect of use a dispensing device is used in the washing method. The preferred dispensing devices can be reused and are designed in such a way that the integrity of the container is preserved both in the dry state and during the wash cycle. Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents: GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP- A-0288345 and EP-A-0288346. An article by J. Bland, published in Manufacturing Chemist, November 1989, pages 41-46, also discloses especially preferred dispensing devices for use with granular laundry products which are of a type commonly known as the "granulette". Another dispensing device that is preferred for use with the compositions of this invention is described in PCT Patent Application No. WO94 / 1 1562. Especially preferred dispensing devices are described in European Patent Applications Nos. 0343069 and 0343070. alternatively, the dispensing device may be a flexible container, such as a bag or sack. The bag may have a fibrous structure coated with a waterproof protective material so as to retain the contents, such as that described in published European patent application No. 0018678. Alternatively, the bag may be formed of an insoluble synthetic polymeric material. in water provided with a seal or edge seal designed to be broken in the aqueous medium as described in published European patent applications Nos. 001 1500, 001 1501, 001 1502 and 001 1968. A convenient form of waterproof closure comprises a water soluble adhesive disposed along and sealing an end of a bag formed of a waterproof polymeric film such as polyethylene or polypropylene.

Dishwashing method in machine Any of the methods suitable for washing dishes in the machine or cleaning tableware, particularly dirty silverware, is envisaged. A machine dishwashing method which is preferred comprises treating dirty items selected from earthenware, glassware, hollow articles, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of an composition for washing dishes in machine according to the invention. For an effective amount of the machine dishwashing composition is tried to say from 8g to 60g of product dissolved or dispersed in a washing solution with a volume of 3 to 10 liters, which are typical product doses and volumes of solution of washing commonly used in conventional machine dishwashing methods.

Abbreviations used in the examples In the detergent compositions, the abbreviated identifications of the components have the following meanings: LAS: Linear sodium alkylbenzene sulfonate of C - ??. 3 TAS: Sodium alkyl sulfate CxyAS: Sodium alkyl sulphate of C- | xC-i and C46SAS: (2, 3) secondary sodium alkylsulfate of C -C 6 CxyEzS: C-] X-Cy sodium alkylsulfate condensed with z moles of ethylene oxide. CxyEz: Primary alcohol of C? XC- | and predominantly linear condensed with an average of z moles of ethylene oxide QAS: R2.N + (CH3) 2 (C2H4OH) with R2 = C12-C14 QAS 1: R2.N + (CH3 ) 2 (C2H4OH) with R2 = C8-Cn SADS. Cu-C22 sodium alkyldisulfate of the formula 2- (R). C4H7.-1, 4- (SO4") 2 wherein R = C? 0-C18 SADE2S C14-C22 sodium alkyldisulfate of the formula 2- (R) .C4H7.-1, 4- (SO4" ) 2 in which R = Cyclo-Ciß, condensed with z moles of ethylen oxide. MBAS C12-C18 alkylsulfate branched in the middle region of the chain that has an average of 1.5 groups of ethyl or methyl branching. MES Ester x-sulfomethyl ester of C-? 8 fatty acid. APA: Amidopropyl dimethylamine of C8-? 0 Soap: Sodium linear alkylcarboxylate derived from an 80/20 mixture of coconut and tallow fatty acids STS: Sodium toluene sulfonate CFAA: (coconut) alkyl (C- | 2-Ci4) -N- methyl glucamide TFAA: alkyl N-methyl glucamide of Ci sC ^ s TPKFA. Whole cut fatty acids of C12-C14 STPP: Sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Sodium aluminosilicate hydrate of the formula Na- | 2 (Al? 2Si? 2) i 2 27H2O, having a primary particle size in the range of 1 to 10 microns (weight expressed on an anhydrous basis) NaSKS-6: Crystalline layered silicate of formula d-Na2Si2? 5 Citric acid: Anhydrous citric acid. Borate: Sodium borate. Carbonate: Anhydrous sodium carbonate with a particle size between 200 μm and 900 μm. Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400 μm and 1200 μm. Silicate: Amorphous sodium silicate (Si? 2: Na2? = 2.0: 1) Sulfate: Anhydrous sodium sulfate Mg sulfate: Anhydrous magnesium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution of between 425 μm and 850 μm. MA / AA: Copolymer 1: 4 of maleic / acrylic acid, average molecular weight of about 70,000 MA / AA (1): Copolymer 4: 6 of maleic / acrylic acid, average molecular weight of about 10,000 AA: Sodium polyacrylate polymer of average molecular weight of 4,500 CMC: Sodium carboxymethylcellulose Cellulose ether: Cellulose methyl ether with a degree of polymerization of 650 available from Shin Etsu Chemicals. Protease: Proteolytic enzyme, which has 3.3% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Savinase. Protease I: Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO95 / 10591, sold by Genencor Int. Inc. Alcalase: Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A / S. Cellulase: Cellulolytic enzyme, which has 0.23% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Carezyme. Amylase: Amylolytic enzyme, which has 1.6% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Termamyl 120T. Amylase II Amylolytic enzyme, as described in PCT / EUA9703635. Lipase: Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the tradename Lipolase. Lipase (I): Lipolytic enzyme, which has 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Lipolase Ultra. Endolase: Enzyme endoglucanase, which has 1.5% by weight of active enzyme, sold by NOVO Industries A / S. PB4: Sodium perborate tetrahydrate of nominal formula NaBO2.3H2? .H2O2 PB1: Anhydrsodium perborate with nominal formula NaB? 2-H2? 2 Percarbonate: Anhydrsodium percarbonate of nominal formula 2Na2CO3.3H2O2 DOBS: Decanoiloxybenzenesulfonate in salt form sodium: DPDA: Diperoxidodecanoic acid. NOBS: Nonanoiloxybenzenesulfonate in the form of sodium salt.

NACA-OBS: (6-nonamidocaproyl) oxybenzenesiufonate. LOBS Dodecanoyloxybenzenesulfonate in the form of sodium salt.

DOBS Decanoiloxybenzenesulfonate in the form of sodium salt.

DOBA decanoyloxybenzoic acid TAED: Tetraacetylethylenediamine. DTPA: Diethylenetriaminpentaacetic acid. DTPMP: Diethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060.

EDDS: Ethylenediamine-N'-disuccinic acid, isomer [S, S] in the form of its sodium salt. Photo-bleach 1: Agent containing zinc phthalocyanine and polyvinylpyrro lidone of average molecular weight from 30,000 to 50,000, at a weight ratio of 1: 80 to 1: 120, encapsulated with starch and with a sugar derivative.

Photo-bleach 2: Agent comprising, at a weight ratio of 1: 80 to 1: 120, an aluminum phthalocyanine and a copolymer of polyvinylpyrrolidone and polyvinylimidazole, of average molecular weight of 30,000 to 50,000. Rinse aid 1: 4,4'-bis (2-sulphotrisyl) biphenyl disodium Rinse aid 2: 4,4'-bis (4-anilino-6-morpholin-1, 3,5-triazin-2-yl) disodium stilben-2,2'-disulfonate HEDP: 1,1-hydroxydanediphosphonic acid. PEGx: Polyethylene glycol with a molecular weight of x (typically 4,000) PEO: Polyethylene oxide, with an average molecular weight of 50,000. TEPAE: Tetraethylenepentamine-ethoxylate. PVI: Polyvinylimidazole, with an average molecular weight of 20,000. PVP: Polyvinylpyrrolidone polymer, with an average molecular weight of 60,000. PVNO: Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000. PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole, with an average molecular weight of 20,000 QEA: bis ((C2H5?) (C2H4?) N) (CH3) -N + -C6H12-N + - (CH3) bis ((C2H5?) - ( C2H4? N)), where n = 20 to 30 SRP 1: Anionically blocked polyesters at the ends SRP 2: Poly-1 (2-propylene) diethoxylated short block polymer. PEI: Polyethylenimine with an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen. Antifoam Silicone polydimethylsiloxane-based foam controller: with siloxane-oxyalkylene copolymer as the dispersing agent with a ratio of said controller to said dispersing agent from 10: 1 to 100: 1 Opacifying: Mixture of monostyrene-latex with aquebase , sold by BASF Aktiengesellschaft under the trade name Lytron 621. Wax: Paraffin wax. In the compositions described later in the present invention, the abbreviated identifications of the components have the following meanings: EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 The following liquid detergent is in accordance with the invention.

EXAMPLE 4 EXAMPLE 5 The following detergent formulations were prepared, in accordance with the invention: EXAMPLE 6 The following liquid detergent formulations are according to the invention (the levels are given in parts by weight). 10 i < fifteen twenty EXAMPLE 7 The following formulations are examples of compositions according to the invention, which may be in the form of granules or in the form of a tablet.

EXAMPLE 8 The following detergent compositions for bar laundry according to the invention were prepared (the levels are given in parts by weight).

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A bleaching composition comprising: (a) from

0. 5 ppm by weight of a photobleaching agent, comprising a polymeric component and a photobleaching component, integrated one with the other; (b) from 0.1% by weight of a bleaching agent that is capable of providing a peroxyacid compound.

2. A bleaching composition according to claim 1, further characterized in that the photobleaching agent can be obtained by a process comprising the steps of: a) forming a molten material or a solution, comprising a photobleaching compound and a polymeric compound; b) in an additional step, form and separate the photobleaching agent.

3. A bleaching composition according to claim 2, further characterized in that the photobleaching agent comprises a polymeric compound with a number average molecular weight of 500 to 1,000,000, comprising polymerized monomer units of which at least 50% of the units, preferably at least 95% comprise a dipolar, aprotic group, and wherein the weight ratio of the polymeric compound to the photobleaching compound in the photobleaching agent is from 1: 1 to 1000: 1, preferably 20 : 1 to 100: 1.

4. A bleaching composition according to claim 2, further characterized in that the polymeric compound comprises one or more monomer units that are selected from the group 5 which consists of N-vinylpyrrolidone, N-vinylacetamide, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine and 4-vinylpyridine N-oxide.

5. A bleaching composition according to any of claims 2 to 4, further characterized in that the photobleaching agent is a metallo-phthalocyanine, preferably metal or phthalocyanine zinc or aluminum, preferably does not contain a solubilizing substituent group.

6. A bleaching composition or component thereof according to any of the preceding claims, further characterized in that the photobleaching agent comprises from 15 90% to 99.9% by weight of the agent, preferably from 92% to 99% by weight, of the polymer component and from 0.1% to 10% by weight of the agent, preferably from 1% to 8% by weight, of the photobleaching component.

7.- A whitening composition or component thereof 20 according to any of the preceding claims, further characterized in that the photobleaching agent comprises at least one precursor which is a precursor compound of alkylperoxy acid substituted with amide of the formula: R - C - N - R2 - C - L R1 - N - C - R2 - C - L II I? II I c IJ II O R5 O R5 O O where L can be essentially any outgoing group, R1 is a aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is a group alkylene.arlene and alkarylene containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms such that R1 and R5 contain no more than 18 carbon atoms in total, preferably (6-octanamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and the highly preferred (6-nonanamido-caproyl) oxybenzenesulfonate and mixtures thereof.

8. A bleaching composition according to any of the preceding claims, further characterized in that the photobleaching agent comprises at least one precursor which is an N, N, N1, N1-tetra acetylated alkylenediamine in which the alkylene group contains 1. to 6 carbon atoms, preferably tetra-acetylethylene diamine

9. A bleaching composition according to any of the preceding claims comprising a hydrogen peroxide, preferably a percarbonate salt or a perborate salt and preferably a chelating agent.

10. A cleaning composition comprising a bleaching composition according to any of the preceding claims, which is preferably a cleaning composition for washing dishes or clothes.