CN1268159A - Detergent compositions comprising a specific oxygenase - Google Patents

Abstract

This invention relates to cleaning compositions comprising protein-based oxidases, including laundry, dishwashing, hard surface cleaners, and oral/dental cleaning compositions, which effectively remove protein-based stains and/or dirt, such as protein-containing food stains/dirt and everyday body grime, and provide disinfection to treated surfaces. Furthermore, when formulated into laundry detergent compositions, the cleaning compositions of this invention provide fabrics with realistic cleaning and whitening properties.

Description

Cleaning compositions containing specific oxygenases

Field of Invention

The present invention relates to cleaning compositions comprising an oxygenase based on a protein substrate, including laundry, dishwashing, hard surface cleaner, oral/dental cleaning compositions.

Background of the Invention

The performance of a laundry product used in a washing or cleaning process is judged by a number of factors, including the ability to remove soil, and the ability to inhibit redeposition of soil, or breakdown products of soil on items being washed.

Many stains of consumer concern contain protein components and are difficult to remove from surfaces being washed. Food stains originating from everyday products such as milk and eggs or occurring in the food or drink area are particularly difficult to remove.

Furthermore, the complex nature of everyday "body" soils commonly found on pillows, T-shirts, collars and socks makes continuous thorough cleaning challenging for detergents. These soils are difficult to remove completely and often the residue builds up on the fabric causing dullness and yellowing. Additionally, human fluid stains, such as blood and menstrual fluid, are often difficult to remove effectively from soiled articles, especially when the stain has aged. Everyday body soiling is also found on surfaces of sanitary and kitchen equipment such as bathtubs, toilet bowls and containers.

The items may be fabrics, hard surfaces, containers such as plastic containers, glass containers or ceramics, teeth and oral cavity.

Traditionally, proteases and/or high levels of bleaching compounds, optionally together with bleach precursors and/or bleach boosters, have been added to cleaning compositions. Bleach is a precursor compound to hydrogen peroxide formed during the washing process. Perborate and percarbonate are the most important examples of such hydrogen peroxide precursors.

In view of the above, it is evident that there is a continuing need to provide cleaning compositions having excellent cleaning performance. It is therefore an object of the present invention to provide a cleaning composition which is effective in cleaning protein based stains and/or soils such as proteinaceous food stains/soils and everyday body soils. It is a further object of the present invention to provide a cleaning composition which provides true-to-life cleaning and whitening of fabrics.

The above objects are achieved by formulating cleaning compositions comprising oxygenases based on protein substrates.

It has been surprisingly found that enzymatic bleaching systems based on oxygenases directed against protein substrates provide cleaning compositions with bleach-like benefits in terms of an unexpectedly wide range of properties, such as smudge cleaning, whiteness maintenance and stain removal. It has also been found that the cleaning compositions of the present invention provide a sanitizing effect on the surface being treated.

It has also been found that the performance of the cleaning compositions of the present invention is improved by adding another enzymatic bleach system, a conventional activated bleach system, a metal catalyst based bleach system and/or another detergent enzyme, especially a protease.

In a preferred embodiment, the present invention is directed to laundry compositions comprising protein substrate based oxygenases which also provide true-to-life cleaning and whitening of fabrics. In a second embodiment, the invention relates to a dishwashing or household cleaning composition comprising a protein substrate-based oxygenase, and in a third embodiment, the invention relates to an oral cavity comprising a protein substrate-based oxygenase. /Dental care composition.

The use of protein substrate-based oxygenases in cleaning compositions for extensive removal of protein-based stains/soils such as protein-containing food stains/soils and everyday body soils and for sanitizing has not previously been recognized. It has also not been recognized that when protein substrate based oxygenases are used in laundry detergent compositions, there is robust and significant cleaning and whitening performance on fabrics.

Summary of Invention

The present invention relates to cleaning compositions comprising oxygenases based on protein substrates, including laundry, dishwashing, hard surface cleaners, oral/dental cleaning compositions, which are effective in cleaning protein-based stains/soils such as protein-containing Food stains/dirt and/or everyday body soiling and provide sanitization to treated surfaces.

In addition, the cleaning compositions of the present invention provide substantial cleaning and whitening performance to fabrics when formulated as laundry detergent compositions.

Detailed description of the invention

An essential component of the cleaning compositions of the present invention are oxygenases based on protein substrates. Preferably, the enzyme is also characterized as an iron-sulfur or heme oxygenase and/or a heavy metal-associated oxygenase.

All oxygen enzymes of the present invention will pass the following stain removal performance test on standard test fabrics and compared with reference products without oxygen enzymes under the same conditions.

Small scale experiments were carried out in a bottle detergency tester Washtec ROACHES with a 500ml stainless steel bottle. This small scale experiment was performed at 30-40°C with a total wash time of 30 minutes. The experiments were carried out using a 1% solution of the detergent described in Example 10, Composition 5. Dissolve the detergent in 400ml of water with a total hardness of 2.0-3.0mmol Ca2+/L. The pH of the 1% detergent solution was adjusted to pH 8-9 with acid (citric acid) or base (NaOH). Each bottle also contains 15 steel balls for better stirring. The standard soiling test fabric was supplied by wfk-Testgewebe Gmbh (Christenfeld, 10-Brueggen, Germany). Each experiment was repeated at least twice. The size of the filth is 3cm x 4cm. The standard experimental fabric with protein substrate was wfk F10 EM (cotton fabric stained with egg yolk+milk). The enzyme content in this small scale experiment was 1 mg enzyme protein/L. When necessary, the amount of cofactor is calculated from the ratio of enzyme to cofactor known in the literature.

For the reference treatment, no enzymes or cofactors were added to the solution. In this experimental treatment, pre-weighed amounts of enzyme and cofactors were added to the solution, and in the second experimental treatment, only cofactors were added to the solution. Afterwards, the experimental tracer was added to the bottle. Fix the bottle detergency tester at the required temperature. Before starting the experiment, preheat the bottle detergency tester to an appropriate temperature so that the experiment is performed at a constant temperature.

Seal the cylinder and place in a preheated cylinder detergency tester. Time the cycle and start the experiment. After 30 minutes, the experiment was stopped and the cylinders were removed from the apparatus and opened. The standard test fabric was taken out and rinsed 3 times in cold city water (hardness 2-3 mmolCa2+/L). After rinsing, the tracer is tumble dried in a normal household dryer until completely dry.

The stain removal performance of the enzymes is analyzed by an expert panel by visual grading or preferably by an instrumental stain removal assay, for example the Spectraflash 500 device available from Datacolor. The Spectraflash 500 orientation used for this experiment was: no specular excluded, aperture small and U.V filter FL40 (= UV cut filter at 400nm) and calibration was relatively standard white and black.

The results expressed as color difference (Cielab) dE between the experimental and reference treatments were calculated. Experiment 1 included a protein substrate-based oxygenase of the invention, and Experiment 2 included a monophenol monooxygenase of EC 1.14.18.1. The enzyme of the invention (Experiment 1) had a dE of 1 or greater relative to the monophenol monooxygenase (Experiment 2) tested under the same conditions.

It has been found that the cleaning compositions of the present invention are effective in cleaning protein-based stains and/or soils such as proteinaceous food stains/soils and everyday body soils and, especially when formulated as laundry detergent compositions, leave fabrics Realistic cleaning and whitening. In fact, it has been surprisingly found that oxygenases based on protein substrates are effective on a wider range of proteinaceous substances than conventional detergent proteases, and also on proteinaceous compounds which cannot be decomposed by conventional detergent proteases.

Without wishing to be bound by theory, it is believed that the enzyme's performance is achieved by decycling, decarboxylation and side chain decomposition reactions of amino acids, peptides and proteins derived from the protein fraction of glycoproteins and lipoproteins present in the stain/soil . These reactions are achieved by catalyzing the direct insertion of molecular oxygen into the amino acid structure.

In addition, the cleaning compositions of the present invention provide a sanitizing effect on the surface being treated.

Disinfection includes all positive effects that result from inhibiting or reducing the mobility of microorganisms on fabrics and other surfaces, such as inhibiting the spread of bad odors and inhibiting the growth of bacteria/mold. For example, it inhibits the development of bad odors on stored and worn fabrics, on stored containers, especially plastic kitchenware, and in toilets. In particular, the compositions according to the invention inhibit or at least reduce the growth of bacteria and/or mold on damp fabrics awaiting further washing operations, thereby inhibiting the formation of bad odors. Furthermore, the growth of bacteria and/or mold on hard surfaces such as tiles and their silicone joints, sanitary fixtures will be inhibited.

The possible disinfecting action of the cleaning compositions according to the invention can be enhanced by the addition of chemical disinfectants such as triclosan and/or hexemidine. Suitable chemical disinfectants are described in Parfums Cosmétiques Actualités No. 125, November 1995, 51-4.

The disinfection effect of the cleaning composition of the present invention can be by such as in Tuber.Lung.Dis.1994 August; 75 (4): 286-90; J.Clin.Microbiol.1994 May; 32 (5): 1261-7 and the minimum inhibitory concentration (MIC) described in J.Clin.Microbiol.1992 October; 30(10):2692-7.

Without wishing to be bound by theory, it is believed that "everyday body soil" contains sebum secreted by the human body. Sebum is believed to contain large amounts of saturated and unsaturated fatty acids, sterols and sterol esters (Physiology and Pathology of the Skin, Vol. 9, A. Jarret, (1986)). Fragmentation of the substrate and formation of ionizable groups or hydrophilic substituents by the action of oxygenases based on protein substrates makes the enzymatic reaction products more soluble and thus easier to remove from soiled items.

Suitable oxygenases based on protein substrates for the purposes of the present invention are listed below: EC Number Designated Name 1.13.11.11 Tryptophan 2,3-Dioxygenase 1.13.11.20 Cysteine Dioxygenase 1.13.11.26 Peptide- Tryptophan 2,3-dioxygenase 1.13.11.29 Carboxy-y-pyronealanine salt synthase 1.13.11.30 Carboxy-a-pyronealanine salt synthase 1.13.12.1 Arginine 2- Monooxygenase 1.13.12.2 Lysine 2-monooxygenase 1.13.12.3 Tryptophan 2-monooxygenase 1.13.12.9 Phenylalanine 2-monooxygenase 1.13.12.10 Lysine 6-monooxygenase 1.13 .99.3 Tryptophan 2'-Dioxygenase 1.14.11.1 γ-Butyrolactam Dioxygenase 1.14.11.2 Collagen Solubilizing Proline 2-Oxoglutarate 4-Dioxygenase 1.14.11.4 Collagen Lysin amino acid 2-oxoglutarate 5-dioxygenase 1.14.11.7 collagenolytic proline 2-oxoglutarate 3-dioxygenase 1.14.11.8 trimethyllysine 2-oxopenta Dioxygenase 1.14.11.16 Peptide-aspartate β-dioxygenase 1.14.16.1 Phenylalanine 4-monooxygenase 1.14.16.2 Tyrosine 3-monooxygenase 1.14.16.4 Tryptophan 5-Monooxygenase 1.14.17.3 Peptidylglycine monooxygenase

Some of the polyphenol/heterocyclic substrate-based oxygenases of the invention require the presence of cofactors. In this case, the cleaning composition according to the invention also comprises cofactors such as ascorbic acid, oxoglutarate, flavin mononucleotide (FMN), flavin adenine dinucleotide (FAD), nicotinamide adenine Dinucleotide (phosphate) (NAD(P)H). When included in the present invention, cofactors are generally 10:1-1:10, preferably 5:1-1:8, more preferably 1:2-1:5 by weight ratio of pure oxygenase to the included cofactors. In the present invention.

Oxygenase based on protein substrates is incorporated in the cleaning composition of the present invention in an amount by weight of the composition, preferably 0.0001%-2%, more preferably 0.001%-0.5%, most preferably 0.002%-0.1% pure enzyme.

A preferred protein substrate-based oxygenase for a particular use is an alkaline protein substrate-based oxygenase, i.e. has an enzyme activity at pH 7-12 of at least 10%, preferably at least 25%, of its maximum activity, More preferably at least 40% enzyme. More preferred oxygenases based on protein substrates are enzymes that have their maximal activity at pH 7-12.

Enzymes homologous to the protein substrate-based oxygenases of the invention are also contemplated. The term "homologous" is meant to refer to a polypeptide encoded by DNA that has been treated under certain conditions (e.g. presoaked in 5×SSC and at ~40° C. in 20% formamide, 5×Denhardt’s solution) , 50 mM sodium phosphate, pH 6.8 and 50 μg denatured sonicated bovine thymus DNA for 1 hour, and then in the same solution supplemented with 100 μM ATP, hybridized at ~40 ° C for 18 hours) The same probe hybridizes to the DNA of the protein substrate oxygenase. The term is meant to include enzyme sequence derivatives of oxygenases based on protein substrates by the addition of one or more amino acid residues at either or both of the C- and N-termini of their original sequence , replacing one or more amino acid residues at one or more positions in its original sequence, deleting at one or both ends of its original amino acid sequence or at one or more positions within its original sequence One or more amino acid residues, or one or more amino acid residues inserted at one or more positions in its original sequence.

The aforementioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. The source may also be mesophilic or extremophilic (psychrophilic, cold-eating, thermophilic, barophilic, basophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes can be used. Currently, it is common practice to modify wild-type enzymes through protein/genetic engineering techniques in order to optimize their performance in the cleaning compositions of the present invention. For example, the variant can be made such that the enzyme has increased compatibility with components normally included in such compositions. In addition, the variant can be tailored such that the optimal pH, bleach or chelator stability, catalytic activity, etc. of the enzyme variant is tailored to a particular cleaning application.

In particular, attention should be focused on oxidation-sensitive amino acids for bleach stability and surface charge for surfactant compatibility. The isoelectric point of this enzyme can be improved by substituting certain charged amino acids, for example, increasing the isoelectric point can help improve the compatibility with anionic surfactants. Enzyme stability can also be enhanced by creating, for example, additional salt bridges and strengthening calcium binding sites to increase chelator stability. detergent components

The cleaning compositions of the present invention may also contain additional detergent components. The exact nature of these additional components and their incorporation levels will depend upon the physical form of the composition and the type of cleaning operation for which it is used.

The cleaning compositions according to the invention preferably also comprise another enzymatic bleach system, a conventional activated bleach system, a metal catalyst based bleach system and/or another detergent enzyme.

In a preferred embodiment, the invention relates to laundry and/or fabric care compositions comprising a protein substrate based oxygenase (Examples 1-18). In a second embodiment, the invention relates to dishwashing or household cleaning compositions, including sanitizing compositions (Examples 19-28), and in a third embodiment, the invention relates to oral/dental care compositions (Example 29-31).

The cleaning compositions according to the invention may be in the form of liquids, creams, gels, bars, tablets, sprays, foams, powders or granules. Granular compositions may also be in "compact" form and liquid compositions may also be in "concentrated" form.

The compositions of the present invention can be formulated, for example, as hand and machine dishwashing compositions, hand or machine laundry detergent compositions, which include laundry additive compositions and compositions suitable for soaking/pretreating soiled fabrics, rinse added Fabric softener compositions, and compositions for use in conventional household hard surface cleaning operations. Compositions containing such protein substrate-based oxygenases can also be formulated as oral/dental care compositions.

When formulated as a composition for use in a hand dishwashing process, the compositions of the present invention preferably contain a surfactant and preferably other detergent components selected from the group consisting of organic polymeric compounds, suds boosters, metal ions of group II, solvents, Hydrotropes and auxiliary enzymes.

When formulated as compositions suitable for use in washing machine washing methods, the compositions of the present invention preferably contain both components, a surfactant and a builder compound, and additionally one or more detergent components, the detergent The components are preferably selected from organic polymeric compounds, bleaching agents, auxiliary enzymes, suds suppressors, dispersants, lime soap dispersants, soil suspending and antiredeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents as additional detergent ingredients.

Such compositions containing protein substrate based oxygenases, when formulated as laundry detergent compositions, provide cleaning, stain removal, whiteness maintenance, softness, bright appearance, dye transfer inhibition and disinfection to fabrics.

The compositions of the present invention are also useful as detergent additive products. Such additive products are used to supplement or boost the performance of conventional detergent compositions.

If desired, the laundry detergent compositions according to the invention have a density measured at 20°C of from 400 to 1200 g/l, preferably from 600 to 950 g/l of composition.

The "compact" form of the compositions of the present invention is best responded by density and, in terms of composition, by the amount of inorganic filler salt. Inorganic filler salts are conventional components of powdered detergent compositions. In conventional detergent compositions filler salts are present in significant amounts, typically 17-35% by weight of the total composition.

In compact compositions, the content of filler salts does not exceed 15%, preferably does not exceed 10%, most preferably does not exceed 5% by weight of the composition.

Inorganic filler salts, for example in the compositions of the present invention are meant to be selected from alkali metal and alkaline earth metal sulfates and chlorides.

A preferred filler salt is sodium sulfate.

The liquid detergent compositions according to the invention may also be in "concentrated form", in which case the liquid detergent compositions according to the invention will contain lower amounts of water than conventional liquid detergents.

Typically concentrated liquid detergents will preferably have a water content of less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition. Regular Detergent Enzyme

The cleaning compositions of the present invention contain, in addition to a protein substrate based oxygen enzyme, one or more enzymes which provide cleaning performance, fabric care and/or sanitizing action. It has been found that the specific oxygenase in combination with a detergent enzyme improves the cleaning of protein based stains and/or soils such as proteinaceous food stains/soils and everyday body soils and when formulated into laundry compositions, makes fabrics There is improved realistic cleaning and whitening.

Preferably, the cleaning compositions of the invention comprise proteases. In fact, it has been surprisingly found that oxygenases based on protein substrates are effective on a wider range of proteinaceous substances than conventional detergent proteases and on proteinaceous compounds which are not broken down by conventional detergent proteases. A combination of protein substrate-based oxygenase and protease has synergistic performance for removal of protein-based stains/soils and everyday body soils.

Said enzymes include those selected from the group consisting of cellulase, hemicellulase, peroxidase, protease, gluco-amylase, amylase, xylanase, lipase, phospholipase, esterase , cutinase, pectinase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase , β-glucanase, arabinosidase, hyaluronase, chondroitinase, laccase and mixtures thereof.

A preferred combination is a cleaning composition comprising an enzyme cocktail of conventionally applicable enzymes such as proteases, amylases, lipases, cutinases and/or cellulases in combination with one or more plant cell wall degrading enzymes.

Suitable proteases are subtilisins, which are obtained from special strains of Bacillus subtilis and Bacillus licheniformis (subtilisins BPN and BPN'). A suitable protease is obtained from the Bacillus strain, which has maximum activity in the pH range of 8-12, developed by Novo Industries A/S, Denmark and sold as ESPERASE ^(R) , hereinafter "Novo". The preparation of this and similar enzymes is described in British Patent Specification GB1243784 to Novo. Other suitable proteases include ALCALASE® ^{, DURAZYM®} and ^SAVINASE® from Novo, and ^MAXATASE® , ^MAXACAL® , PROPERASE® ^{and MAXAPEM®} (Maxacal for Protein Engineering) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases such as those described in European Patent Application Serial No. 87303761.8 filed April 28, 1987 (particularly pages 17, 24 and 98), which are referred to herein as "Protease B", and those described in European Patent Application 199404, Venegas, published October 29, 1986, are modified bacterial serine proteolytic enzymes, referred to herein as "Protease A". Suitable are the proteases referred to herein as "Protease C", which are variants of alkaline serine proteases obtained from Bacillus in which lysine is substituted for arginine at position 27 and tyrosine is substituted for valine at position 104 acid, serine for asparagine at position 123, and alanine for threonine at position 274. Protease C is described in EP90915958:4 which corresponds to WO91/06637 published May 16,1991. Genetically modified variants, especially variants of Protease C are also included in the present invention.

A preferred protease known as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a carbonyl hydrolase precursor according to the Bacillus amyloliquefaciens subtilisin , at the position corresponding to +76 in the carbonyl hydrolase, it is also preferred to bind correspondingly to the group selected from +99, +101, +103, +104, +107, +123, +27, +105, + 109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or at one or more amino acid residue positions of +274, substituting different amino acids for multiple amino acid residues at said positions, as in WO95/10591 and C. Ghosh et al. filed on October 13, 1994 described in U.S. Patent Application Serial No. 08/322,677 entitled "Bleaching Compositions Containing Proteases." Also suitable are variants having different proteolytic activity, stability, substrate specificity, pH range and/or performance characteristics compared to the carbonyl hydrolase precursor, the amino acid sequence of which variant is determined by the carbonyl hydrolysis Enzyme precursors are obtained. As previously stated, the protease is designed to have trypsin-like specificity and is also preferably bleach-stable. The carbonyl hydrolase precursor may be a naturally occurring carbonyl hydrolase or a recombinant hydrolase. Specifically, the carbonyl hydrolase variant has an amino acid sequence not found in nature, which is obtained by substituting different amino acids for various amino acid residues in the carbonyl hydrolase precursor. Multiple amino acid residues of this precursor enzyme correspond to position +210 and bind one or more residues at the following positions: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 , and +222, where the numbered positions correspond to the equivalent amino acid residues of naturally occurring subtilisins or other carbonyl hydrolases or subtilisins such as Bacillus lentus from B. amyloliquefaciens.

Carbonyl hydrolase variants of proteases suitable for use in the compositions of the invention include substitution of the amino acid residue at position +210 in combination with one or more additional modifications. While any combination of amino acid substitutions listed above may be used, preferred variant proteases for use in the present invention include substitutions, deletions or insertions of amino acid residues at the following combined positions: 210/156; 210/166; 210/76; 210 /103; 210/104; 210/217; 210/156/166; 210/156/217; 210/166/217; 210/76/156; /156/166; 210/76/156/217; 210/76/166/217; 210/76/103/156; 210/76/103/166; 210/76/103/217; 210/76/104 /156; 210/76/104/166; 210/76/104/217; 210/76/103/104/156; 210/76/103/104/166; 210/76/103/104/217; 210 /76/103/104/156/166; 210/76/103/104/156/217; 210/76/103/104/166/217; and/or 210/76/103/104/156/166/ 217; 210/76/103/104/166/222; 210/67/76/103/104/166/222; 210/67/76/103/104/166/218/222. The most preferred variant enzymes for use in the present invention comprise substitutions, deletions or insertions of amino acid residues at the following combined residue positions of B. lentus subtilisin: 210/156; 210/166; 210/217; 210/156/ 166; 210/156/217; 210/166/217; 210/76/156/166; /104/156/166 are most preferred.

Variant DNA sequences encoding such carbonyl hydrolase or subtilisin variants are derived from precursor DNA sequences encoding naturally occurring or recombinant precursor enzymes. The variant DNA sequence is obtained by modifying the precursor DNA sequence. This modification is encoded by the precursor DNA sequence corresponding to +210, +33, +62, +67, +76, +100, + 101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, Substitution of one or more specific amino acid residues at positions +217, +218, and +222, or any combination thereof. Although the modified amino acid residues identified here are determined according to the numbering applicable to Bacillus amyloliquefaciens (which has become a routine method for determining residue positions in all subtilisins), the preferred precursors applicable to the present invention The DNA sequence is that of Bacillus lentus. These recombinant DNA sequences encode carbonyl hydrolase variants having novel amino acid sequences and, generally, having at least one property that is completely different from the same property of the enzyme encoded by the carbonyl hydrolase precursor DNA sequence. Such properties include proteolytic activity, substrate specificity, stability, variable pH range and/or enhanced performance characteristics.

Proteases useful in the present invention include substitutions for any nineteen naturally occurring L-amino acids at the indicated amino acid residue positions. This substitution can be made in any precursor subtilisin (prokaryotic, eukaryotic, mammalian, etc.). Throughout this application, various amino acids are designated by the common one- and three-letter codes. This code is determined in Dale, M.W. (1989), Molecular Genetics of Bacteria, John Wiley & Son, Ltd., Appendix B.

Preferably, substitutions made at each defined amino acid residue position include, but are not limited to, substitutions including I, V, L and A at positions +210, substitutions at +33, +62, +67, +76, +100 , +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, + D or E substitutions at 215, +217, and +218, including D, H, E, G, F, K, P, and N substitutions at position 76; including Q, T, D, E, Y at position 103 , K, G, R, and S substitutions and substitutions including S, Y, I, L, M, A, W, D, T, G, and V at position 104; and substitutions including S, C, A at position 222 replace. Specific preferred amino acids to be substituted at each position are indicated in Table 1 below. Although specific amino acids are given in Table 1, it is understood that any amino acid may be substituted at the indicated residue.

Table 1

Amino acid residue Preferred amino acid to be substituted/inserted

+210 I, V, L, A

+33, +62, +100, +101, +107, D, E

+128, +129, +130, +135, +156,

+158, +164, +166, +167, +170,

+209, +215, +217 and +218

+76 D, H

+103 A, Q, T, D, E, Y, K, G, R

+104 I, Y, S, L, A, T, G

+222 S, C, A

A comparison of the preferred amino acid residues identified herein for substitution with the preferred substitutions at each position is given in Table II.

Table II

+210 +156 +166 +217 +76 +103 +104 Bacillus amyloliquefaciens (wild P E G Y N Q Q Y growth type) Bacillus lentus (wild P S S S L N S V type) the most preferred replacement I E /D E/D E/D D A I/Y

Also suitable for the present invention are the proteases described in patent applications EP251446 and WO91/06637, the protease BLAP ^(R) described in WO91/02792 and their variants described in WO95/23221.

See also the high pH protease from Bacillus NCIMB 40338 described in WO9318140A to Novo. Enzyme detergents containing a protease, one or more other enzymes, and a reversible protease inhibitor are described in WO9203529A to Novo. When desired, proteases with reduced adsorption and increased hydrolysis can be obtained as described in WO9507791 to Procter & Gamble. Recombinant trypsin-like proteases suitable for the detergents of the present invention are described in WO9425583 to Novo. Other suitable proteases are described in EP516200 to Unilever.

Preferred proteases for the purposes of the present invention are serine proteases, more preferably bacterial serine proteases obtained from Bacillus, preferably Bacillus subtilis and/or Bacillus licheniformis.

The amount of proteolytic enzyme incorporated in the detergent composition of the present invention is 0.0001%-2%, preferably 0.001%-0.2%, more preferably 0.005%-0.1% pure enzyme by weight of the composition.

Cellulases useful in the present invention include bacterial and fungal cellulases. Preferably they have an optimum pH range of 5-12 and an activity above 50 CEVU (Cellulose Viscosity Units). Suitable cellulases are disclosed in U.S. Patent No. 4,435,307 to Barbesgoard et al., J61078384 and WO96/02653, which disclose molds produced by Humicola insolens, Trichoderma, Rhizopus and Sporothrix, respectively. Cellulase. EP739982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275; DE-OS-2247832 and WO95/26398.

Examples of such cellulases are cellulases produced by strains of Humicola insolens (Humicola griseus var. thermoidea), in particular Humicola strain DSM1800.

Other suitable cellulases are cellulases derived from Humicola insolens, having a molecular weight of about 50 KDa, an isoelectric point of 5.5 and containing 415 amino acids, and cellulases derived from Humicola insolens, DSM1800 having Active ~43 kD endoglucanase; preferred endoglucanase components have the amino acid sequence disclosed in PCT application WO91/17243. Also suitable cellulases are the EGIII cellulases obtained from Trichoderma longibrachiatum and described in WO 94/21801, Genencor, published September 29,1994. Particularly suitable cellulases are cellulases with a color care effect. Examples of such cellulases are those described in European Patent Application No. 91202879.2, filed November 6,1991. Carezyme and Celluzyme (Novo Nordisk A/S) are particularly suitable. See also WO91/17244 and WO91/21801. Other suitable cellulases having fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471.

The cellulase is generally incorporated in the detergent composition in an amount of 0.0001%-2% active enzyme by weight of the detergent composition.

Other preferred enzymes which may be included in the detergent compositions of the present invention include lipases. Suitable lipases for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1372034. Suitable lipases include those produced by the microorganism Pseudomonas fluorescens IAM 1057 that exhibit a positive immunological cross-reaction with antibodies to the lipase. This lipase is commercially available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, a lipase obtained from Chromobacter viscosum, e.g., Chromobacter viscosum variant lipolyticum NRRLB 3673, obtained from Toyo Jozo Corporation, Tagata, Japan; available from U.S. Biochemical Company, U.S.A. and the lipase obtained from Chromobacterium viscosus and from Pseudomonas gladioli obtained from Disoynth Company of the Netherlands. Particularly suitable lipases are lipases such as M1 LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and LipolaseUltraR (Novo), which have been found to be very effective when used in combination with the compositions of the invention. Also suitable are the lipolytic enzymes described by Novo Nordisk in EP258068, WO92/05249 and WO95/22615 and by Unilever in WO94/03578, WO95/35381 and WO96/00292.

Also suitable enzymes are cutinases [EC 3.1.1.50], which are considered to be a special class of lipases called lipases that do not require interfacial activation. The incorporation of cutinases in detergent compositions has been described eg in WO-A-88/09367 (Genencor); WO90/09446 (Plant Genetic System) and WO94/14963 and WO94/14964 (Unilever).

Lipase and/or cutinase are generally incorporated in detergent compositions in an amount of 0.0001% to 2% active enzyme by weight of the detergent composition.

Amylases (alpha and/or beta) may be included for removal of carbohydrate based stains. WO/94/02597, Novo Nordisk A/S, published February 3, 1994, describes cleaning compositions incorporating mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1995. Other known amylases for use in cleaning compositions include alpha- and beta-amylases. α-Amylases are known in the art and include those disclosed in US5003257; EP252666; WO91/00353; FR 2676456; EP285123; Other suitable amylases are the stability-enhanced amylases described in WO 94/18314, published 18.08.1994 and WO 96/05295, Genencor, published 22.02.1996; and in 04.95. Amylase variants commercially available from Novo Nordisk A/S with additional modifications to the immediate parent disclosed in published WO 95/10603. Also suitable are the amylases described in EP277216, WO95/26397 and WO96/23873 (all filed by Novo Nordisk).

Examples of commercial a-amylase products are Purafect Ox ^Am® and Termamyl® from Genencor, ^Ban® , ^Fungamyl® and ^Duramyl® , all available from Novo Nordisk A/ ^S Denmark. WO95/26397 describes other suitable amylases: α-amylases characterized by specific activities at temperatures from 25°C to 55°C and pH values in the range 8-10 as determined by the ^Phadebas® α-amylase activity assay At least 25% greater than the specific activity of ^Termamyl® . Suitable are variants of the above enzymes described in WO96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to activity levels and thermostability combined with higher activity levels are described in WO95/35382.

The amount of amylolytic enzyme incorporated in the detergent composition of the present invention is 0.0001%-2%, preferably 0.00018%-0.06%, more preferably 0.00024%-0.048% pure enzyme by weight of the composition.

The aforementioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. The source may also be mesophilic or extremophilic (psychrophilic, cold-eating, thermophilic, barophilic, basophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes can be used. Also included by definition are mutants of the native enzyme. Mutants can be obtained, for example, by protein and/or genetic engineering, chemical and/or physical modification of native enzymes. It is common practice to express the enzyme by a host organism in which the genetic material responsible for the production of the enzyme is cloned.

The enzymes are typically incorporated into detergent compositions at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. The enzyme can be added as a separate single component (pellets, granules, stabilized liquid, etc. containing one enzyme) or as a mixture of two or more enzymes (eg composite granules).

Other suitable detergent ingredients that may be added are enzyme oxidation scavengers, which are described in co-pending European patent application 92870018.6, filed January 31,1992. An example of such an enzyme oxidation scavenger is ethoxylated tetraethylenepolyamine.

Various enzyme materials and methods of incorporating them into synthetic detergent compositions are also disclosed in WO 9307263A and WO 9307260A of Genencor International, WO 8908694A of Novo, and U.S. Patent No. 3,553,139 issued January 5, 1971 to McCarty et al. middle. Some enzymes are also disclosed in US Pat. No. 4,101,457, Place et al., issued July 18, 1978, and US Pat. Enzyme materials useful in liquid detergent formulations and methods of their incorporation into such formulations are disclosed in US Patent 4,261,868, Hora et al., issued April 14,1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in US Patent 3,600,319, Gedge et al., issued August 17, 1971, EP 199,405, and EP 200,586, Venegas, October 29, 1986. Enzyme stabilization systems are also described eg in US Pat. No. 3,519,570. A useful Bacillus AC13 producing proteases, xylanases and cellulases is described in WO 9401532A to Novo. bleach

Preferred additional optional detergent ingredients that can be included in the cleaning compositions of the present invention include conventional activated, other enzymatic and/or metal catalyst based bleach systems. It has been found that the specific oxygenase in combination with another bleaching system improves the cleaning of protein based stains and/or soils such as proteinaceous food stains/soils and everyday body soils and when formulated into laundry compositions, enables Fabrics have improved realistic cleaning and whitening while being color safe.

The bleach component for use in the present invention can be any bleaching agent suitable for use in cleaning compositions, including oxygen bleaches and others known in the art. Bleaching agents suitable for use in the present invention may be activated or non-activated bleaching agents.

Bleaching agents are eg hydrogen peroxide, PB1, PB4 and percarbonates with a particle size of 400-800 microns. These bleach components may include one or more oxygen bleaches, and depending on the bleach selected, one or more bleach activators. When present, oxygen bleaching compounds are generally present at levels of from about 1% to about 25%.

其中R₁是C₇-C₁₃直链或支链的饱和或不饱和烷基，R₂是C₁-C₈直链或支链的饱和或不饱和烷基和R₃是C₁-C₄直链或支链的饱和或不饱和烷基。Hydrogen peroxide releasing agents can be combined with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5-trimethylhexanoloxy Benzenesulfonate (ISONOBS, described in EP 120,591), pentaacetylglucose (PAG) or phenolsulfonate of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO94/28106) combined Used together, these bleach activators perhydrolyze to form peracids as the active bleaching species, resulting in improved bleaching results. Also suitable activators are acylated citrates, such as those disclosed in co-pending European Patent Application No. 91870207.7, and asymmetric acyclic imide bleach activators having the formula, as disclosed in Procter & Gamble In pending U.S. Patent Application Serial Nos. 60/022786 (filed July 30, 1996) and 60/028122 (filed October 15, 1996):

Wherein R ₁ is C ₇ -C ₁₃ straight chain or branched saturated or unsaturated alkyl, R ₂ is C ₁ -C ₈ straight chain or branched saturated or unsaturated alkyl and R ₃ is C ₁ -C ₄ Straight-chain or branched saturated or unsaturated alkyl.

One class of oxygen bleaches which can be used includes percarboxylic acid bleaches and their salts. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, magnesium 4-nonylamino-4-oxoperoxybutyrate and diperoxydodecane di Magnesium acid. These bleaching agents are disclosed in US Patent 4,483,781, US Patent Application 740,446, European Patent Application 0133354 and US Patent 4,412,934. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in US Patent No. 4,634,551.

Another class of bleaches that can be used includes halogen bleaches. Examples of hypohalite bleaches include, for example, trichloroisocyanuric acid, sodium and potassium dichloroisocyanurates and N-chloro and N-bromoalkanesulfonamides. Such substances are generally added in an amount of 0.5-10% by weight of the finished product, preferably 1-5% by weight.

Suitable bleaching agents, including peroxyacids, and bleaching systems comprising bleach activators and peroxygen bleaching compounds for use in the detergent compositions of the present invention are described in our co-pending applications USSN 08/136,626, PCT/US95/07823 , WO95/27772, WO95/27773, WO95/27774 and WO95/27775.

Hydrogen peroxide can also be provided by adding an enzymatic system (ie enzyme and corresponding substrate) capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. This enzymatic system is disclosed in EP patent application 912022655.6 filed on October 9, 1991.

Peroxidases are used in combination with oxygen, a source of hydrogen peroxide such as percarbonate, perborate, persulfate, hydrogen peroxide, etc., and a bleach booster. They are used to "bleach the solution", ie to inhibit the migration of dyes or pigments that have been released from a substrate during the wash to other substrates in the wash solution. Peroxidases are known in the art herein and include, for example, horseradish peroxidase, ligninase, and haloperoxidase, such as chloro- or bromo-peroxidase. Detergent compositions containing peroxidase are disclosed, for example, in PCT International Application WO89/099813, WO89/09813 and in European Patent Application No. 91202882.6 filed on November 6, 1991 and in EP96870013.8. Also suitable are laccases.

Builders generally comprise from 0.1% to 5% by weight of the total composition. Preferred synergists are substituted phenothiazines and phenoxazines, 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO94/12621) and substituted syringyl esters (C3-C5 substituted alkyl syringyl esters) and phenols. Sodium percarbonate or sodium perborate are preferred sources of hydrogen peroxide.

The peroxidase is generally incorporated in the detergent composition in an amount of 0.0001%-2% active enzyme by weight of the detergent composition.

Metal-containing catalysts for use in bleach compositions include cobalt-containing catalysts such as cobalt(III) pentaamine acetate and manganese-containing catalysts, for example in EPA549271, EPA549272; EPA458397; US5246621; EPA458398; EPA458397; US5194416 and US5114611 those described. Bleaching compositions containing peroxygen compounds, manganese-containing bleach catalysts and chelating agents are described in patent application 94870206.3.

Preferred metal-containing catalysts for the purposes of the present invention are transition metal complexes of polycyclic rigid ligands. The phrase "macrocyclic rigid ligand" is sometimes abbreviated "MRL" in the discussion below. The amount used is a catalytically effective amount, suitably about 1 ppb or more, such as up to about 99.9%, more typically about 0.001 ppm or more, preferably about 0.05 ppm to 500 ppm (where "ppb" means parts per billion parts by weight, "ppm" means parts per million by weight).

Suitable transition metals such as manganese are exemplified below. "Polycyclic" means that the MRL is both macrocyclic and polycyclic. "Polycyclic" means at least two rings. The term "rigid" as used herein includes "having a superstructure" and "crosslinking". "Rigid" is defined as the flexibility transition is limited: see D.H Bush. Chemical Reviews (1993), 93, 847-860, which is incorporated herein by reference. More specifically, "rigid" as used herein means that the MRL must be more identical (with the same ring size and type and number of atoms in the main ring) but lacks the superstructure present in the MRL (especially the connecting moiety, or preferably the cross-linking moiety) (the "parent macrocycle") is measurably more rigid. In determining the comparative rigidity of macrocycles with and without superstructure, the skilled artisan uses the free form (not the metal-bound form) of the macrocycle. It is known that stiffness can be used to compare macrocycles; suitable methods for determining, measuring or comparing stiffness include computational methods (see e.g. Zimmer,. Chemical Reviews (Chemical Reviews) (1995), 95(38), 2629-2648 or Hancock et al. Inorganic Chimica Acta, (1989), 164, 73-84). Determining whether one macrocycle is more rigid than another is usually performed by simply preparing a molecular model, so it is generally not necessary to know the absolute structural energies or to calculate them precisely. An optimal comparative determination of the rigidity of one macrocycle relative to another can be made using inexpensive personal calculator-based calculations, such as ALCHEMY III, commercially available from Tripos Associates. Tripos also has more expensive software that allows not only comparative but also absolute measurements; alternatively, SHAPES is available (see Zimmer cited above). A notable observation of the present invention is that it is optimal for the purposes of the present invention when the parent macrocycle has significant flexibility compared to the cross-linked form. Thus, unexpectedly, it is preferred to use parent macrocycles containing at least 4 electron-donating atoms, such as cyclam derivatives, and to crosslink them, but not to initiate crosslinking from a more rigid parent macrocycle. Another observation is that cross-linked macrocycles are significantly better than otherwise bridged macrocycles.

The preferred MRLs of the present invention are a special class of cross-linked ultrarigid ligands. "Crosslinking" is non-limitatively described in 1.11 below. In 1.11, the crosslink is _{the -CH2CH2-} moiety that bridges ^N1 and ^N8 in this example structure. By contrast, "same side" bridges, such as one bridged if added across ^N1 and ^N12 in 1.11, do not sufficiently constitute a "crosslink" and are therefore not preferred.

Suitable metals in rigid ligand complexes include Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I) , Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III) , Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV) , W(V), W(VI), Pd(II), Ru(II), Ru(III) and Ru(IV). Preferred transition metals in the transition metal bleach catalysts of the present invention include manganese, iron and chromium. Preferred oxidation states include (II) and (III) oxidation states. Manganese(II) complexes in low-spin and high-spin configurations are included. It should be noted that eg low spin Mn(II) complexes are rather rare in all coordination chemistries. The symbols (II) or (III) indicate a coordinating transition metal having the desired oxidation state; the coordinating metal atom is not a free ion or one in which only water is used as a ligand.

Generally, a "ligand" as used in the present invention is any moiety capable of directly covalently binding a metal ion. Ligands can be charged or neutral, and range widely, including simple monovalent donors such as chlorine, or simple amines, which form a dative bond and have one point of attachment to the metal; oxygen or ethylene , which can form three-membered rings with metals and thus can be said to have two possible points of attachment; larger segments such as ethylenediamine or azamacrocycles, which form the greatest number of single bonds with one or more metals, This is permitted by the number of available sites present on the metal and the number of lone pairs or bonding sites that the free ligands have. Many ligands can form bonds other than simple electron-donating bonds and can have multiple points of attachment.

The ligands useful in the present invention can be divided into several groups: MRLs, preferably cross-linked macrocycles (in useful transition metal complexes there is preferably one MRL, but there can be more, for example 2, but in preferred not in mononuclear transition metal complexes); other optional ligands, which are generally different from the MRL (generally there are 0-4, preferably 1-3 such ligands); and A ligand to which a portion of a metal is temporarily attached, the latter generally involving water, hydroxide, oxygen, or peroxide. The third group of ligands is not necessary to define a metal bleach catalyst as a stable, independent, well-characterized compound. A ligand bound to a metal by means of an electron-donating atom, each of which has at least one lone pair of electrons suitable for donating to the metal, the ligand having a donor capacity or a possible degree of coordination at least equal to that of the electron-donating atom number. Typically, donor capabilities may be fully or only partially implementable.

In general, the MRLs of the present invention can be viewed as the result of additional structural rigidity imposed on a specially selected "parent macrocycle".

More generally, the MRLs (and corresponding transition metal catalysts) of the present invention suitably comprise:

(a) at least one major macrocycle containing 4 or more heteroatoms; and

(b) Covalently linked non-metallic superstructures capable of enhancing the rigidity of the macrocycle, preferably selected from:

(i) bridging superstructures, such as connecting parts;

(ii) cross-linked superstructures, such as cross-linked linkages; and

(iii) mixtures thereof.

The term "superstructure" as used herein is as defined in Busch et al., see eg Busch in Chemical Reviews.

其中n是整数，例如为2-8，优选低于6，一般为2-4，或其中m和n是约1-8的整数，更优选1-3；Z是N或CH；T是匹配的取代基，例如H、烷基、三烷基铵、卤素、硝基、磺酸根等。在1.10中的芳环可被饱和环代替，其中连接环的Z中的原子可含N、O、S或C。The preferred superstructure here not only enhances the rigidity of the parent macrocycle, but also facilitates the folding of the macrocycle, allowing it to coordinate with the metal at the gap. Suitable superstructures can obviously be simple, e.g. any connection moieties such as those described in 1.9 and 1.10 below can be used:

Wherein n is an integer, such as 2-8, preferably lower than 6, generally 2-4, or wherein m and n are integers of about 1-8, more preferably 1-3; Z is N or CH; T is a matching substituent, such as H, alkyl, trialkylammonium, halogen, nitro, sulfonate, etc. . The aromatic rings in 1.10 may be replaced by saturated rings, where the atoms in Z connecting the rings may contain N, O, S or C.

Without intending to be bound by theory, it is believed that the preorganization built in the MRLs herein, results in additional kinetic and/or thermodynamic stability of their metal complexes due to, compared to the free parent macrocycle without superstructure , resulting in either or both of the properties of topological constraints and increased rigidity (loss of flexibility). The MRLs defined herein and their preferred cross-linked subfamily, which may be referred to as "ultrarigid", combine two sources of fixed pre-organization. In preferred MRLs of the invention, the linking moiety and the parent macrocycle combine to form a ligand with a substantial degree of "folding", generally greater than that found in many well-known superstructure ligands where the superstructure is linked at On a large plane, it is often an unsaturated macrocycle. See eg: D.H Busch. Chemical Reviews (1993), 93, 847-880. In addition, the preferred MRLs of the present invention have a number of specific properties, including (1) they are characterized by very high proton affinity, as in so-called "proton sponges"; (2) they tend to bind slowly with multivalent transition metals The reaction, when combined with the above (1), makes it difficult to synthesize their complexes with certain hydrolyzable metal ions in hydroxylic solvents; (3) when they coordinate with the transition metal atoms identified herein, this MRL leads to The complexes have excellent kinetic stability such that the metal ion dissociates only extremely slowly under conditions that disrupt complexes with common ligands; and (4) these complexes have excellent thermodynamic stability; but The unusual kinetics of MRL dissociation from transition metals can invalidate conventional equilibrium assays to determine this property.

In one aspect of the invention, MRLs include those comprising:

(i) contains 4 or more electron-donating atoms (preferably at least 3, more preferably at least 4 of these electron-donating atoms) separated from each other by at least 1, preferably 2 or 3 non-electron-donating atoms by covalent bonds 2-5 (preferably 3-4, more preferably 4) of these electron-donating atoms are coordinated to the same transition metal in the complex; and

(ii) linking moieties, preferably cross-linked chains, which covalently link at least 2 (preferably non-adjacent) electron-donating atoms in the organic macrocycle, said covalently-linked (preferably non-adjacent) electron-donating atoms being A bridgehead electron-donating atom that coordinates to the same transition metal in the complex, and wherein the linking moiety (preferably a cross-linked chain) comprises 2 to about 10 atoms (preferably the cross-linked chain is selected from 2, 3 or 4 non-donating atoms, and 4-6 non-donating atoms with additional electron-donating atoms).

其是根据本发明的MRL，其是高度优选的交联的甲基取代的(所有氮原子是叔氮)cyclam的衍生物。正规地讲，使用推广的von Baeyer系统，该配位体的名称为5，12-二甲基-1，5，8，12-四氮杂双环[6.6.2]十六烷。参见“有机化合物IUPAC命名法介绍指南1993”，(A Guide to IUPACNomenclature of Organic Compounds：Recommendations 1993)，R.Panico，W.H.Powell和J-C Richer(编辑)，Blackwell科技出版社，波士顿，1993；特别参见R-2.4.2.1部分。根据常规术语，N1和N8是“桥头原子”；如本文定义的，更具体地是“桥头供电子原子”，因为它们具有能够给予金属的孤对电子。N1通过性质不同的饱和碳链2，3，4和14，13与两个非桥头供电子原子N5和N12连接，并通过“连接部分”a，b，这里它们是2个碳原子的饱和碳链，与桥头供电子原子N8相连。N8通过性质不同的链6，7和9，10，11与两个非桥头供电子原子N5和N12连接。链a.b是本文定义的“连接部分”，是特殊的，优选的类型，称为“交联”部分。上述配位体的“大环”，或“主要的环”(IUPAC)包括所有4个供电子原子和链2，3，4；6，7；9，10，11和13，14，但不包括a，b。该配位体常规地是双环。短的桥键或“连接部分”a，b是如本文定义的“交联”部分，a，b平分该大环。Suitable MRLs are also illustrated, without limitation, by the following compounds:

It is an MRL according to the present invention, which is a derivative of a highly preferred cross-linked methyl-substituted (all nitrogen atoms are tertiary nitrogen) cyclam. Formally, using the generalized von Baeyer system, the ligand is named 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane. See "A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993", (A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993), R. Panico, WH Powell and JC Richer (eds.), Blackwell Scientific Press, Boston, 1993; see especially R- Section 2.4.2.1. According to conventional terminology, N1 and N8 are "bridgehead atoms"; as defined herein, more specifically "bridgehead donating atoms" because they have a lone pair of electrons capable of donating to the metal. N1 is connected to two non-bridgehead electron-donating atoms N5 and N12 through saturated carbon chains 2, 3, 4 and 14, 13 of different nature, and through "connecting moieties" a, b, here they are saturated carbons of 2 carbon atoms chain, connected to the bridgehead electron-donating atom N8. N8 is connected to two non-bridgehead donating atoms N5 and N12 through chains 6, 7 and 9, 10, 11 with different properties. Chains ab are "linking moieties" as defined herein and are of a special, preferred type known as "crosslinking" moieties. The "macrocycle", or "principal ring" (IUPAC) of the above ligands includes all 4 electron-donating atoms and chains 2,3,4; 6,7; 9,10,11 and 13,14, but not Including a, b. The ligand is conventionally bicyclic. Short bridges or "linking moieties" a, b are "crosslinking" moieties as defined herein, a, b bisecting the macrocycle.

The MRLs of the invention are of course not limited to synthesis from any prefabricated macrocycle plus prefabricated "rigid" or "conformation-improved" elements; rather, various synthetic methods can be used, such as templated synthesis methods. See, eg, the synthesis described by Bush et al. in "Heterocyclic compounds: Aza-crown macrocycles", J.S. Bradshaw et al.

Transition metal bleach catalysts useful in the compositions of the present invention may generally include known compounds meeting the definition of the present invention, and more preferably a number of novel compounds specifically designated for laundry or cleaning applications of the present invention, illustrated without limitation by: -5,12-Dimethyl-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecane manganese(II); Dichloro-4,10-dimethyl-1,4, 7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II); dihydrate-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]deca Hexadecanemanganese(II) hexafluorophosphate; Hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(III) hexafluorophosphate Salt; dihydrate-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecyl manganese(II) hexafluorophosphate; dihydrate-5,12-di Methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese(II) tetrafluoroborate; dihydrate-4,10-dimethyl-1,4,7, 10-Tetraazabicyclo[5.5.2]tetradecanemanganese(II) tetrafluoroborate; Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6. 2] Cetyl manganese (III) hexafluorophosphate; dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo [6.6. ); Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane manganese(II); Dichloro-5-n-butyl-12-methyl Base-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanyl manganese(II); Dichloro-5-n-octyl-12-methyl-1,5,8,12- Azabicyclo[6.6.2]hexadecane manganese(II); Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II); Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecyliron(II); Dichloro-4,10-dimethyl Base-1,4,7,10-tetraazabicyclo[5.5.2]tetradecyliron(II); Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] Hexadecanecopper(II); Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanecopper(II); Chloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanecobalt(II); dichloro-4,10-dimethyl-1,4, 7,10-tetraazabicyclo[5.5.2]tetradecanecobalt(II); Dichloro-5,12-dimethyl-4-phenyl-1,5,8,12-tetraazabicyclo[ 6.6.2] Hexadecanemanganese (II); Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese ( II); Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecane manganese(II); Dichloro -4,10-Dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II); Dichloro-5,12-di Methyl-2,11-diphenyl-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecane manganese(II); dichloro-4,10-dimethyl-4, 9-Diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II); Dichloro-2,4,5,9,11,12-hexamethyl- 1,5,8,12,-tetraazabicyclo[6.6.2]hexadecane manganese(II); dichloro-2,3,5,9,10,12-hexamethyl-1,5,8 ,12,-tetraazabicyclo[6.6.2]hexadecane manganese(II); dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8, 12,-tetraazabicyclo[6.6.2]hexadecane manganese(II); dichloro-2,2,4,5,9,11,11,12-octamethyl-1,5,8,12 ,-tetraazabicyclo[6.6.2]hexadecane manganese(II); dichloro-3,3,5,10,10,12-hexamethyl-1,5,8,12,-tetraaza Bicyclo[6.6.2]hexadecane manganese(II); dichloro-3,5,10,12-tetramethyl-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecane Manganese(II); Dichloro-3-butyl-5,10,12-trimethyl-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecanemanganese(II); Chloro-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecane manganese(II); dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecyl Alkanemanganese(II); Dichloro-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecyliron(II); Dichloro-1,4,7,10-tetraazabicyclo [5.5.2] Tetradecyliron(II); Hydrated-chloro-2-(2-hydroxyphenyl)-5,12-dimethyl-1,5,8,12,-tetraazabicyclo[6.6 .2] Cetyl manganese(II); hydrate-chloro-10-(2-hydroxybenzyl)-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2] Tetradecylmanganese(II); Chloro-2-(2-hydroxybenzyl)-5-methyl-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecanylmanganese(II) ; Chloro-10-(2-hydroxybenzyl)-4-methyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecanemanganese(II); Chloro-5-methyl- 12-(2-pyridylmethyl)-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecanyl manganese(II) chloride; Chloro-4-methyl-10-(2- Pyridylmethyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetradecylmanganese(II) chloride; dichloro-5-(2-sulfato)dodecyl-12 -Methyl-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecylmanganese(III); hydrated-chloro 5-(2-sulfato)dodecyl-12-methan Base-1,5,8,12,-tetraazabicyclo[6.6.2]hexadecanyl manganese(II); hydrated-chloro 5-(3-sulfonylpropyl)-12-methyl-1,5 ,8,12,-Tetraazabicyclo[6.6.2]hexadecane manganese(II); Dichloro-5-(trimethylaminopropyl)dodecyl-12-methyl-1,5, 8,12,-tetraazabicyclo[6.6.2]hexadecane manganese(III) chloride; dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo[ 8.5.2] Heptadecanyl manganese(II); Dichloro-14,20-dimethyl-1,10,14,20-tetraazatricyclo[8.6.6]doco-3(8) , 4,6-triene manganese (II); dichloro-4,11-dimethyl-1,4,7,11-tetraazabicyclo[6.5.2]pentadecane manganese (II); dichloro -5,12-dimethyl-1,5,8,12-tetraazabicyclo[7.6.2]heptadecanyl manganese (II); dichloro-5,13-dimethyl-1,5,9 , 13-tetraazabicyclo[7.7.2]heptadecanyl manganese(II); dichloro-3,10-bis(butylcarboxy)-5,12-dimethyl-1,5,8,12- Tetraazabicyclo[6.6.2]hexadecane manganese(II); Dihydrate-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6. 2] Hexadecanemanganese(II); Chloro-20-methyl-1,9,20,24,25-pentaazatetracyclo[7.7.7.1 ^{3,7,1 11,15} .]Pentapentacarbon -3,5,7(24),11,13,15(25)-hexaene manganese(II) hexafluorophosphate; trifluoromethanesulfonyl-20-methyl-1,9,20,24,25 -pentaazatetracyclo[7.7.7.1 ^{3,7,1 11,15} .]pentaca-3,5,7(24),11,13,15(25)-hexaene manganese(II) tri Fluoromethanesulfonate; Trifluoromethanesulfonyl-20-methyl-1,9,20,24,25-pentaazatetracyclo[7.7.7.1 ^{3,7,1 11,15} .]pentacyl -3,5,7(24),11,13,15(25)-hexaenyliron(II) triflate; Chloro-5,12,17-trimethyl-1,5,8, 12,17-Pentaazabicyclo[6.6.5]nonadecanemanganese(II) hexafluorophosphate; Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaaza Bicyclo[5.5.5]heptadecanemanganese(II) hexafluorophosphate; Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]deca Nonadecanemanganese(II) chloride; Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecanemanganese(II) chloride.

Those skilled in the art will benefit further if some terms have additional definitions and descriptions. A "macrocycle" as used herein is a ring formed by the covalent linkage of 4 or more electron donating atoms (i.e. heteroatoms such as nitrogen or oxygen) to the carbon chains linking them, in which any macrocycle as defined herein must Contains a total of at least 10 atoms, preferably at least 12 atoms. The MRLs herein may contain more than 1 ring of any kind per ligand, but at least 1 macrocycle must be recognizable. Additionally, in preferred embodiments, no two heteroatoms are directly linked. Preferred transition metal bleach catalysts are those wherein the MRL comprises an organic macrocycle (main ring) containing at least 10-20 atoms, preferably about 12-18, more preferably about 12-20, most preferably 12-16 atoms.

An "electron donating atom" herein is a heteroatom, such as nitrogen, oxygen, phosphorus or sulfur, which, when incorporated into a ligand, also has at least one lone pair of electrons suitable for forming a donor-acceptor bond with a metal. Preferred transition metal bleach catalysts are those wherein the electron donating atoms in the organic macrocycles of the crosslinked MRL are selected from N, O, S and P, preferably N and O, most preferably both N. Also preferred are crosslinked MRLs comprising 4 or 5 electron donating atoms all coordinated to the same transition metal. The most preferred transition metal bleach catalysts are those wherein the crosslinked MRL comprises 4 nitrogen electron donating atoms all coordinated to the same transition metal, and wherein the crosslinked MRL comprises 5 nitrogen atoms all coordinated to the same transition metal those catalysts.

A "non-electron-donating atom" for an MRL herein is most commonly carbon, although many atom types can be included, especially in optional exocyclic substituents of macrocycles (such as the "side group" moieties described below), which are both Not the electron-donating atoms necessary to form metal catalysts, nor carbon. Thus, in its broadest sense, the term "non-donating atom" refers to any atom which is not necessary to form a donor bond with the metal of the catalyst. Examples of such atoms may include heteroatoms such as sulfur incorporated in non-coordinating sulfo groups, phosphorus incorporated in phosphonium salt moieties, phosphorus incorporated in oxide P(V), non-transition metals, and the like. In certain preferred embodiments, all non-donating atoms are carbon.

The transition metal complexes of MRL can be prepared by any suitable method. Two such preparations are illustrated below:

(a)方法1Synthesis of [Mn(Bcyclam)Cl ₂ ]

(a) Method 1

"Bcyclam" (5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane) was developed by GR Weisman et al., in J. American Chemical Society (J.Amer.Chem .Soc.), (1990), 112,8604 described in the synthetic method to prepare. Bcyclam (1.00 g, 3.93 mmol) was dissolved in anhydrous _CH3CN (35 ml, distilled from _CaH2 ). The solution was then evacuated at 15mm pressure until _CH3CN started to boil. The flask was then connected to atmospheric Ar. This degassing step was repeated 4 times. Under an Ar atmosphere, Mn(pyridine) ₂ Cl ₂ (1.12 g, 3.93 mmol) synthesized according to the method in HT Witteveen et al. ). The cloudy reaction solution slowly started to turn black. After stirring overnight at room temperature, the reaction solution turned dark brown with suspended fine particles. The reaction solution was filtered through 0.2 μ filter paper. The filtrate was light brown. The filtrate was evaporated to dryness using a rotary evaporator. After drying at 0.05 mm at room temperature overnight, 1.35 g of off-white solid was collected, 90% yield. Elemental analysis: theoretical value of [Mn(Bcyclam)Cl ₂ ], %Mn, 14.45; %C, 44.22; %H, 7.95; MnC ₁₄ H ₃₀ N ₄ Cl ₂ , MW=380.26. Experimental values: %Mn, 14.98; %C, 44.48; %H, 7.86; Ion spray mass spectrometry analysis showed a larger peak corresponding to [Mn(Bcyclam)(formate)] ⁺ at 354 mu. (b) Method II

Freshly distilled Bcyclam (25.00 g, 0.0984 mol), prepared as above, was dissolved in anhydrous _CH3CN (900 ml, distilled from _CaH2 ). The solution was then evacuated at 15 mm pressure until _CH3CN started to boil. The flask was then connected to atmospheric Ar. This degassing step was repeated 4 times. Under Ar atmosphere, _MnCl2 (11.25 g, 0.0894 mol) was added. The cloudy reaction solution immediately turned black. After stirring at reflux for 4 hours, the reaction solution became dark brown with suspended fine particles. The reaction solution was filtered through 0.2 μ filter paper under dry conditions. The filtrate was light brown. The filtrate was evaporated to dryness using a rotary evaporator. The resulting tan solid was dried overnight at 0.05 mm at room temperature. The solid was suspended in toluene (100ml) and heated to reflux. The toluene was decanted and the procedure repeated with an additional 100 ml of toluene. Equilibrium toluene was removed using a rotary evaporator. After drying overnight at room temperature at 0.05 mm, 31.75 g of light blue solid product was collected, yield 93.5%. Elemental analysis: [Mn(Bcyclam)Cl ₂ ] theoretical value, %Mn, 14.45; _% C, 44.22; %H, _7.95 ; %N, _14.73 ; %Cl, _18.65 ; 380.26. Experimental values: %Mn, 14.69; %C, 44.69; %H, 7.99; %N, 14.78; %Cl, 18.90 (Karl Fischer water, 0.68%). Ion spray mass spectrometry showed a larger peak at 354 mu corresponding to [Mn(Bcyclam)(formate)] ⁺ .

Bleaching agents other than oxygen bleaching agents are also well known in the art and may be used in the present invention. A particularly preferred class of non-oxygen bleaches includes photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyanines. These substances can deposit on the substrate during washing. In the presence of oxygen, the sulfonated zinc phthalocyanine is activated when exposed to light, such as when clothes are hung out to dry in the sun, and the substrate is bleached as a result. A preferred zinc phthalocyanine and photoactivated bleaching process is described in US Patent No. 4,033,718. Detergent compositions typically contain from about 0.025% to about 1.25% by weight of the sulfonated zinc phthalocyanine. Surfactant system

The cleaning compositions of the present invention generally comprise a surfactant system, wherein the surfactant can be selected from non-ionic and/or anionic and/or cationic and/or amphoteric and/or zwitterionic and/or semi-polar surface active agent.

Surfactants are generally present at levels of from 0.1% to 60% by weight, more preferably incorporated at levels of from 1% to 35% by weight of the cleaning compositions of the present invention, most preferably from 1% to 30%.

Surfactants are preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzymes in these compositions.

Preferred surfactant systems for use according to the invention comprise one or more nonionic and/or anionic surfactants described herein as surfactants.

Polyoxyethylene, polyoxypropylene and polyoxybutylene condensation products of alkylphenols are suitable for use as nonionic surfactants in the surfactant system of the present invention, preferably polyoxyethylene condensates. These compounds include the condensation products of alkylphenols with alkylene oxides having an alkyl group having from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in a linear or branched configuration. In a preferred embodiment, the oxyethylene is present in an amount equal to about 2 to about 25 moles, more preferably about 3 to about 15 moles, per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ^™ CO-630, sold by GAF Corporation; and Triton ^™ X-45, X-114, X-100 and X-102, all of which are Sold by Rohm & Haas. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

The condensation products of primary and secondary fatty alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant in the nonionic surfactant system of the present invention. The alkyl chains of the fatty alcohols can be straight or branched, primary or secondary, and generally contain from about 8 to about 22 carbon atoms. Preferred are condensation products of alcohols with from about 2 to about 10 moles of ethylene oxide, per mole of alcohol, wherein the alkyl group of the alcohol contains from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms . From about 2 to about 7 moles of oxyethylene, most preferably from 2 to 5 moles of oxyethylene, are present in the condensation product per mole of alcohol. Commercially available nonionic surfactants of this type include Tergitol ^TM 15-S-9 (a condensation product of C ₁₁ -C ₁₅ linear alcohols with 9 moles of ethylene oxide), Tergitol ^TM 24-L- 6 NMW (condensation product of C ₁₂ -C ₁₄ primary alcohols with 6 moles of ethylene oxide, and has a narrow molecular weight distribution), both sold by UnionCarbide Corporation; and Neodol ^TM 45-9 sold by Shell Chemical Company ( Condensation product of C ₁₄ -C ₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol ^TM 23-3 (condensation product of C ₁₂ -C ₁₃ linear alcohol with 3.0 moles of ethylene oxide), Neodol ^TM 45- 7 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol with 7 moles of ethylene oxide), Neodol ^TM 45-5 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol with 5 moles of ethylene oxide); by Procter & Gamble Company Kyro ^™ EOB (condensation product of C ₁₃ -C ₁₅ alcohols with 9 moles of ethylene oxide); and Genapol LA030 or LA 050 (C ₁₂ -C ₁₄ alcohols with 3 or 5 moles of ethylene oxide) sold by Hoechst condensation products). The preferred HLB range for these products is 8-11, most preferably 8-10.

Also suitable for use as the nonionic surfactant in the surfactant system of the present invention are the alkyl polysaccharides disclosed in U.S. Patent No. 4,565,647 issued to Llenado on January 21, 1986, which have from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, a hydrophobic group and a polysaccharide such as a polyglycoside hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably about 1.3 to about 2.7 sugar units. Any reducing sugar containing 5 or 6 carbon atoms can be used, for example glucose, galactose and galactosyl moieties can be used to replace the glycosyl moieties (hydrophobic groups are optionally attached at 2-, 3-, 4-, etc. positions, thereby to obtain glucose or galactose as opposed to glucoside or galactoside). An intersugar linkage may be, for example, between the 2-, 3-, 4- and/or 6-position of a previous saccharide unit and a position of another saccharide unit.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x

wherein R ^is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains from about 10 to about 18 carbon atoms, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; x is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl polyethoxy alcohol is first prepared and then reacted with glucose or a source of glucose to form the glucoside (attachment at the 1-position). The 1-position of the further glycosyl units can then be linked to the 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position, of the preceding glycosyl units.

Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant system of the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Addition of a polyoxyethylene moiety to the hydrophobic moiety tends to increase the water solubility of the overall molecule, and the liquid character of the product is maintained to the point where the polyoxyethylene content is about 50% by weight of the total condensation product, which is equivalent to Up to about 40 moles of ethylene oxide condense. Examples of compounds of this type include certain commercially available Plurafac ^™ LF404 and Pluronic ^™ surfactants, which are sold by BASF.

Also suitable for use as the nonionic surfactant in the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of from about 2500 to about 3000. The hydrophobic moiety is condensed with ethylene oxide to such an extent that the condensation product contains from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of nonionic surfactants of this type include some of the commercially available Tetronic ^™ compounds, sold by BASF.

Preferred for use as the nonionic surfactant in the surfactant system of the present invention are polyoxyethylene condensates of alkylphenols, condensation products of primary and secondary fatty alcohols with about 1 to about 25 moles of ethylene oxide, alkanes Glycans and their mixtures. Most preferred are C ₈ -C ₁₄ alkylphenol ethoxylates with 3 to 15 ethoxy groups and C ₈ -C ₁₈ alcohol ethoxylates with 2 to 10 ethoxy groups (preferably C ₁₀ average ), and mixtures thereof.

其中R¹是H，或R¹是C_1-4烃基、2-羟基乙基、2-羟基丙基或其混合物，R²是C_5-31烃基，Z是具有直接连有至少3个羟基的直链烃基链的多羟基烃基，或其烷氧基化的衍生物。优选R¹是甲基，R²是直链C_11-15烷基或C_16-18烷基或链烯基例如椰子油烷基或其混合物，Z是由在还原胺化反应中的还原糖例如葡萄糖、果糖、麦芽糖、乳糖得到。Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

Wherein R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C _5-31 hydrocarbyl, Z is a Polyhydroxyl hydrocarbyls of linear hydrocarbyl chains, or alkoxylated derivatives thereof. Preferably ^R is methyl, ^R is straight chain C _11-15 alkyl or C _16-18 alkyl or alkenyl such as coconut oil alkyl or mixtures thereof, Z is formed by a reducing sugar in a reductive amination reaction For example glucose, fructose, maltose, lactose are obtained.

Suitable anionic surfactants for use are linear alkylbenzene sulfonate, alkyl ester sulfonate surfactants, including those described in "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329 for sulfonated linear _C8 - _C20 carboxylic acid (ie fatty acid) esters with gaseous _SO3 . Suitable materials include natural fatty materials such as those derived from tallow, palm oil and the like.

其中R³是C₈-C₂₀烃基，优选烷基，或其混合物，R⁴是C₁-C₆烃基，优选烷基，或其混合物，M是阳离子，其与烷基酯磺酸根形成水溶性盐。适合的形成盐阳离子包括金属例如钠、钾和锂，以及取代或未取代的铵阳离子例如单乙醇胺、二乙醇胺和三乙醇胺。优选R³是C₁₀-C₁₆烷基，R⁴是甲基、乙基或异丙基。特别优选的是甲基酯磺酸盐其中R³是C₁₀-C₁₆烷基。Preferred alkyl ester sulfonate surfactants, particularly for laundry applications, include those having the formula:

Wherein R ³ is a C ₈ -C ₂₀ hydrocarbon group, preferably an alkyl group, or a mixture thereof, R ⁴ is a C ₁ -C ₆ hydrocarbon group, preferably an alkyl group, or a mixture thereof, and M is a cation that forms a water-soluble compound with an alkyl ester sulfonate sexual salt. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates wherein R ³ is C ₁₀ -C ₁₆ alkyl.

Other suitable anionic surfactants include alkyl sulfate surfactants, which are water-soluble salts or acids of the formula ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ hydrocarbon group, preferably an alkyl group or has a C ₁₀ -C ₂₀ alkane hydroxyalkyl moiety, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation such as an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl, Dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and quaternary ammoniums derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof cations, etc.). _C12 - _C16 alkyl chains are generally preferred for lower wash temperatures (e.g., below about 50°C), and _C16 - _{C18 alkyl} chains are preferred for higher wash temperatures (e.g., above about 50°C). chain.

Other anionic surfactants useful for detersive purposes may also be included in the cleaning compositions of the present invention. These may include salts of soaps (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), C ₈ -C ₂₂ primary or secondary alkane sulfonates, C ₈ -C ₂₄ alkene sulfonates acid salts, sulfonated polycarboxylic acids prepared by sulfonating pyrolysis products of alkaline earth metal citrates, such as described in British Patent Specification No. 1,082,179; C ₈ -C ₂₄ alkyl polyglycol ethers Sulfates (containing up to 10 moles of oxyethylene); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkylphenol oxyethylene ether sulfates, paraffin sulfonates, alkyl Phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, sulfosuccinic acid monoesters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and sulfosuccinic acid diesters (especially saturated and unsaturated C ₆ -C ₁₂ diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as alkyl polyglucose Glycoside sulfates (nonionic, nonsulfated compounds described _below ), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those having the formula RO( _CH2CH2O ) _{kCH 2} COO ^- M ⁺ salts, wherein R is a C ₈ -C ₂₂ alkyl group, k is an integer from 1 to 10, and M is a cation that forms a soluble salt. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.

Other examples are described in "Surface Active Agents and Detergents" (Volumes I and II, edited by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 23, line 58 through column 29, line 23 (incorporated herein by reference).

When present, the laundry detergent compositions herein will typically contain from about 1% to about 40%, preferably from about 3% to about 20%, by weight of such anionic surfactants.

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants which are water soluble salts or acids of formula RO(A) _m SO ₃ M where R is an unsubstituted C ₁₀ -C ₂₄ alkane or hydroxyalkyl having a C ₁₀ -C ₂₄ alkyl moiety, preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is ethoxy or propyl Oxygen units, m value greater than 0, generally between about 0.5 to about 6, more preferably between about 0.5 to about 3, M is H or a cation, which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cations. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated by the present invention. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and those formed from alkylamines such as ethylamine, diethylamine, Cations derived from amines, triethylamine and their mixtures, etc. Exemplary surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C ₁₈ E(1.0)M), C ₁₂ -C ₁₈ alkyl polyethoxylate ( 2.25) Sulfate (C ₁₂ -C ₁₈ E(2.25)M), C ₁₂ -C ₁₈ Alkyl Polyethoxylate (3.0) Sulfate (C ₁₂ -C ₁₈ E(3.0)M) and C ₁₂ - C ₁₈ alkyl polyethoxylate (4.0) sulfate (C ₁₂ -C ₁₈ E(4.0)M), where M is suitably selected from sodium and potassium.

The cleaning compositions of the present invention may also contain cationic, amphoteric, zwitterionic and semi-polar surfactants, as well as nonionic and/or anionic surfactants not already described herein.

Cationic detersive surfactants suitable for use in the cleaning compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium salt surfactants such as alkyltrimethylammonium halides, and those of the formula:

[R ² (OR ³ ) _Y ][R ⁴ (OR ³ ) _Y ] ₂ R ⁵ N ⁺ X ^-

wherein ^R2 is an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in its alkyl chain, _{and each R3 is selected from the group consisting of -CH2CH2-, -CH2CH} ⁽ _{CH3 ) -} , -CH ₂ CH(CH ₂ OH)-, -CH ₂ CH ₂ CH ₂ -, and mixtures thereof; each R ⁴ is selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, by connecting two A benzyl ring structure formed by R ⁴ groups, -CH ₂ CHOH-CHOHCOR ⁶ CHOHCH ₂ OH, wherein R ⁶ is any hexose or hexose polymer group having a molecular weight less than about 1000, and hydrogen (when y is not 0); ^R5 is the same group as ^R4 , or an alkyl chain, wherein the total number of carbon atoms of ^R2 plus ^R5 is not more than about 18; each y is from 0 to about 10, and the value of y The sum is from 0 to about 15; x is any compatible anion.

Quaternary ammonium surfactants suitable for use in the present invention have the formula (I):

Formula I

Wherein _R is an alkyl group (C6-C10) of short chain length, or an alkylamidoalkyl group of formula (II):

Formula II

y is 2-4, preferably 3.

Wherein R ₂ is H or C1-C3 alkyl,

Wherein x is 0-4, preferably 0-2, most preferably 0, wherein R ₃ , R ₄ and R ₅ are the same or different, and can be short-chain alkyl (C1-C3), or alkoxy of formula III ylated alkyl, wherein X ^- is a counterion, preferably a halide, such as chloride or methylsulfate,

Formula IIIR ₆ is C ₁ -C ₄ , z is 1 or 2.

Preferred quaternary ammonium surfactants are those defined by formula I: wherein R ₁ is C ₈ , C ₁₀ or mixtures thereof, x=0, R ₃ , R ₄ =CH ₃ , R ₅ =CH ₂ CH ₂ OH.

Highly preferred cationic surfactants suitable for use in the compositions of the present invention are water-soluble quaternary ammonium compounds having the formula:

R ₁ R ₂ R ₃ R ₄ N ⁺ X ^- (i) wherein R ₁ is C ₈ -C ₁₆ alkyl, each of R ₂ , R ₃ and R ₄ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl, and -(C ₂ H ₄ O) _x H, where x has a value from 2 to 5 and X is an anion. R ₂ , R ₃ , R ₄ should not be more than one benzyl group.

Preferred alkyl chain lengths for R ₁ are C ₁₂ -C ₁₅ . In particular, the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or derived synthetically from alkenes or oxo alcohols. Preferred groups for R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl, and the anion X may be selected from halide, methylsulfate, acetate and phosphate ions.

烷基，和R₂、R₃、R₄是甲基)；Examples of suitable quaternary ammonium compounds of formula (i) for use in the present invention are: cocotrimonium chloride or ammonium bromide; cocomethyldihydroxyethylammonium chloride or ammonium bromide; Triethyl ammonium chloride; Decyl dimethyl hydroxyethyl ammonium chloride or ammonium bromide; C ₁₂ -C ₁₅ dimethyl hydroxyethyl ammonium chloride or ammonium bromide; Coconut oil dimethyl hydroxyethyl ammonium ammonium chloride or ammonium bromide; myristyl trimethyl ammonium methyl sulfate; lauryl dimethyl benzyl ammonium chloride or ammonium bromide; lauryl dimethyl(oxyethylene) ₄ ammonium chloride or bromide ammonium chloride; choline ester (compound of formula (i), wherein R ₁ is

Alkyl, and R ₂ , R ₃ , R ₄ are methyl);

Dialkylimidazolines [compounds of formula (i)].

Other cationic surfactants useful herein are also described in US Patent 4,228,044, Cambre, issued October 14,1980, and European Patent Application EP 000,224.

Typical cationic fabric softening ingredients include water insoluble quaternary ammonium fabric softening actives or their corresponding amine precursors, most commonly methylated di-long chain alkylammonium chlorides or sulfates.

Wherein preferred cationic softener includes following:

1) ditallow dimethyl ammonium chloride (DTDMAC);

2) dihydrogenated tallow dimethyl ammonium chloride;

3) Dihydrogenated tallow dimethyl ammonium methyl sulfate;

4) distearyl dimethyl ammonium chloride;

5) dioleyl dimethyl ammonium chloride;

6) dipalmityl hydroxyethyl methyl ammonium chloride;

7) stearyl benzyl dimethyl ammonium chloride;

8) tallow trimethylammonium chloride;

9) tallow trimethyl ammonium hydrochloride;

10) C _12-14 alkyl hydroxyethyl dimethyl ammonium chloride;

11) C _12-18 alkyl dihydroxyethyl methyl ammonium chloride;

12) Di(stearyloxyethyl)dimethylammonium chloride (DSOEDMAC);

13) Di(tallowyloxyethyl)dimethylammonium chloride;

14) Ditallow imidazolinium methyl sulfate;

15) Methyl sulfate methylation of 1-(2-tallowamidoethyl)-2-tallowyl imidazolinium.

Biodegradable quaternary ammonium compounds have emerged as alternatives to the traditionally used chlorinated and methylsulfated di-long-chain alkylammonium compounds. Such quaternary ammonium compounds contain long chain alkenyl groups interrupted by functional groups such as carboxyl groups. Said materials and fabric softening compositions containing them are disclosed in a number of publications, for example EP-A-0040562 and EP-A-0239910. The quaternary ammonium compounds and amine precursors of the present invention have the following formula (I) or (II): or Wherein Q is selected from -OC(O)-, -C(O)-O-, -OC(O)-O-, -NR ⁴ -C(O)-, -C(O)-NR ⁴ -; R ¹ is (CH ₂ ) _n -QT ² or T ³ ; R ² is (CH ₂ ) _m -QT ⁴ or T ⁵ or R ³ ; R ³ is C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkane or H; R ⁴ is H or C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl; T ¹ , T ² , T ³ , T ⁴ , T ⁵ are independently C ₁₁ -C ₂₂ alkyl Or alkenyl; n and m are integers from 1 to 4; and X ^- is a softener compatible anion.

Non-limiting examples of softener compatible anions include chloride or methylsulfate.

The alkyl, or alkenyl, chain ^T1 , ^T2 , ^T3 , ^T4 , ^T5 must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain can be straight or branched.

Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl species. Compounds in which T ¹ , T ² , T ³ , T ⁴ , T ⁵ represent typical tallow mixed long chain mixtures are particularly preferred.

Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions of the present invention include: 1) N,N-bis(tallowoyloxyethyl)-N,N-dimethylammonium chloride; 2) N, N-bis(tallowoyloxyethyl)N-methyl, N-(2-hydroxyethyl)ammonium methylsulfate; 3) N,N-bis(2-tallowoyloxy-2-oxo 4) N,N-di(2-tallowoyloxy-ethylcarbonyloxyethyl)-N,N-dimethylammonium chloride Ammonium; 5) N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowoyloxy-2-oxyethyl)-N,N-dimethylammonium chloride ; 6) N, N, N-tris(tallowoyloxy-ethyl)-N-methylammonium chloride; 7) N-(2-tallowoyloxy-2-oxyethyl)- N-(tallowoyl-N,N-dimethylammonium chloride); and 8) 1,2-ditallowoyloxy-3-trimethylammoniumpropane chloride;

and mixtures of any of the above substances.

When included, the cleaning compositions of the present invention typically contain from 0.2% to about 25%, preferably from about 1% to about 8%, by weight of such cationic surfactants.

Amphoteric surfactants are also suitable for use in the cleaning compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary or tertiary amines, where the aliphatic group may be straight or branched. One aliphatic substituent contains at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one aliphatic substituent contains a water-soluble anionic group, eg, carboxy, sulfonate, sulfate. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, lines 18-35, for examples of amphoteric surfactants.

When included, the cleaning compositions of the present invention typically contain from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of such amphoteric surfactants.

Zwitterionic surfactants are also suitable for use in cleaning compositions. These surfactants can be broadly described as derivatives of secondary or tertiary amines, derivatives of heterocyclic secondary or tertiary amines, or derivatives of quaternary ammonium salts, quaternary phosphonium or tertiary sulfonium compounds. See US Patent No. 3,929,678, issued December 30, 1975 to Laughlin et al., at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.

When included, the cleaning compositions of the present invention typically contain from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of such zwitterionic surfactants.

Semi-polar nonionic surfactants are a specific class of nonionic surfactants that include water-soluble amine oxides that contain an alkyl moiety of about 10 to about 18 carbon atoms and two alkyl moieties selected from the group consisting of about 1 to Alkyl and hydroxyalkyl moieties of about 3 carbon atoms; water-soluble phosphine oxides comprising an alkyl moiety of about 10 to about 18 carbon atoms and 2 alkyl moieties selected from the group consisting of about 1 to about 3 carbon atoms and a hydroxyalkyl moiety; and a water-soluble sulfoxide comprising an alkyl moiety of about 10 to about 18 carbon atoms and an alkyl and hydroxyalkyl moiety selected from about 1 to about 3 carbon atoms.

其中R³是含有约8至约22个碳原子的烷基、羟烷基或烷基苯基、或它们的混合物；R⁴是含有约2至约3个碳原子的亚烷基或羟亚烷基或它们的混合物；x为0至约3；每个R⁵是含有约1至约3个碳原子的烷基或羟烷基或含有约1至约3个氧乙烯基团的聚氧乙烯基团。R⁵基团可彼此连接，例如通过氧或氮原子连接形成环状结构。Semi-polar nonionic detergent surfactants include amine oxide surfactants having the formula:

wherein ^R3 is alkyl, hydroxyalkyl or alkylphenyl, or mixtures thereof containing from about 8 to about 22 carbon atoms; ^R4 is alkylene or hydroxyalkylene containing from about 2 to about 3 carbon atoms Alkyl or mixtures thereof; x is from 0 to about 3; each ^R is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyoxyl group containing from about 1 to about 3 oxyethylene groups Vinyl group. The ^R5 groups may be linked to each other, for example via an oxygen or nitrogen atom to form a ring structure.

These amine oxide surfactants include in particular C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides.

When included, the cleaning compositions of the present invention typically contain from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of such semi-polar nonionic surfactants.

The cleaning compositions of the present invention may also contain cosurfactants selected from primary or tertiary amines. Suitable primary amines for use in the present invention include amines of the formula R ₁ NH ₂ , wherein R ₁ is a C ₆ -C ₁₂ , preferably C ₆ -C ₁₀ alkyl chain, or R ₄ X(CH ₂ ) _n , where X is -O-, -C(O)NH- or -NH-, R ₄ is a C ₆ -C ₁₂ alkyl chain n is 1-5, preferably 3. The _R1 alkyl chain may be straight or branched and may contain up to 12, preferably less than 5, oxyethylene moieties at intervals.

According to the above formula, the preferred amines are n-alkylamines. Suitable amines for use in the present invention may be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyloxypropylamine, laurylamidopropylamine and amidopropylamine.

R₃是C₆-C₁₂，优选C₆-C₁₀烷基链，或R₃是R₄X(CH₂)_n，其中X是-O-，-C(O)NH-或-NH-，R₄是C₄-C₁₂，n是1-5，优选2-3，R₅是H或C₁-C₂烷基，x是1-6。R₃和R₄可以是直链或支链；R₃烷基链可间隔含有多至12个，优选少于5个氧乙烯部分。Suitable tertiary amines for use in the present invention include tertiary amines of the formula R ₁ R ₂ R ₃ N, wherein R ₁ and R ₂ are C ₁ -C ₈ alkyl chains or

R ₃ is C ₆ -C ₁₂ , preferably C ₆ -C ₁₀ alkyl chain, or R ₃ is R ₄ X(CH ₂ ) _n , where X is -O-, -C(O)NH- or -NH- , R ₄ is C ₄ -C ₁₂ , n is 1-5, preferably 2-3, R ₅ is H or C ₁ -C ₂ alkyl, x is 1-6. _R3 and _R4 may be linear or branched; the _R3 alkyl chain may contain up to 12, preferably less than 5, oxyethylene moieties in intervals.

其中R₅是H或CH₃，x＝1-2。Preferred tertiary amines are R ₁ R ₂ R ₃ N, where R ₁ is a C ₆ -C ₁₂ alkyl chain, R ₂ and R ₃ are C ₁ -C ₃ alkyl or

Wherein R ₅ is H or CH ₃ , x=1-2.

其中R₁是C₆-C₁₂烷基；n是2-4，优选n是3；R₂和R₃是C₁-C₄。Also preferred are amidoamines of the formula:

Wherein R ₁ is C ₆ -C ₁₂ alkyl; n is 2-4, preferably n is 3; R ₂ and R ₃ are C ₁ -C ₄ .

The most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C8-C10 oxypropylamine, N-coconut oil 1-3 diaminopropane, coconut Oleyl Dimethylamine, Lauryl Dimethylamine, Lauryl Di(Hydroxyethyl)amine, Coco Di(Hydroxyethyl)amine, 2 Moles Propoxylated Laurylamine, 2 Moles Propoxy Octylamine, lauryl amidopropyl dimethylamine, C8-C10 amidopropyl dimethylamine and C10 amidopropyl dimethylamine.

The most preferred amines for use in the compositions of the present invention are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly suitable are n-dodecyldimethylamine and dihydroxyethylcocoalkylamine and 7-fold ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine. Color care and fabric care

Techniques to provide a color-care effect may also be included. Examples of these technologies are metal catalysts for color retention. Such metal catalysts are described in co-pending European Patent Application No. 92870181.2. Further examples of color care/fabric care technologies are dye fixatives, polyolefin dispersants for wrinkle resistance and improved water absorption, fragrance and amino functional polymers for color care treatments and substantivity of fragrance, which are described In copending patent application No. 96870140.9, filed November 7, 1996.

Fabric softening agents can also be incorporated into the cleaning compositions of the present invention. These softeners can be of inorganic or organic type. Examples of inorganic softeners are the smectites disclosed in GB-A-1400898 and USP 5,019,292. Organic fabric softeners include water-insoluble tertiary amines as disclosed in GB-A 1 514 276 and EP-B 0 011 340 and as disclosed in EP-B-0 026 527 and EP-B-0 026 528. Mixtures of mono-C12-C14 quaternary ammonium salts, and di-long-chain amides as disclosed in EP-B-0242919. Other suitable organic components for fabric softener systems include the high molecular weight polyoxyethylene materials disclosed in EP-A-0 299 575 and 0 313 146.

The content of smectite clay is usually 2% to 20%, more preferably 5% to 15% by weight, this material is added as a dry blend component to the remaining ingredients of the formulation. The blending amount of organic fabric softener such as water-insoluble tertiary amine or double long-chain amide material is 0.5% to 5% by weight, usually 1% to 3% by weight, while the addition of high molecular weight polyoxyethylene material and water-soluble cationic material The amount is 0.1% to 2%, usually 0.15% to 1.5% by weight. These materials are usually added to the spray-dried portion of the composition, although in some cases it may be more convenient to add them as dry-mixed granules or to spray them as a molten liquid onto the other solid components of the composition. Builder system

The compositions of the present invention may also comprise a builder system. Any conventional builder system is suitable for use herein, including aluminosilicate materials, silicates, polycarboxylates, alkyl or alkenyl succinic acids and fatty acids, such as ethylenediaminetetraacetic acid, diethylene materials such as triaminepentamethyleneacetic acid, metal ion sequestrants such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Phosphate builders are also useful herein.

Suitable builders may be inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials, more particularly hydrated synthetic zeolites such as hydrated zeolites A, X, B, HS or MAP.

Another suitable inorganic builder material is layered silicate, eg SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate composed of sodium silicate (Na ₂ Si ₂ O ₅ ).

Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and their ether derivatives as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, hydroxymalonic acid and fumaric acid, As well as ether carboxylates described in German Patents 2,446,686 and 2,446,687 and US Patent No. 3,935,257, and thionyl carboxylates described in Belgian Patent 840,623. Polycarboxylates containing three carboxy groups include, inter alia, the water-soluble citrates, aconitates and citraconates, and succinate derivatives such as carboxymethoxysuccinate as described in British Patent 1,379,241 , lactyloxysuccinates as described in Dutch Patent Application 7205873, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylates as described in British Patent No. 1,387,447 .

Polycarboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates disclosed in British Patent No. 1,261,829 Carboxylate and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Patent No. 3,936,448, and the sulfonated pyrolytic Citrates, and polycarboxylates containing phosphine substituents are disclosed in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylate, cyclopentadiene pentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis -tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,2,5,5-tetrahydrofuran tetracarboxylate, 1,2,3,4,5,6-hexane hexacarboxylate and carboxymethyl derivatives of polyols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include derivatives of melitaric acid, pyromellitic acid and phthalic acid disclosed in British Patent No. 1,425,343.

Among the above compounds, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

Preferred builder systems for use in the compositions of the present invention include a water-insoluble aluminosilicate builder such as zeolite A or a layered silicate (SKS-6) with a water-soluble carboxylate chelating agent such as lemon A mixture of acids.

A preferred builder system comprises a mixture of a water insoluble aluminosilicate builder such as zeolite A with a water soluble carboxylate chelating agent such as citric acid. Preferred builder systems for use in the liquid detergent compositions of the present invention are soaps and polycarboxylates.

Other builder materials that may form part of the builder system for use in granular compositions include inorganic materials such as alkali metal carbonates, bicarbonates, silicates and organic materials such as organic phosphonates, aminopolyethylene Alkylphosphonates and aminopolycarboxylates.

Other suitable water-soluble organic salts are homo- or co-polymeric acids or their salts, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates with MW 2000-5000, and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20,000 to 70,000, especially about 40,000.

Detergency builder salts generally comprise from 5% to 80%, preferably from 10% to 70%, most usually from 30% to 60%, by weight of the composition. Chelating agent

The cleaning compositions of the present invention may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all chelating agents being as defined hereinafter. Without being bound by theory, it is believed that the advantages of these materials lie in part in their extraordinary ability to remove iron and manganese from wash solutions by forming soluble chelates.

Amino carboxylates used as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, Triethylenetetraamine hexaacetate, diethylenetriaminepentaacetate and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts and mixtures thereof.

When at least low levels of total phosphorus are permitted in the detergent compositions herein, amino phosphonates are also suitable for use as chelating agents in the compositions herein, including: ethylenediamine tetrakis (methylene phosphonates) for DEQUEST. These amino phosphonates preferably do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents may also be used in the compositions of the present invention. See US Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), especially as described in US Pat. S, S] isomers.

The compositions of the present invention may also contain water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a chelating agent, or as an adjunct to, for example, insoluble builders such as zeolites, layered silicates, etc. Builder.

If utilized, chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. If utilized, chelating agents are more preferably present in an amount of from about 0.1% to 3.0% by weight of the composition. Foam suppressor

Another optional ingredient is a suds suppressor, exemplified by silicones and silica-polysiloxane mixtures. Polysiloxanes are generally represented by alkylated polysiloxane substances, while dioxides are generally used in the form of fine powders. Examples include silica aerogels and xerogels and various types of hydrophobic dioxanes. silicon oxide. These materials may be incorporated in the form of granules wherein the suds suppressor is incorporated into a water-soluble or water-dispersible, substantially non-surface-active, detergent-impermeable carrier, but is advantageously releasable. Additionally, the suds suppressor can be dissolved or dispersed in a liquid carrier or applied by spraying onto one or more of the other ingredients.

Preferred silicone suds control agents are disclosed in US Patent 3,933,672 to Bartollota et al. Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors described in German Patent Application DTOS 2,646,126, published April 28,1977. An example of such a compound is DC-544, commercially available from Dow corning, which is a silicone-glycol copolymer. Especially preferred suds control agents are suds suppressor systems comprising a mixture of silicone oils and 2-alkyl alkanols. A suitable 2-alkyl alkanol is 2-butyloctanol, which is commercially available under the tradename Isofol 12 R.

Such suds suppressor systems are described in co-pending European Patent Application No. 92870174.7, filed November 10,1992.

Particularly preferred silicone suds control agents are described in co-pending European Patent Application No. 92201649.8. The composition may comprise a polysiloxane/silica mixture in combination with a fumed non-porous silica such as Aerosil ^R.

The above-mentioned anti-foaming agent is generally used in an amount of 0.001% to 2%, preferably 0.01% to 1%, by weight of the composition. other

Other components used in cleaning compositions, such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, colorants, and/or encapsulated or non-encapsulated spices.

A particularly suitable encapsulating material is a water-soluble capsule consisting of a matrix of polysaccharides and polyols such as described in GB 1,464,616.

Other suitable water-soluble encapsulating materials include dextrins derived from non-gelling starch acid-esters of substituted dicarboxylic acids, such as described in US 3,455,838. These acid-ester dextrins are preferably prepared from such starches as waxy corn, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating material include N-Lok manufactured by National Starch. The N-Lok encapsulant consists of modified corn starch and dextrose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic anhydride.

Antiredeposition and soil suspension agents suitable for use herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts. Polymers of this type include the aforementioned polyacrylates as builders and copolymers of maleic anhydride and acrylic acid, and copolymers of maleic anhydride and ethylene, methyl vinyl ether or methacrylic acid, maleic anhydride, The anhydride comprises at least 20 mole percent of the copolymer. These materials are generally used in amounts of from 0.5% to 10%, more preferably from 0.75% to 8%, most preferably from 1% to 6%, by weight of the composition.

Preferred optical brighteners are anionic, examples of which are 4,4'-bis(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'-di Disodium sulfonate, 4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene-2: Disodium 2'-disulfonate, 4,4' -Bis(2,4-dianilino-s-triazin-6-ylamino)stilbene-2: 2'-disodium disulfonate, 4',4"-bis(2,4-dianilino- s-triazin-6-ylamino)stilbene-2'-sulfonate monosodium, 4,4'-bis(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)- s-triazin-6-ylamino)stilbene-2: disodium 2'-disulfonate, 4,4'-bis(4-phenyl-2,1,3-triazol-2-yl)stilbene- 2: Disodium 2'-disulfonate, 4,4'-bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene -2: Disodium 2'-disulfonate, 2-(stilbene-4"-(naphtho-1',2':4,5)-1,2,3-triazole-2"-sulfonic acid Sodium and 4,4'-bis(2-thiostyryl)biphenyl. Highly preferred brighteners are those specified in co-pending European Patent Application No. 95201943.8.

Other useful polymeric materials are polyethylene glycols, especially those having a molecular weight of 1,000-10,000, more preferably 2,000-8,000, most preferably about 4,000. These substances are used in amounts of 0.20% to 5%, more preferably 0.25% to 2.5% by weight. These polymers and the aforementioned homo- or co-polymeric polycarboxylates are useful for improving whiteness maintenance, fabric dust deposition and cleaning performance on earthy, proteinaceous and oxidizable soils in the presence of transition metal impurities. All aspects are valuable.

Soil release agents useful in the compositions of the present invention are generally copolymers or terpolymers of terephthalic acid and ethylene glycol and/or propylene glycol units in various arrangements. Examples of such copolymers are disclosed in commonly assigned US Patents 4,116,885 and 4,711,730 and European Published Patent Application No, 0 272 033. According to EP-A-0272033, a particularly preferred polymer has the formula: (CH ₃ (PEG) ₄₃ ) _0.75 (POH) _0.25 [T-PO) _2.8 (T-PEG) _0.4 ]T(POH) _0.25 (( PEG) ₄₃ CH ₃ ) _0.75

where PEG is -(OC ₂ H ₄ )O-, PO is (OC ₃ H ₆ O), and T is (pcOC ₆ H ₄ CO).

Also very useful are modified polyesters such as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol, the end groups of which are mainly composed of sulfo benzoate and, secondarily, monoesters of ethylene glycol and/or propylene glycol. The aim is to obtain a polymer terminated at both ends by sulfobenzoate groups. "Predominantly" in this context means that the majority of said copolymers are terminated with sulfobenzoate groups. However, some copolymers are not completely capped, so their end groups may consist of monoesters of ethylene glycol and/or 1,2-propanediol, which are "minor" constituents of this class.

The polyester selected herein contains about 46% by weight dimethyl terephthalate, about 16% by weight 1,2-propanediol, about 10% by weight ethylene glycol, about 13% by weight dimethyl sulfobenzoate and about 15% weight sulfoisophthalic acid, which has a molecular weight of about 3000. The polyesters and their preparation are described in detail in EPA311342.

It is known in the art that free chlorine in tap water can rapidly inactivate enzymes included in detergent compositions. Thus, the use of chlorine scavengers such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine in formulations greater than 0.1% by weight of the total composition will provide improved detergent throughout the wash cycle. Enzyme stability. Compositions comprising chlorine scavengers are described in European Patent Application 92870018.6 filed 31 January 1992

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are also suitable for use herein to provide additional grease removal performance. Such materials are described in WO91/08281 and PCT90/01815, pages 4 et seq., incorporated herein by reference. Chemically, these materials include polyacrylates having one ethoxy side chain per 7-8 acrylate units. The side chain has the formula: -(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , where m is 2-3 and n is 6-12. The side chains are attached to the polyacrylate "backbone" by ester linkages, resulting in a "comb" structure type of polymer, the molecular weight of which can vary, but is generally in the range of about 2,000-50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the compositions herein. Dispersant

The cleaning compositions of the present invention may also contain dispersants: suitable water-soluble organic salts which are homo- or copolymeric acids or salts thereof, wherein the polycarboxylic acid comprises at least two polycarboxylic acids separated from each other by not more than 2 carbon atoms. carboxyl. Polymers of this type are disclosed in GB-A-1596756. Examples of such salts are polyacrylates of MW 2000-5000, and their copolymers with maleic anhydride, such polymers having a molecular weight of 1,000-100,000.

In particular, copolymers of acrylate and methacrylate, such as 480N with a molecular weight of 4000, may be added to the cleaning compositions of the present invention at 0.5% to 20% by weight of the composition.

The compositions of the present invention may contain a calcium soap peptizer compound which preferably has a calcium soap dispersing power (LSDP), as defined below the LSDP does not exceed 8, preferably does not exceed 7, most preferably does not exceed 6. The content of the calcium soap peptizer compound is preferably 0%-20% by weight of the composition.

A numerical measure of the effectiveness of lime soap peptizers is given by the Lime Soap Dispersant Power (LSDP) as measured by HC Borghetty and CA Bergman, J.Am. in Oil.Chem.Soc. ) Vol. 27, pp. 88-90 (1950) for the experimental determination of calcium soap dispersants described in the article. This calcium soap dispersion test method is widely used by professionals in the art, see for example, the following review articles; WN Linfield, Surfactant Science Series, Vol. 7, p. 3; WN Linfield, Surfactant Detergents (Tenside Surf. Det.), Vol. 27, pp. 159-163 (1990); and MK Nagarajan, WF Masler, Cosmetic and Toiletries, Vol. 104, pp. 71-73 (1989) . LSDP is the weight % ratio of the dispersant and sodium oleate needed for dispersing calcium soap deposits, said calcium soap deposits are made of 333ppm CaCO in 30ml ₃ (Ca: Mg=3: 2) 0.025g in water of equivalent hardness Formed from sodium oleate.

Surfactants with good lime soap peptizing capabilities include certain amine oxides, betaines, sultaines, alkyl ethoxy sulfates and ethoxylated alcohols.

Examples of surfactants useful in the present invention having an LSDP of not more than 8 include C ₁₆ -C ₁₈ dimethyl amine oxide, C ₁₂ -C ₁₈ alkyl ethoxy sulfates having an average degree of ethoxylation of 1-5 , especially C ₁₂ -C ₁₅ alkyl ethoxysulfate surfactants having a degree of ethoxylation of 3 (LSDP=4), and having an average degree of ethoxylation of 12 (LSDP=6) or 30 C ₁₄ -C ₁₅ ethoxylated alcohols sold by BASF GmbH under the trade names Lutensol A012 and Lutensol A030, respectively.

Polymeric calcium soap peptizers suitable for use in the present invention are described in the article by M.K. Nagarajan, W.F. Masler, Cosmetic and Toiletries, Vol. 104, pp. 71-73 (1989).

Hydrophobic bleaches such as 4-[N-octanoyl-6-aminocaproyl]benzenesulfonate, 4-[N-nonanoyl-6-aminocaproyl]benzenesulfonate, 4-[N-decanoyl- 6-aminocaproyl]benzenesulfonate and mixtures thereof; and nonanoyloxybenzenesulfonate in combination with hydrophilic/hydrophobic bleach formulations are also useful as soap peptizer components. dye transfer inhibition

The cleaning compositions of the present invention may also include compounds useful for inhibiting the transfer of dissolved and suspended dyes from one fabric to another encountered during laundering operations involving colored fabrics. polymeric dye transfer inhibitor

The cleaning compositions of the present invention also comprise from 0.001% to 10%, preferably from 0.01% to 2%, more preferably from 0.05% to 1%, by weight of a polymeric dye transfer inhibiting agent. Said polymeric dye transfer inhibiting agents are generally incorporated into cleaning compositions in order to inhibit the transfer of dyes from colored fabrics to fabrics which are simultaneously laundered. These polymers have the ability to sequester or adsorb fugitive dyes washed from colored fabrics before they have a chance to contact other items in the wash.

Particularly suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinyl imidazoles or their mixtures.

The addition of such polymers also enhances the performance of the enzymes of the invention. a) Polyamine N-oxide polymers

Suitable polyamine N-oxide polymers contain units of the formula: wherein P is a polymerizable unit to which the RNO group may be attached or wherein the RNO group forms part of the polymerizable unit

part or a mixture of both.

-O-，-S-，-N-；x是O或1；R是脂族、乙氧基化脂族、芳族、杂环或脂环基团或它们的任何组合，其中N-O基团的氮原子可连接在其上或其中N-O基团的氮原子是这些基团的一部分。A is

-O-, -S-, -N-; x is O or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof, wherein the NO group to which the nitrogen atom of the NO group may be attached or wherein the nitrogen atom of the NO group is part of these groups.

其中R₁、R₂和R₃是脂族基团、芳族、杂环或脂环基团或它们的混合物，x或/和y或/和z是0或1，其中N-O基团的氮原子可连接在其上或其中N-O基团的氮原子是这些基团的一部分。The NO group can be represented by the following general structural formula:

wherein R ₁ , R ₂ and R ₃ are aliphatic groups, aromatic, heterocyclic or alicyclic groups or mixtures thereof, x or/and y or/and z are 0 or 1, wherein the nitrogen of the NO group The nitrogen atom to which the atom may be attached or where the NO group is part of these groups.

The N-O group is part of the polymerizable unit (P) or can be attached to the polymeric backbone or a mixture of both.

Suitable polyamine N-oxides in which the N-O group forms part of the polymerisable unit include polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.

One class of said polyamine N-oxides includes polyamine N-oxides in which the nitrogen atom of the N-O group forms part of the R group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of said polyamine N-oxides includes polyamine N-oxides in which the nitrogen atom of the N-O group is attached to the R group.

Other suitable polyamine N-oxides are polyamine N-oxides in which the N—O group is attached to the polymerisable unit.

A preferred class of these polyamine N-oxides are polyamine N-oxides having the general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen atom of the N-O functional group is said part of the R group.

Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and their derivatives.

Another preferred class of polyamine N-oxides are polyamine oxides of general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, wherein the nitrogen atom of the N-O functional group is attached to said R on the group.

Examples of these types are polyamine oxides wherein the R group is an aromatic group such as phenyl.

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

The amine N-oxide polymers of the present invention typically have a ratio of amine to amine N-oxide of from 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or by suitable degree of N-oxidation. Preferably the ratio of amine to amine N-oxide is from 2:3 to 1:1000000, more preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present invention actually include random and block copolymers in which one type of monomer is an amine N-oxide and the other type of monomer is an amine N-oxide or not. The amine oxide units in the polyamine N-oxides have a PK _a <10, preferably a PK _a <7, more preferably a PK _a <6.

Polyamine oxides are available in virtually any degree of polymerization. The degree of polymerization is not critical so long as the material has the required water solubility and dye-suspending abilities.

Typically, its average molecular weight is from 500 to 1,000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The N-vinylimidazole N-vinylpyrrolidone polymer used in the present invention has an average molecular weight of 5,000-1,000,000, preferably 5,000-200,000.

Highly preferred polymers for use in the detergent compositions of the present invention include polymers selected from N-vinylimidazole N-vinylpyrrolidone copolymers, wherein said polymers have an average molecular weight of 5,000 to 50,000, more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.

The average molecular weight is determined by light scattering methods such as described in Barth H.G. and Mays J.W. Chemical Analysis Vol. 113, "Modern Methods of Polymer Characterization".

Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight of 5,000 to 50,000, more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.

N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties without adversely affecting the cleaning performance of formulated detergent compositions.

The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1 to 0.2, more preferably 0.8 to 0.3, most preferably 0.6 to 0.4. c) polyvinylpyrrolidone

The detergent compositions of the present invention can also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, most preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the product designations PVP K-15 (viscosity molecular weight 10,000); PVP K-30 (average molecular weight 40,000); PVP K-60 ( Average molecular weight 160,000) and PVP K-90 (average molecular weight 360,000) were purchased. Other suitable polyvinylpyrrolidones commercially available from the company BASF include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones well known to those skilled in the detergent art (see e.g. EP-A-262,897 and EP-A-256,696) . d) polyvinyl oxazolidinone

The detergent compositions herein can also employ polyvinyloxazolidinones as polymeric dye transfer inhibiting agents. The polyvinyloxazolidinone has an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, most preferably from about 5,000 to about 15,000. e) Polyvinyl imidazole

The detergent compositions herein can also employ polyvinylimidazole as a polymeric dye transfer inhibiting agent. The polyvinylimidazole has an average molecular weight of about 2,500 to about 400,000, preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000, most preferably about 5,000 to about 15,000.

f) Cross-linked polymers

A cross-linked polymer is a polymer whose backbone is interconnected to some extent; these linkages can be chemical or physical, and there can be reactive groups on the backbone or on the branches. Cross-linked polymers have been described in Journal of Polymer Science, Vol. 22, pp. 1035-1039.

In one embodiment, the crosslinked polymers are prepared in such a way that they form a three-dimensional rigid structure that is capable of trapping the dye in the pores formed by the three-dimensional structure. In another embodiment, the crosslinked polymer entraps the dye by protuberances.

Such cross-linked polymers are described in pending patent application 94870213.9. cleaning method

The compositions of the present invention may be used in essentially any washing or cleaning method, including soaking methods, pretreatment methods and methods with a rinse step in which a separate rinse-boosting composition may be added.

The methods described herein involve contacting the fabrics with a laundry solution in the usual manner and as exemplified below.

The method of the present invention is suitably carried out during the cleaning process. The cleaning method is preferably carried out at a temperature of 5°C to 95°C, especially at a temperature of 10°C to 60°C. The pH of the treatment solution is preferably 7 to 12.

A preferred machine dishwashing method comprises treating soiled items with an aqueous solution having dissolved or dispersed an effective amount of a machine dishwashing or rinsing composition. A typical effective amount of a machine dishwashing composition is to dissolve or disperse 8-60 g of product in a wash volume of 3-10 liters.

According to the hand dishwashing method, soiled dishes are contacted with an effective amount of the dishwashing composition, typically 0.5-20 g (per 25 dishes treated). A preferred method of hand dishwashing involves applying a concentrated solution to the surface of the dish or soaking the dish in a substantially dilute solution of the detergent composition.

The following examples are intended to illustrate the compositions of the present invention and are not intended to limit or otherwise define the scope of the invention.

In cleaning compositions, enzyme levels are expressed by weight of pure enzyme based on the total composition and, unless otherwise stated, detergent components are expressed by weight of the total composition. Wherein the abbreviated component symbols have the following definitions: LAS: linear C _11-13 sodium alkylbenzene sulfonate TAS: sodium tallow alkyl sulfate C _xy AS: C _1X -C _1y sodium alkyl sulfate C _xy SAS: C _1x -C _1y sodium secondary (2,3) alkyl sulfate C _xy E _Z ; condensed average z moles of ethylene oxide are mostly linear C _1X -C _1y

Primary Alcohol C _xy E _Z S : Sodium C _1X -C _1y Alkyl Sulfate QAS : R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₁₂ -C ₁₄ QAS1 : R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ ＝C ₈ -C ₁₁ APA : C _8-10 Amidopropyl dimethylamine soap: made from bovine 80/20 blend of oil and coconut oil fatty acids

   Sodium Alkanyl Carboxylate Nonionic: Has an average degree of ethoxylation of 3.8 and an average degree of propoxylation of

4.5 _C13 - _C15 mixed ethoxylated/propoxylated fatty alcohol Neodol 45-13: C14-C15 linear primary alcohol sold by Shell Chemical

Ethoxylates STS: Sodium Toluene Sulfonate CFAA: C ₁₂ -C ₁₄ Alkyl N-Methyl Glucamide TFAA: C ₁₆ -C ₁₈ Alkyl N-Methyl Glucamide TPKFA: C12-C14 Fatty Acid Top Full Fraction DEQA: Di(tallowyloxyethyl)dimethylammonium chloride DEQA(2): Di(soft tallowyloxyethyl)hydroxyethylmethylammonium methyl sulfate DTDMAMS: Ditallow Dimethylammonium methyl sulfate SDASA: 1:2 stearyl dimethylamine: triple pressure stearic acid silicate: amorphous sodium silicate (SiO ₂ : Na ₂ O = 1.6-3.2) partial silicon Salt: sodium metasilicate (SiO ₂ : Na ₂ O = 1.0) Zeolite A: hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ ·27H ₂ O, mainly

Particle size 0.1 to 10 microns ₍ weight expressed on anhydrous basis ₎ NaSKS-6: crystalline layered silicate of formula δ- _Na2Si2O5 Citrate: trisodium citrate dihydrate, activity 86.4%, particle size distribution

Citric acid at 425-850 microns: Anhydrous citrate borate: Sodium borate carbonate: Anhydrous sodium carbonate bicarbonate with a particle size between 200-900 microns: Anhydrous with a particle size distribution between 400-1200 microns Aqueous Sodium Bicarbonate Sulfate : Anhydrous Sodium Magnesium Sulfate : Anhydrous Magnesium Sulfate STPP : Sodium Tripolyphosphate TSPP : Tetrasodium Pyrophosphate MA/AA : 4:1 Acrylate/Maleate Random Copolymer, Average molecular weight

About 70000-80000MA/AA1 : 6:4 acrylate/maleate random copolymer, average molecular weight

About 10000AA : Sodium polyacrylate polymer PA30 with an average molecular weight of 4500: Polyacrylic acid 480N with an average molecular weight of about 4500-8000: Random copolymer with acrylate/methacrylate of 7:3,

The average molecular weight is about 3500 polygel/carbopol: high molecular weight cross-linked polyacrylate PB1: standard formula NaBO ₂ .H ₂ O ₂ anhydrous sodium perborate monohydrate PB4: standard formula NaBO ₂ .3H ₂ OH ₂ O ₂ sodium perborate tetrahydrate percarbonate: anhydrous sodium percarbonate with standard formula 2Na ₂ CO ₃ 3H ₂ O ₂ NaDCC: sodium dichloroisocyanurate TAED: tetraacetylethylenediamine NOBS: sodium Nonanoyloxybenzenesulfonate in salt form NACA-OBS: (6-nonanoylaminocaproyl)oxybenzenesulfonate DTPA: diethylenetriaminepentaacetic acid HEDP: 1,1-hydroxyethanediphosphonic acid DETPMP: Diethyl, sold under the tradename Dequest 2060 by Monsanto

Triaminepenta(methylene)phosphonate EDDS : Ethylenediamine-N,N'-disuccinic acid in sodium salt form, (S,S) isomer MnTACN : Manganese 1,4,7-trimethyl -, 1,4,7-triazacyclononane photoactivated bleaching agent : sulfonated zinc phthalocyanine encapsulated with soluble dextrin polymer Photoactivated bleach 1 : encapsulated with soluble dextrin polymer Sealed Sulfonated Aluminum Phthalocyanine PAAC : Cobalt(III) Pentaamine Acetate Salt Paraffin: Paraffin oil sold under the tradename Winog 70 by Wintershall NaBz : Sodium Benzoate BzP : Benzoyl Peroxidase Oxygenase P 2 Sig 6 sold under code 6 by: Phenylalanine Oxygenase,

and as a cofactor sold by Sigma under number M4758

        6-methyltetrahydropteridine (ptarine) and numbered by Sigma

       DL-Dithiothreitol for sale in D0632, pure enzyme with cofactors

Protease with a weight ratio of 1:2-1:5: produced by Novo Nordisk A/S under the trade name Savinase,

      Alcalase, Durazym, and Merchandise by Gist Brocades

Proteolytic enzymes sold under the name Maxacal, Maxapem, and in

In WO91/06637 and/or WO95/10591 and/or EP251446

Protease Amylase described: Genencor described in WO94/18314, WO96/05295

By trade name Purafact Ox Am ^R and by Novo Nordisk A/S

Sold under the tradenames ^Termamyl® , ^Fungamyl® and ^Duramyl®

Amylolytic enzymes of , and those starches described in WO95/26397

    

Ultra and sold under the trade name Lipomax by Gist Brocades

The lipolytic enzyme cellulase; marketed by Novo Nordisk A/S under the trade names Carezyme,

Cellulase sold by Celluzyme and/or Endolase CMC : sodium carboxymethylcellulose PVP : polyvinyl polymer, average molecular weight 60,000 PVNO : polyvinylpyridine-N-oxide, average molecular weight 50,000 PVPVI : vinylimidazole and ethylene Copolymers of pyrrolidone, average

The sub-weight is 20000 Brightener 1 : 4,4'-bis(2-sulfostyrene)biphenyl disodium Brightener 2 : 4,4'-bis(4-phenylamino-6-morpholino -1,3,5-triazin-2-yl)

       Stilbene-2: 2’-Disodium Disulfonate Polysiloxane Antifoam Agent: Polydimethylsiloxane foam control agent with siloxane-oxygen as a dispersant

A mixture of vinylene copolymers, the foam control agent and the dispersant

The weight ratio is 10:1-100:1 Foam suppressor: 12% polysiloxane/silicon dioxide, 18% stearyl alcohol, 70% granules

Form starch shading agent: Monoplastic lacture mixture of water -based, by BASF

Sold by Aktiengesellschaft under the tradename Lytron 621 SRP1 : Anionic group-terminated polyester SRP2 : Short blocks of diethoxylated poly(1,2-propylene terephthalate)

Polymer QEA: bis((C ₂ H ₅ O)(C ₂ H ₄ O) _n )(CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -(CH ₃ ) bis

((C ₂ H ₅ O)-(C ₂ H ₄ O)) _n , where n=20-30PEI: polyethyleneimine, average molecular weight 1800, average of each nitrogen

The average degree of ethoxylation is 7 oxyethylene residues SCS : Sodium cumene sulfonate HMWPEO : High molecular weight polyoxyethylene PEGx : Polyethylene glycol, molecular weight xPEO : Polyoxyethylene, average molecular weight 5000TEPAE : Tetra Pentaamine ethoxylate BTA : Benzotriazole silica dental abrasive : Precipitate identified as Zeodent 119 provided by J.M. Huber

Silica carboxyvinyl polymer: Carbopol carrageenan provided by B.F. Goodrich Chemical Company: Iota carrageenan provided by Hercules Chemical Company pH: Measured by 1% distilled aqueous solution at 20°C

Example 1

The following high density laundry detergent compositions according to the present invention were prepared:

               I     II     III    IV       V       VILAS               8.0    8.0    8.0    2.0     6.0      6.0TAS                -     0.5     -     0.5     1.0      0.1C46(S)AS          2.0    2.5     -      -       -        -

I     II     III    IV       V       VIC25AS              -      -      -     7.0     4.5      5.5C68AS             2.0    5.0    7.0     -       -        -C25E5              -      -     3.4    10.0    4.6      4.6C25E7             3.4    3.4    1.0     -       -        -C25E3S             -      -      -     2.0     5.0      4.5QAS                -     0.8     -      -       -        -QAS1               -      - -0.8 0.5 1.0 Biite A 18.1 18.0 14.1 18.1 20.0 18.1 Citric acid--2.5-2.5 carbonate 13.0 13.0 27.0 10.0 13.0NA-SKS-6-10.0-10.0 silicate 1.4 3.0 0.3 0.5 0.3 lemon Acids-1.0-3.0-sulfate 26.1 26.1 26.1 6.0-0.3-0.2 — 0.2mA/AA 0.3 0.3 0.3 4.0 1.0 1.0cmc 0.2 0.2 0.4 0.4 0.4 9.0 5.0---overcarbonated carbonated carbonated carbonated carbonated carbonated carbonate Salt---18.0 18.0TAed 1.5 0 4 1.5-3.9 4.2NACA-OBS-2.0 1.0--DETPMP 0.25 0.25 0.25-SRP1-0.2-0.2edds-0.25 0.5 0.5CFAA-1.0-2.0 -        -HEDP              0.3    0.3    0.3    0.3     0.4      0.4QEA                -      -      -     0.2      -       0.5氧酶              0.05   0.05   0.02   0.002   0.005    0.005蛋白酶           0.009    0.009   0.01    0.04     0.05     0.03淀粉酶           0.002    0.002   0.002   0.006    0.008    0.008纤维素酶         0.0007    -       -      0.0007   0.0007   0.0007脂肪酶0.006 - - - 0.01 0.01 0.01 Photoactivated 15 15 15 - 20 20 Bleach (ppm)

II III IV VIPVNO/PVPVI--0.1-Glander 1 0.09 0.09-0.09 0.09 Spice 0.3 0.3 0.4 0.4 0.4 Poly Silicone Antima 0.5 0.5 0.3 0.3 density G/Loin 850 850 850 850 850 850 850 850 850 850 850 850 850 850 850 850 850 850 850 850 850 850 850 Miscellaneous and auxiliary up to 100%

Example 2

The following granular laundry detergent compositions especially suitable for European washing machine conditions were prepared according to the present invention:

II III IV V vid 5.5 7.5 5.0 5.0 6.0 7.0TAS 1.25 1.9-0.8 0.4 0.3C24AS/C25AS-2.2 5.0 5.0 2.25E3S-0.8 1.5 3.0C45E7--3.0TFAA-2.0--C25E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5E5 -      5.5       -      -      -      -QAS           0.8      -        -      -      -      -QAS1           -      0.7      1.0    0.5    1.0    0.7STPP          19.7     -        -      -      -      -沸石A          -      19.5     25.0   19.5   20.0   17.0NaSKS-6/柠檬酸       -     10.6    -      10.6     -      -(79∶ 21) NA-SKS-6-9.0-10.0 10.0 carbonate 6.1 21.4 9.0 10.0 10.0 18.0 Bxyfndromicar-2.0 7.0 5.0-2.0 silicate 6.8-0.3 0.5-citrate-4.0 4.0-sulfate sulfate Salt 39.8 - - - 5.0 - 12.0

II III IV VI sulfate-0.2 0.2 0.2 -ma/AA 0.5 1.6 3.0 4.0 1.0cmc 0.2 0.4 1.0 1.0 0.4 0.4 5.0 12.7---18.0 15.0TAed 0.5 3.1 -5.0 -NACA-OBS 1.0 3.5--2.5DetpMP 0.25 0.3 0.3 0.2Hedp-0.3 0.3 0.3QEA-1.0 1.0 1.02 0.006 0.008 0.01 0.03 0.03 0.055.055.055.055.055.055.055.05555.055.055.055.05555555.055.0555.0555.05.055 0.03 0.03 0.055 0.03 0.03 0.03 0.03 0.055 0.03 0.03 0.03 0.03 0.03 0.03 0. 0.09 0.0-lipter that Enzyme 0.003 0.003 0.006 0.006 0.006 0.004 cellulose enzyme 0.0006 0.0006 0.0005 0.0007 0.0007 0.002 0.002 0.006 0.006 0.003pvno/PVPVI-0.2 0.9 1.3-0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2-01.-019--0.9SRP-0-lyt that 15 27-20 20 bleaching agents (PPM) Light activation 15----bleach (1) (1) (PPM) whitening agent 1 0.08 0.2-0.09 0.15 white agent 2-0.04---spice 0.3 0.5 0.4 0.3 0.4 0.3 Polyxide anti -foaming agent 0.5 2.4 0.3 0.5 0.3 2.0 density G/liter 750 750 750 750 750 Other and auxiliary objects to 100 % Example 3 Preparation is specifically applicable to European washing machine conditions. detergent composition:

I I II II III IV Blown powder

LAS 6.0 5.0 11.0 6.0

TAS 2.0 - - - 2.0

Zeolite A 24.0 - - 20.0

STPP - 27.0 24.0 -

Sulfates 4.0 6.0 13.0 -

MA/AA 1.0 4.0 6.0 2.0

Silicate 1.0 7.0 3.0 3.0

CMC 1.0 1.0 0.5 0.6

  Brightener 1       0.2 0.2 0.2 0.2

  Polysiloxane Antifoam 1.0 1.0 1.0 0.3

DETPMP 0.4 0.4 0.2 0.4 Spray on

                                                                                           

C45E7 - - - - - 5.0

C45E2 2.5 2.5 2.0 -

C45E3 2.6 2.5 2.0 -

Spices 0.5 0.3 0.5 0.2

  Polysiloxane Antifoam 0.3 0.3 0.3 - Dry Additive

QEA - - - - - 1.0

EDDS 0.3 - - - -

Sulfate 2.0 3.0 5.0 10.0

Carbonate 6.0 13.0 15.0 14.0

citric acid 2 5 - - - 2.0

                                                               

Na-SKS-6 10.0 - - -

Percarbonate 18.5 - - -

PB4 - 18.0 10.0 21.5

TAED 2.0 2.0 - 2.0

NACA-OBS 3.0 2.0 4.0 -

Oxygenase 0.05 0.07 0.1 0.01

Protease 0.03 0.03 0.03 0.03

      Lipase   0.008 0.008 0.008 0.004

      Amylase   0.003 0.003 0.003 0.006

I II II III III IV

Brightener 1 0.05 - - - 0.05 Others and Auxiliaries to 100% Example 4 Prepare the following granular detergent compositions according to the invention:

I Blown II II III III IV V V VI Blown Powder

LAS 23.0 8.0 7.0 9.0 7.0 7.0

TAS - - - - - - 1.0 -

C45AS 6.0 6.0 5.0 8.0 - -

C45AES - 1.0 1.0 1.0 -

C45E35 - - - - - - - 2.0 4.0

  Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0

MA/AA - 0.5 - - - - 2.0

MA/AA 1 7.0 - - - - - - - -

AA - 3.0 3.0 2.0 3.0 3.0

Sulfate 5.0 6.3 14.3 11.0 15.0 19.3

Silicate 10.0 1.0 1.0 1.0 1.0 1.0

Carbonate 15.0 20.0 10.0 20.7 8.0 6.0

PEG4000 0.4 1.5 1.5 1.0 1.0 1.0

DTPA - 0.9 0.5 - 0.5

Brightener 2 0.3 0.2 0.3 - 0.1 0.3 Spray on

C45E7 - 2.0 - - - 2.0 2.0

C25E9 3.0 - - - - - - -

C23E9 - - - 1.5 2.0 - 2.0

Fragrance 0.3 0.3 0.3 2.0 0.3 0.3 Agglomerates

C45AS - 5.0 5.0 2.0 - 5.0

LAS - 2.0 2.0 - - 2.0

I I II II III III IV V V VI

Zeolite A - 7.5 7.5 8.0 - 7.5

Carbonate - 4.0 4.0 5.0 - 4.0

PEG4000 - 0.5 0.5 - 0.5

Others (water, etc.) - 2.0 2.0 2.0 - 2.0 dry additives

QAS - - - - - - - 1.0 -

Citric acid - - - - - - - 2.0 -

PB4 - - - - - - - 12.0 1.0

PB1 4.0 1.0 3.0 2.0 -

Percarbonate - - - - - - - 2.0 10.0

Carbonate - 5.3 1.8 - 4.0 4.0

NOBS 4.0 - 6.0 - 0.6

Methylcellulose 0.2 - - - - - - - -

Na-SKS-6 8.0 - - - - -

STS - - - 2.0 - - 1.0 -

cumenesulfonic acid - 1.0 - - - - 2.0

Oxygenase 0.2 0.02 0.05 0.09 0.1 0.05

Protease 0.02 0.02 0.02 0.01 0.02 0.02

Lipase 0.004 - 0.004 - 0.004 0.008

  Amylase 0.003 - 0.002 - 0.003 -

  Cellulase 0.0005 0.0005 0.0005 0.0007 0.0005 0.0005

PVPVI - - - - - - - 0.5 0.1

PVP - - - - - - - 0.5 -

PVNO - - - - 0.5 - 0.3 - -

QEA - - - - - - - 1.0 -

SRP1 0.2 0.5 0.3 - 0.2 -

  Polysiloxane Antifoam 0.2 0.4 0.2 0.4 0.1 -

Magnesium Sulfate - - - 0.2 - - 0.2 -Others and Auxiliaries to 100% Example 5 The following bleach-free detergent composition according to the invention, especially for washing colored clothes, is prepared:

I Blown II II III Blown Powder

Zeolite A 15.0 15.0 -

Sulfates - - 5.0 -

LAS 3.0 3.0 -

DETPMP 0 4 0.5 -

CMC 0.4 0.4 -

MA/AA 4.0 4.0 - Agglomerates

C45AS - - - - 11.0

LAS 6.0 5.0 -

TAS 3.0 2.0 -

Silicate 4.0 4.0 -

Zeolite A 10.0 15.0 13.0

CMC - - - - 0.5

MA/AA - - - - 2.0

Carbonate 9.0 7.0 7.0 Spray on

Spices 0.3 0.3 0.5

C45E7 4.0 4.0 4.0

C25E3 2.0 2.0 2.0 dry additive

- - - - 3.0

Na-SKS-6 - - - 12.0

Citric Acid 10.0 - 8.0

Bicarbonate 7.0 3.0 5.0

Carbonate 8.0 5.0 7.0

PVPVI/PVNO 0.5 0.5 0.5

Oxygenase 0.0009 0.002 0.005

Protease 0.03 0.02 0.05

                                                                                                    

                                                                     

I II II III

                                                                           

                                                                                                                                                                              ,

Sulfate-9.0-density (G/liter) 700 700 700 other and auxiliary to 100 % Example 6 Preparation according to the following detergent composition of the present invention:

                                                                               

Zeolite A 30.0 22.0 24.0 10.0

Sulfate 10.0 5.0 10.0 7.0

MA/AA 3.0 - - - -

AA - - 1.6 2.0 -

MA/AA1 - 12.0 - 6.0

LAS 14.0 10.0 9.0 20.0

C45AS 8.0 7.0 9.0 7.0

C45AES - 1.0 1.0 -

Silicate - 1.0 0.5 10.0

Soap - - 2.0 - -

  Brightener 1 0.2 0.2 0.2 0.2

Carbonate 6.0 9.0 10.0 10.0

PEG4000 - 1.0 1.5 -

DTPA - 0.4 - Spray on

C25E9 - - - - - 5.0

C45E7 1.0 1.0 - -

C23E9 - 1.0 2.5 -

Fragrances 0.2 0.3 0.3 - Dry Additives

I I II II III III IV

Carbonate 5.0 10.0 18.0 8.0

  PVPVI/PVNO 0.5 - 0.3 -

Oxygenase 0.002 0.05 0.0015 0.1

Protease 0.03 0.03 0.03 0.02

Lipase 0.008 - - 0.008

  Amylase                                                              

  Cellulase 0.0002 0.0005 0.0005 0.0002

NOBS - 4.0 - 4.5

PB1 1.0 5.0 1.5 6.0

Sulfates 4.0 5.0 - 5.0

SRP1 - 0.4 -

                                                                                                 

Others and Auxiliaries Up to 100% Example 7 Preparation of the following granular detergent composition according to the present invention

I Blown II III Blown Powder

Zeolite A 20.0 - 15.0

                                                        

Sulphate - - - - 5.0

Carbonate - - - - 5.0

TAS - - - - 1.0

LAS 6.0 6.0 6.0

C68AS 2.0 2.0 -

Silicate 3.0 8.0 -

MA/AA 4.0 2.0 2.0

CMC 0.6 0.6 0.2

Whitening agent 1 0.2 0.2 0.1

DETPMP 0.4 0.4 0.1

STS - - - - 1.0

I Spray on II II III Spray on

C45E7 5.0 5.0 4.0

      Polysiloxane antifoam agent 0.3   0.3   0.1

Spices 0.2 0.2 0.3 dry additives

QEA - - - - 1.0

Carbonate 14.0 9.0 10.0

PB1 1.5 2.0 -

PB4 18.5 13.0 13.0

TAED 2.0 2.0 2.0

QAS - - - - 1.0

                                                                                                                                                                        

Na-SKS-6 - - - 3.0

Oxygenase 0.01 0.02 0.007

Protease 0.03 0.03 0.007

                                                                         

                                                                                           

      Cellulase                                                                      

Sulfate 10.0 20.0 5.0 Density (g/L) 700 700 700 Others and Auxiliaries: The preparation of the detergent according to the following invention 10%

I II II III Blown powder

Zeolite A 15.0 15.0 15.0

Sulfate - 5.0 -

LAS 3.0 3.0 3.0

                                                                                                                                          

DETPMP 0.4 0.2 0.4

I II II III

EDDS - 0.4 0.2

CMC 0.4 0.4 0.4

MA/AA 4.0 2.0 2.0 agglomerates

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.0 3.0 4.0

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 4.0 Spray on

Spices 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

                                                   

Citrate 5.0 - 2.0

Bicarbonate - 3.0 -

Carbonate 8.0 15.0 10.0

TAED 6.0 2.0 5.0

PB1 14.0 7.0 10.0

PEO - - - 0.2

Bentonite - - - 10.0

Oxygenase 0.008 0.01 0.009

Protease 0.03 0.03 0.03

Lipase 0.008 0.008 0.008

                                                                                   

                                                                             

      Polysiloxane Antifoam   5.0   5.0   5.0

Sulfates 850 Others and Auxiliaries - 3.0 - Density (g/L) 850 850 850 Detergents prepared according to the embodiment of the invention 9 to 0% below

II III IVLAS 18.0 14.0 20.0QAS 0.7 1.0-0.7TFAA-1.0 -C23E56.5-1.0 -C45E7-1.0 -C45E3S 1.0 1.0 -STPP 32.0 18.0 22.0 Silicate 9.0 9.0 8.0 carbonate 11.0 7.5 10.0 5.0 bicarbonate-7.5-PB1 3.0 1.0 -PB4-1.0 -NOBS 2.0 1.0 -DetPMP-1.0 -DTPA 0.5-0.2 0.3SRP1 0.3 0.1MA/AA 1.5 2.0 0.5cmc 0.8 0.4      0.4     0.2PEI                       -        -       0.4      -硫酸盐                   20.0     10.0     20.0    30.0硫酸镁                 0.2         -        0.4     0.9氧酶                   0.01       0.01      0.02    0.02蛋白酶                 0.03       0.03      0.02    0.02淀粉酶                 0.008      0.007      -      0.004脂肪酶                 0.004       -        0.002    -纤维素酶               0.0003      -         -      0.0001 Light-activated bleach 30ppm 20ppm-10ppm spice 0.3 0.3 0.1 0.2 whitening agent 1/2 0.05 0.02 0.08 0.1 other and auxiliary to 100 % Example 10 Preparation 10 The numbers are given, the enzymes are expressed as pure enzymes):

II III IV VLAS 11.5 8.8-3.9 -C25E2.5S-3.0 18.0-16.0C45E2.25S 11.5 3.0-15.7 -C23E9-2.7 1.8 1.0C23E7 3.2--5.2-3.1TPKFA 1.6-2.0 0.5 2.0 2.0 Citric acid (50 %) 6.5 1.2 2.5 4.4 2.5 calcium 0.1 0.06 0.1-0.5 0.06 0.1 0.05 0.05SCS 4.0 1.0 3.0 1.2-Borate 0.6-3.0 2.0 2.9 Sodium hydroxide 1.75 1.75 1.0.0 3.666 4.2 2.91, 2-propylene glycol 3.3 2.0 8.0 7.9 5.3 Monitolylamine 3.0 1.5 1.3 2.5 0.8tepae 1.6-1.3 1.2 1.2 1.2 oxygenase 0.007 0.002 0.01 0.01 protease 0.03 0.03 0.02 0.002-0.002-0.00.-amylology -Vender enzyme-0.0002 0.0005 0.0001SRP 1 0.2-0.1 -DTPA-0.3 -PVNO-0.3-0.2 White agent 1 0.2 0.07 0.1-polysilicine anti-foaming agent 0.04 0.02 0.1 0.1 other other And water embodiment 11 prepares according to following liquid detergent composition of the present invention (content is given by weight, and enzyme is represented by pure enzyme):

II III IVLAS 10.0 13.0 9.0 -C25AS 4.0 1.0 2.0 10.0C25E3S 1.0-3.0C25E7 6.0 8.0 13.0 2.5TFAA-4.5APA-TPKFA 2.0-13.0 7.0 Citizens 2.0 1.0 1.5 Twelve Carbonat/ Carbonat/ Carbonat/ Fourteen carbonine base amber 12.0 10.0--Caizi fatty acid 4.0 2.0 1.0-ethanol 4.0 4.0 7.0 2.01, 2-propane 4.0 4.0 2.0 7.0 single ethanlamine--5.0-8.0-TEPAE 0.5-0.5 0.2DetPMP 1.0 1.0 1.0 0.5    1.0氧酶                            0.02     0.02     0.009  0.009蛋白酶                          0.02     0.02     0.01   0.008脂肪酶                           -       0.002     -     0.002淀粉酶                          0.004    0.004    0.01   0.008纤维素酶                         -        -        -     0.002SRP 2                           0.3       -       0.3    0.1硼酸                            0.1      0.2      1.0    2.0氯化钙                           -       0.02      -     0.01 1-0.4--0.1 0.3-0.1 Optical agent 0.5 0.4-0.3NAOH is adjusted to pH 8.0 8.0 7.6 7.7 other and water embodiments 12 Preparation. Parts by weight are given, enzymes are represented by pure enzymes):

II III IVLAS 250--C25AS-13.0 18.0 15.0C25E3S-2.0 2.0 4.0C25E7-4.0TFAA-6.0 8.0APA 3.0 1.0 -TPKFA-15.0 11.0 Cither Fourteen carbonhene-based 15.0--amber sauerkraut fatty acid 1.0-3.5-ethanol 7.0 2.0 2.01, 2-propylene glycol 6.0 8.0 10.0 13.0 single ethanlamine-9.0 9.0tepae-0.3detpmp 2.0 1.2 1.0-oxyase 0.02 0.04 0.08 0.1 protease 0.08 0.02 0.01 0.02 lipase-0.003 0.003 amylase 0.04 0.01 0.01 cellulose enzyme-0.004 0.003SRP2-0.2 0.1 boric acid 1.5 2.5 2.5 Patono soil 4.0-add white agent 1 0.2 0.3-抑 suppression Foaming agent 0.4---0.8 0.7 -naoh to pH 8.0 7.5 8.0 8.2 Other and Water Implementation Examples 13 Preparations according to the following liquid detergent composition (the content is given by weight, enzyme is pressed according to the weight, and enzymes are pressed according to the weight. pure enzyme expression):

IILAS 27.6 18.9C45AS 13.8 5.9C13E8 3.0 3.1 Citic acid 5.4 5.4 5.4 Sodium hydroxide 0.4 3.6 Calcium Pacilitate 0.2 sodium methyl acid-0.5 ethanol 16.5 8.01, 2-propylexol 5.9 5.5 dhabenzine sulfonic acid 1.5 0.8 protease 0.05 0.02 oxygase 0.05 0.08peg-0.7 white whitening agent 2 0.4 0.1 spice 0.5 0.3 other and water embodiments 14 Preparation based on the following invention.

IIC45AS-10.0LAS 7.6 -C68AS 1.3 -C45E7 4.0-

I IIC25E3 - 5.0 Cocoalkyl Dimethyl Hydroxy 1.4 1.0 Ethyl Ammonium Chloride Citrate 5.0 3.0 Na-SKS-6 - 11.0 Zeolite A 15.0 15.0MA/AA 4.0 4.0DETPMP 0.4 0.4PB1 15.0 - Percarbonate Salt - 15.0 TAED 5.0 5.0 Smectite 10.0 10.0 HMWPEO - 0.1 Oxygenase 0.05 0.05 Protease 0.02 0.01 Lipase 0.02 0.01 Amylase 0.03 0.005 Cellulase 0.001 - Silicate 3.0 5.0 Carbonate 10.0 10.0 Foam Suppressant 1.0 2.0 CMC 0.0 0.1 Water and Auxiliary to 100% Example 15 Prepare the following rinse added fabric softener composition according to the present invention: DEQA(2) 20.0 Oxygenase 0.01 Cellulase 0.001 HCL 0.03 Antifoam 0.01 Blue Dye 25 ppm _CaCl 0.20 perfume 0.90 other and water to 100% Example 16 The following fabric softener and dryer added fabric conditioner compositions according to the present invention were prepared:

II III IV VDEQA 2.6 19.0--DEQA (2)---51.8dtmams-26.0 -SDASA-70.0 40.2IV = 0 Harm acid 0.3----Neodol 45-13.0 13.0 --0.02 0.02----1.0--1.0-oxyase 0.02 0.07 0.07 0.1 spice 1.0 1.0 0.75 1.0 1.5glycopers S-20---15.4 Glycerin single hard fatty acid salt--26.0-amber acid 2nd 2nd Somol--0.38--polysilicine anti-foaming agent 0.01 0.01--electrolyte-0.--clay--3.0-dye 10ppm 25PPM 0.01-water and auxiliary 100 % 100 %--- Example 17 Preparation of the following laundry bar detergent composition according to the present invention (contents are given in parts by weight, enzymes are expressed as pure enzymes):

II III VI VI Vi Vi VLAS-19.0 15.0 21.0 6.75 8.8 -C28AS 30.5--15.75 11.2 22.5 May Cinnamin 2.5 9.0-----1.25 1.25 1.25 carbonate 20.0 20.0 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0 calcium carbonate 27.5 39.0 35.0-40.0-40.0 Sulfate 5.0 5.0 3.0 3.0 3.0-5.0TSPP 5.0-5.0 -Stpp 5.0 10.0-7.0 8.0 10.0-10.0--10.0---- 10.0-- 5.0--DETPMP-0.7 0.6 0.7 0.7 0.7 0.7cmc-1.0 1.0 1.0 1.0-1.0 talc-10.0 15.0 10.0--silicate-4.0 5.0 3.0--PVNO 0.03 — 0.02- 0.02- -MA/AA 0.0-0.2 0.4 0.5 0.4SRP 1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 oxygenase 0.002 0.005 0.008 0.01 0.01 0.5 amylase-0.01-0.002-protease-0.004-0.003 0.003--- 0.003 lipase-0.002 — 0.002----cellulose enzyme-.0003-.0003 .0002 -PEO-0.2 — 0.2 0.3-0.3 spice 1.0 0.3 0.2 0.4-0.4 magnesium-3.0 3.0 3.0 3.0 ---0.15 0.1 0.1 0.15--0.1 Light activation-15.0 15.0 15.0-15.0 bleaching agent (PPM) Example 18 Preparation based on the following detergent additives of the following invention:

II IIIILAS-5.0 5.0Stpp 30.0-20.0 Burle A-35.0 20.0 15.0 15.0 -TAed 10.0 8.0-protease-0.3 0.3 amylase-0.06 oxyase 0.1 0.1 auxiliary objects, water and others to 100 % implementation example 19 Preparation 19 The following compact high density (0.96 Kg/l) dishwashing detergent compositions according to the invention:

II III IV VI VII VIIISTPP-54.3 51.4 51.4-50.9 Citrate 35.0 17.0-46.1 40.2-Carbonate-17.0 14.0 14.0-8.0 32.1 Bareshydrocarbarbonate Acid 32.0 14.8 14.8 10.0 10.0 1.0 25.0 3.1 Silicate-2.5-9.0 9.0--PB1 1.9 9.7 7.8 7.8- -PB4 8.6------6.7-6.7-6.7 11.8 4.8 Non-ion type 1.5 2.0 1.5 1.7 1.5 2.6 1.9 5.3TAed 5.2 2.4-2.2-1.4Hedp-1.0---Detpmp-0.6----Mntacn ----0.008-PAAC -0.008 0.01 0.007- -BZP---1.4--lade 0.5 0.5 0.5 0.5 0.6-oxygenase 0.002 0.008 0.01 0.02 0.05 0.1 0.2 protease 0.072 0.053 0.046 0.059 0.06 0.06 0.059 0.06 0.059 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06

II III IV VI VII VIII amylase 0.012 0.012 0.006 0.012 0.013 0.09 0.017 0.03 lipase — 0.001-0.005--BTA 0.3 0.3 0.3 0.3 0.3mA/AA--4.2 -480N 3.3 3.3 3.3 6.0----0.9 Fast 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.1 0.1 Sulfate 7.0 20.0 5.0 2.2 0.8 12.0 4.6 -PH 10.0 10.8 11.3 9.6 10.8 10.9 Other and Water to 100 % Implementation Example 20 Preparation based on the heap of the invention of the invention The following granular dishwashing detergent compositions having a density of 1.02 Kg/l:

II III IV VI VII VIISTP 30.0 30.0 33.0 34.2 29.6 31.1 26.6 17.6 carbonate 30.5 30.0 31.0 39.0 39.4 4.2 45.0 Silicate 7.4 7.5 7.2 13.4 43.7 12.4 Polarate salt Over-carbonate----4.0 -PB1 4.4 4.5 4.5 4.5---NADCC---2.0-1.6 1.0 non-ion type 1.2 1.0 0.7 0.8 1.9 0.7 0.3TAed 1.0---0.8-0.8-0.8-0.8-0.8-0.8-0.8-0.8-0.8-0.8- PAAC            -      0.004   0.004   0.004   -      -     -     -BzP             -       -       -      1.4     -      -     -     -石蜡           0.25    0.25    0.25    0.25    -      -     -     -氧酶           0.007   0.005   0.01    0.02   0.04   0.06  0.08  0.1蛋白酶         0.036   0.015   0.026   0.028   -     0.01   -     -淀粉酶         0.003   0.003 0.006 0.006-0.006-Lipse enzyme 0.005-0.001----BTA 0.15 0.15 0.15--

II III IV Vi Vii Vii Vii Fast 0.2 0.2 0.2 0.1 0.2 0.2 0.2 0.2-sulfate 23.4 25.0 22.0 18.5 30.3 23.1 23.6Ph 10.8 11.3 10.7 11.5 12.7 10.9 Implementation Example 21

The following detergent bar compositions according to the present invention were prepared by extruding a granular dishwashing detergent composition at a pressure of 13 KN/ ^cm2 using a standard 12 head rotary molding machine:

I      II      III      IV       V       VISTPP            -      48.8    49.2     38.0     -       46.8柠檬酸盐       26.4     -       -        -      31.1      -碳酸盐          -      5.0     14.0     15.4    14.4     23.0硅酸盐         26.4    14.8    15.0     12.6    17.7     2.4氧酶           0.05    0.07    0.02     0.01    0.04     0.1蛋白酶         0.058   0.072 0.041 0.033 0.052 0.013 amylase 0.01 0.012 0.012 0.007 0.016 0.002 lipase 0.005- -PB 1.6 7.7 12.2 10.6 15.7 -PB4 6.9--14.4 Non-ion type 1.5 1.5 1.65 0.8 6.3paac-0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.0 Mntacn---0.007 -TAed 4.3 2.5-1.3 1.8Hedp 0.7-0.7-0.4DetpMP 0.65----Paraffin 0.4 0.5 0.55-BTA 0.3 0.3-PA30--MA-MA-MAMA--MA-MAMA--Maa--Maa--Maa--Maa--Maa--Maa--Maa 30- -Maa 30- -Maa 30- -Maa 30- -Maa 30- -MA--MA /AA - - - - - - 4.5 0.55 Spice - - - 0.05 0.05 0.2 0.2

II III IV VI sulfate 24.0 13.0 2.3-10.7 3.4 blocks weigh 25g 25g 20g 30g 10.6 10.7 10.7 10.9 11.2 Other and Water to 100 % Implement Example 22 Preparation is 1.40kg/L. The following liquid dishwashing detergent compositions:

II III IVSTPP 17.5 17.5 17.2 16.0 carbonate 2.0-2.4-silicate 5.3 6.1 14.6 15.7NAOCL 1.15 1.15 1.15 1.25polygen/Carbopol 1.1 1.0 1.25 Non-ion-0.75 0.75---oxye enzyme 0.008 0.01 0.02NAOH-1.9-3.5KOH 2.8 3.5 3.0 -PH 11.0 11.7 10.9 11.0 sulfate, other and 100 % embodiments of the water 23 Preparation based on the following invention drifting liquid composition:

II III non-ion-type 12.0-14.5 non-ion-type mixture-64.0 -Citric 3.2-6.5

II IIIHEDP 0.5-PEG-5.0-Oxyase 0.01 0.03 0.02SCS 4.8-7.0 ethanol 6.0 8.0-The pH 2.0 7.5/Example of the liquid is prepared according to the liquid scrubbing composition according to the following invention:

II III IV VC17ES 28.5 27.4 19.2 34.1 34.1 Oxide 2.0 2.0 3.0 3.0C12 glucosamide-6.0-beet-alkaline 0.9-2.0 2.0 diopine sulfonate 2.0-2.0 -Neodol C11E9-5.0-multicast Hydroxyl fatty acid — --6.5 6.5 6.5 Two sub-ethyl-. Sulfate---2.3 Calcium acid--0.5 1.1 lying citrate 0.06 0.1---1.0----Maphinium 3.3-0.7-Calcium chloride-0.4-sodium sulfate-0.06-0.06 - - Magnesium Sulfate - 0.08 - - - - -

II III IV V hydrogen hydroxide--2.2 2.2 Sodium hydroxide--1.1 1.1 Portrait 200ppm 0.16 0.006-oxyase 0.01 0.02 0.02 0.2 protease 0.05.005.003 0.002 spice 0.09 0.2 0.2 water and Auxiliaries to 100% Example 25 Prepare the following liquid hard surface cleaning compositions according to the invention:

I II III Oxygenase 0.1 0.002 0.01 Amylase 0.01 0.002 0.005 Protease 0.05 0.01 0.02EDTA ^* 0.05 0.05 0.05 Citrate 2.9 2.9 2.9 LAS 0.5 0.5 0.5C12 AS 0.5 0.5 0 5C10.5 0 5C10.5(E) 5 Nonionic 7.0 7.0 7.0 Fragrance 1.0 1.0 1.0 Hexyl Carbitol ^** 1.0 1.0 1.0SCS 1.3 1.3 1.3 Water Equilibrium to 100% ^* Tetrasodium EDTA ^** Diethylene Glycol Monohexyl Ether ^*** All formulations adjusted to pH 7-12 Example 28 Prepare the following spray-on composition for cleaning hard surfaces and removing household mold according to the present invention: Oxygenase 0.05 Amylase 0.01 Protease 0.01 Sodium Octyl Sulfate 2.0 Lauryl Sulfate Sodium 4.0 Sodium Hydroxide 0.8 Silicate 0.04 Butyl Carbitol ^* 4.0 Fragrance 0.35 Water/Auxiliary to 100% ^* Diethylene Glycol Monobutyl Ether Example 27 The following lavatory cleanser bar compositions according to the present invention were prepared.

II IIIC16-18 fat alcohol/50EO 80.0 -las-80.0 non-ion type-1.0-oilide surface active agent-26.0-partial polymerization of partial polymerization of ethylene basin ether and Malo acid 5.0-anhydrodial , The viscosity is 0.1-0.5 polyethylene glycol MW 8000-39.0-water-soluble polyacrylate MW4000-8000-12.0-acrylamide (70 %) and acrylic acid (30 %) -19.0-water-soluble NA conjugate three Sodium Polyphothexate 10.0--oxyase 0.05 0.09 0.15 Dyes 2.5 1.0 1.0

II III spice 3.0-7.0koh/HCL solution PH6-11 Example 28 Preparation according to the following invention toilet cleaning composition:

IIC14-15 Straight Chain Alcohol 7EO7EO 2.0 10.0 Citric acid 10.0 5.0 oxyase 0.05 0.1detpmpMP-1.0 Dyes 2.0 1.0 spice 3.0NAOH PH6-11 Water and auxiliary items Establishment Example 29 Preparation is based on the following invention. Teeth cleaning tablets:

I ii oxyase 0.1 0.08 protease 0.05 2.0 sodium bicarbonate 39.0 39.0 apple acid 14.0 14.0 amino sulfonic acid 3.0TAed 2.0 2.0 dye/spice 2.0pb1 16.0eda 3.0 3.0 3.0

IIPEG 10,000 6.0 6.0 Potassium sulfate 13.0 13.0 sodium carbonate 1.0 1.0las 1.0 1.0 Thermal silicon 2.0 2.0 Implementation Example 30 Preparation based on the following cleansing agent composition according to the present invention:

I ii III IV sorrine glycol (70 % aqueous solution) 35.0 35.0 35.0 35.0peg-6 1.0 1.0 1.0 1.0 silicon tooth abrasive 20.0 20.0 20.0 20.0 sodium fluoride 0.2 0.2 titanium dioxide 0.5 0.5 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 oxyase 0.05 0.08 0.1 0.2 protease 0.05 0.1 0.9 2.0 sodium sodium sulfate (27.9 % 4.0 4.0 4.0 4.0 aquatic solution) Sperm 1.0 1.0 1.0 carboxyl polymer 0.3 0.3 0.3 corner fork gum 0.8 0.8 0.8 other and water. To 100% Example 31 Prepare the following oral rinse compositions according to the invention:

II III IVSDA 40 alcohol 8.0 8.0 8.0 8.0 spices 0.08 0.08 0.08 0.08

I         II       III      IV乳化剂                  0.08      0.08     0.08     0.08氟化钠                  0.05      0.05     0.05     0.05甘油                    10.0      10.0     10.0     10.0增甜剂                  0.02      0.02     0.02     0.02氧酶                    0.05      0.08     0.1      0.2蛋白酶                  0.01      0.09     0.2      2.0苯甲酸                  0.05      0.05     0.05     0.05氢氧化钠                0.2 0.2 0.2 0.2 Dye 0.04 0.04 0.04 0.04 Others and water Up to 100%

Claims (22)

1. cleaning combination, it comprises the oxygenase based on protein substrate.

2. according to the cleaning combination of claim 1, so wherein said oxygenase feature based on protein substrate is also at iron sulphur or iron heme oxygenase and/or the oxygenase relevant with heavy metal.

3. according to the cleaning combination of claim 1-2, the content of wherein said oxygenase based on protein substrate by the weight of total composition, is 0.0001%-2%, preferred 0.001%-0.5%, the more preferably pure enzyme of 0.002%-0.1%.

4. according to the cleaning combination of arbitrary aforesaid right requirement, wherein said oxygenase based on protein substrate is alkaline.

5. according to the cleaning combination of arbitrary aforesaid right requirement, it also comprises cofactor.

6. according to the cleaning combination of claim 5, wherein cofactor is being 10 based on the pure oxygen enzyme of protein substrate and the weight ratio of cofactor: 1-1: 10, preferred 5: 1-1: 8, more preferably 1: 2-1: 5 are included in the said composition.

7. according to the cleaning combination of arbitrary aforesaid right requirement, it also comprises detergent enzyme, is preferably selected from cellulase, lipase, proteolytic enzyme, amylase and/or its mixture.

8. according to the cleaning combination of claim 6, wherein said enzyme is a serine protease, is more preferably by genus bacillus, the bacterial serine proteolytic enzyme that preferred subtilis and/or Bacillus licheniformis obtain.

9. according to the cleaning combination of arbitrary aforesaid right requirement, it also comprises another kind of bleach system.

10. according to the cleaning combination of claim 9, wherein said bleach system is conventional activatory bleach system.

11. according to the cleaning combination of claim 10, wherein SYNTHETIC OPTICAL WHITNER is selected from perborate and/or percarbonate, activator is selected from tetraacetyl ethylene diamine, nonanoyl oxygen benzene sulfonate and/or 3,5-trimethyl hexanol oxygen base (hexanoloxy) benzene sulfonate.

12. according to the cleaning combination of claim 9, wherein said bleach system is that another kind of enzyme is urged bleach system.

13. according to the cleaning combination of claim 9, wherein said bleach system is based on the bleach system of metal catalyst.

14. according to the cleaning combination of claim 13, wherein said metal catalyst is the transition metal complex that encircles the rigidity ligand mostly.

15. according to the cleaning combination of claim 13-14, wherein said metal catalyst is a manganese.

16. according to the cleaning combination that arbitrary aforesaid right requires, it is the form of additive.

17. a fabric sofetening composition, it comprises based on proteic oxygenase and the cats product that contains two long-chains.

18. be used for cleaning fabric and/or removing textile stains and/or keep the whiteness and/or the soft fabric of fabric and/or make fabric that bright-coloured outward appearance be arranged and/or suppress cleaning that dye for fabrics shifts and/or the purposes of soft compound based on the oxygenase of protein substrate.

19. the oxygenase based on protein substrate is being used for cleaning for example purposes of the cleaning combination of floor, wall, bathroom tile etc. of crust.

20. based on the oxygenase of protein substrate purposes at the cleaning combination that is used for craft and machine wash up.

21. the purposes of oxygenase in oral cavity and/or tooth usefulness cleaning combination based on protein substrate.

22. the oxygenase based on protein substrate is being used for the sterilize cleaning on processed surface and/or the purposes of soft compound.