CN1233278A - Detergent compositions comprising antibody controlled enzymatic activity - Google Patents

Abstract

The present invention relates to detergent compositions including laundry, dishwashing, household cleaning compositions, comprising an enzyme and an enzyme-directed antibody in order to provide excellent cleaning performance and controlled enzymatic activity.

Description

Detergent composition containing antibodies to control enzyme activity

Field of Invention

The present invention relates to detergent compositions, including laundry, dishwashing and household washing compositions, which contain enzymes and antibodies directed against said enzymes to provide excellent wash performance and control of enzyme activity.

Background of the Invention

An important part of the system that protects vertebrates against bacterial and viral infection is the humoral immune system. Specialized cells present in the bone marrow, lymphoid tissues, and blood produce immunoglobulins (antibodies), which arise in response to external small or large molecules entering the body and bind to structures outside the body causing their destruction. This molecule outside the body is called an antigen. Antibodies are directed against an antigenic determinant or hapten of an antigen, such as an amino acid sequence, oligosaccharide, polysaccharide, lipopolysaccharide, glycoprotein, lipoprotein, lipoteichoic acid portion.

Specific antibodies produced in this manner can bind to the antigen that caused their formation to form antigen-antibody complexes. Antibody molecules have binding sites that are very specific and complementary to the structural properties of the antigen that caused their formation.

This highly specific antigen-antibody recognition and binding has found several applications in various fields such as analytical chemistry, therapeutic treatment, health care and beauty, such as recognition agents, binding agents or carrier agents.

EP479600, EP453097 and EP450800 relate to the use of antibodies or fragments thereof to provide an active ingredient at a target site. EP481701 discloses a therapeutic composition for topical application comprising microcapsules comprising a beneficial agent at a target site and which microcapsules contain antibodies or antibody fragments specific for the target site or lectins.

WO92/04380 describes shaped human antibodies or shaped human antibody fragments to human polymorphic mucin for use in the treatment and diagnosis of cancer. The use of Epstein-Barr virus specific polypeptides to generate antibodies and diagnose and treat the disease is disclosed in WO94/06470.

Oral compositions containing antibodies for caries prevention or periodontal disease treatment are described in detail in WO95/01155, WO95/00110, WO95/10612, EP140498, GB2151923, GB2176400, GB2167299, DE4324859, US5401723 and EP280576.

EP673683 and EP542309 disclose hair cosmetic compositions containing antibodies and polymer emulsions of hair or hair extracts derived from egg yolks or poultry immunoreacted with the hair or hair extracts to provide reduced hair damage, softness, moist feel And smooth, the composition is absorbed only on specific parts of the hair.

Compositions containing antagonists (tyrphostins or antibodies) of epidermal and transforming growth factors useful in the treatment of acne are described in WO 95/24896.

The use of antibodies throughout detergents has been suggested in Unilever Researchprijs "Moleculezoekt partner" 1992, where modified antibodies for specific stains were suggested for bleaching processes.

The production of antibodies by hyperimmune reactions of mammals, such as cattle, with vaccines derived from E. coli is described in EP102831. EO400569 discloses a method for preparing a vaccine composition for dental caries in nasal drops containing an antigen produced by binding a protein antigen expressing gene in a chromosomal gene of a Streptococcus var. GS-5 strain. WO 94/25591 discloses preparation of antibodies or functionalized fragments thereof from heavy chain immunoglobulins of camelidae.

Detergent compositions now include a complex combination of active ingredients for some specific needs: surfactant systems, detergent enzymes, bleaching agents, builder systems, suds suppressors, soil suspending agents, soil release agents, fluorescent Brighteners, softeners, dispersants, dye transfer inhibiting compounds, abrasives, fungicides, fragrances, have really improved their overall performance over the years.

Current laundry detergent formulations typically include enzymes, among others, to provide cleaning and fabric care benefits.

However, excessive exposure of the substrate to enzymatic activity and/or transfer of enzymatic activity to the post-main wash portion of the wash cycle, such as the rinse, spin and/or drying steps can lead to undesirable effects. This is illustrated by various examples where residual enzyme activity at the end of the wash cycle, during the rinse and/or drying steps can have a negative effect. For example, detergent proteolytic enzymes are known to reduce the tensile strength of the wool component of fabrics in some cases, lipolytic enzymes to potential odor formation, cellulolytic enzymes to potential loss of tensile strength, starch Enzymes will interfere with post-wash starch treatments and peroxidases will cause discoloration.

However, it should be noted that loss of tensile strength of the fabric due to use/wear is also an unavoidable consequence and can be caused by damage to the bleaching components during the laundry process, especially if the fabric is stained with metallic compounds.

We have now surprisingly found that antibodies generated using specific enzymes avoid unwanted residual enzyme activity at the end of the wash cycle, during the rinse and/or drying steps. Enzyme activity can be fully controlled during washing, so negative effects due to over-exposure of the substrate to enzymes can now be avoided.

It is therefore an object of the present invention to provide laundry, dishwashing or household cleaning detergent compositions which provide excellent cleaning performance and controlled enzyme activity.

The above needs can be met by special detergent compositions including laundry, dishwashing and hard surface cleaning which contain enzymes and antibodies directed to said enzymes.

Invention Summary

The present invention relates to detergent compositions, including laundry, dishwashing and household cleaning compositions, which contain enzymes and antibodies raised against said enzymes to provide excellent wash performance and controlled enzyme activity.

Detailed description of the invention Antibody

An essential component of the detergent compositions of the present invention are antibodies.

Immunoglobulins are classified into five classes, namely IgM, IgG, IgA, IgD and IgE. Preferred classes of immunoglobulins are IgG and IgA. Secreted sIgAs found in human secreted body fluids such as milk, saliva, respiratory and intestinal fluids are specifically designed to survive in said secretions, where they have improved binding characteristics and resistance to proteolysis.

Antibodies, which may be monoclonal or polyclonal or antibody fragments, can be produced by conventional techniques in the art, for example by using recombinant DNA techniques to produce antibody variants with novel properties such as reduced immunogenicity, increased affinity, Changed dimensions etc. Special bindings can also be used. For the present invention, monoclonal antibodies are preferred, more preferably fragments thereof. These fragments can similarly be produced by conventional techniques, such as enzymatic digestion with papain or pepsin, or using recombinant DNA techniques. Antibody fragments can also be prepared by conventional recombinant DNA techniques. Antibodies and antibody fragments may be humanized as in Meded.-Fac.Landbouwkd.ToegepastBio1.Wet.(Univ.Gent)(1995), 60(4a, Forum for Applied Biotechmology, 1995, p. 1 part), 2057-63.

Heavy and light chains consist essentially of constant and variable domains. In organisms that produce immunoglobulins in their native state, constant domains are important for many functions, but variable domains are sufficient for many applications in industrial processes and products. A number of methods have thus been described to generate antibody fragments.

The antibody fragments used may be Fab, Fv, scFv or any other fragment with similar binding properties, the preferred method of making antibody fragments is by recombinant DNA techniques whereby the fragments are expressed in genetically transformed organisms.

Antibodies and antibody fragments produced by recombinant DNA techniques are not necessarily identical to antibody fragments produced in vertebrates, but have the same binding properties as assessed by their Km, Ki and Kcat. For example, they may include different amino acid sequences and/or glycosylation, especially at the ends of the fragments, than are found in fragments in antibodies produced by other methods. Somewhat similarly, antibody fragments produced by recombinant DNA techniques may include additional amino acid sequences at their termini that have no counterparts in antibodies produced by other methods.

A related possibility is that the binding agents used in the invention are natural or synthetic polymers that mimic the specific binding activity of the complementary regions of natural antibodies. The polymer is eg a polypeptide or a polymer imprint (Angew. Chem. Int. Ed. Engl. 1995, 34, pp. 1812-1832).

Mammals or poultry with corresponding antigens can be immunized by the usual methods for preparing antibodies. As mammals to be immunized, mice, rabbits, goats, sheep, horses, cows and the like can be used. Antibody (immunoglobulin part) can be separated from antiserum, milk or egg according to conventional antibody purification methods, including salting out method, Polson extraction method, gel filtration chromatography, ion exchange chromatography, affinity chromatography, etc., salt The precipitation method uses ammonium sulfate to produce a precipitate, which is then dialyzed against saline to obtain a purified precipitate for use as an antibody.

As described in Tibtech.Dec 1995, Vol. 13, pp. 522-527; Plant Mol. Biol., 26, pp. 1701-1710, 1994 and Biotechnol.proj.1991, 7, pp. 455-461 and US5202422, Plants are also capable of synthesizing and assembling each antibody molecule, and antibodies can be produced on a large scale. Antibodies can also be produced by biofermentation in microorganisms such as E. coli or S. cerevisiae as described in EP667394.

Techniques for producing antibody fragments are known in Saiki et al., Science 2301350-54 (1985); Orlandi et al., PNAS USA 863833-7 (1989); WO89/09825; EP368684; WO91/08482 and WO94/25591.

The disadvantage due to prolonged activity of the enzyme can be avoided by effectively controlling the enzyme activity by adding specific corresponding antibodies. The antibody can be polyclonal - directed against the entire enzyme structure - or monoclonal - directed against a specific epitope controlling the enzymatic activity of the region of the enzyme structure. Antibodies raised against specific enzymes effectively inactivate the enzyme through antibody-antigen binding at or very close to the active site. Formation of this complex results in deactivation of the enzyme, which can be explained by deformation of the three-dimensional structure and/or steric hindrance at the cleft of the substrate. Enzyme deactivation can also be achieved by precipitation of the complex antibody-antigen from the wash solution. Due to the very high specificity and efficiency of the antibody-antigen interaction, other detergent actives are not affected.

Enzyme-directed antibodies are preferably included in the detergent compositions of the invention at a level of 10E-6-10E+1% by weight of the total composition. In some cases, antibodies raised against specific enzymes have the ability to bind other enzymes with a highly similar structure, providing cross-reactivity. The molecular ratio of antibody to enzyme is usually 100:1 or less, preferably 50:1 or less. For monoclonal antibodies or fragments thereof, the molecular ratio of antibody to enzyme is usually 50:1 or less, preferably 20:1 or less.

The enzyme-directed antibodies are released in the wash solution after a delay time allowing for excellent enzyme performance achieved at the end of the wash process.

Thus, the antibodies are preferably added to a release agent to control the time and rate of their release in the wash solution, the physical form of the antibody-containing release agent being adapted to that of the corresponding detergent or additive.

For granular and powder detergents and cleaning products, antibodies and release agents can be included in the granule. The antibody particles may suitably contain various granulation aids, binders, fillers, plasticizers, lubricants, cores and the like. Examples of them include cellulose (e.g. cellulose fibers or in microcrystalline form), cellulose derivatives (CMC, MC, HPC, HPMC), gelatin, starch, dextrin, sucrose, polyvinylpyrrolidone, PVA, PEG, salts (such as sodium sulfate, calcium sulfate), titanium dioxide, talc, clays (kaolin or bentonite) and nonionic surfactants. Other related substances added to the granules are described in EP304331.

The release agent can be, for example, a coating. The coating protects the particles in the wash environment for a certain period of time. Coatings are generally added to the granules at levels of 1% to 50% by weight (based on the weight of the uncoated dry granule), preferably 5% to 40% by weight. The amount of coating applied to the particle will depend to a considerable extent on the nature and composition of the coating and the type of protection the coating should provide to the particle. For example, the thickness of the coating or multilayer coating applied to any of the above particles will determine the release time of the contents of the particle. One possible multilayer coating could be a coating in which eg a fast release coating is applied on top of a slow release coating.

Helper granules can also be constructed by comprising detergent enzymes and fast release agents in the outer layer and antibodies and slow release agents in the inner core.

Suitable release coatings are coatings which, under the conditions prevailing during their use, result in release of the antibody-containing particle content. Thus, for example, when a formulation of the invention is added to a wash liquor containing a detergent (typically containing, for example, one or more types of surfactants), the coating should ensure that when it is added to the wash medium, the particles contain The substance is released by the release agent.

Preferred release agent coatings are substantially water insoluble coatings. The release coating suitable for the wash medium may suitably contain a material selected from the group consisting of cellulose and cellulose derivatives, PVA, PVP, tallow, hydrogenated tallow, partially hydrogenated tallow, fatty acids and fats of natural and synthetic origin Alcohols, long-chain fatty acid mono-, di- and triglycerides (eg glycerol monostearate), ethoxylated fatty alcohols, latexes, hydrocarbons with a melting point of 50-80°C, and waxes. Melt coating agents are a preferred class of fast or slow release coating agents which can be used without dilution with water. See Controlled Release Systems: Fabrication Technology, Vol. I, CRC Press, 1988 for additional information on slow release coatings.

The coating may also suitably contain substances such as clays (eg kaolin), titanium dioxide, pigments, salts (eg calcium carbonate) and the like. Those skilled in the art will know of other coating components of relevance in the present invention.

In liquid detergent compositions, the antibody may be added as a dispersion of particles containing a release agent other than the antibody. Antibodies can be in liquid or solid form. Such as Surutzidis A． As described in EP583512 by et al., suitable particles consist of a porous hydrophobic material (such as silica with an average pore diameter of 500 angstroms or greater) containing a solution of antibody and surfactant in the pores.

The release agent may be a coating that protects the particles for a certain period of time during the wash cycle. The coating is preferably a hydrophobic coating material, such as a hydrophobic liquid polymer. The polymer may be an organopolysiloxane oil, or a high molecular weight hydrocarbon or a water-insoluble but water-permeable polymeric substance such as carboxymethylcellulose, PVA, PVP. The properties of the polymer are chosen to obtain a suitable release profile of the antibody in the wash solution. detergent enzyme

An essential component of the detergent compositions of the present invention is one or more enzymes which provide wash performance and/or fabric care benefits.

Described enzyme comprises and is selected from hemicellulase, peroxidase, protease, glucoamylase, amylase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, polygalactose Aldolase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malic enzyme, beta-glucanase , arabinosidase, hyaluronidase, chondroitinase, laccase, or a mixture thereof.

Preferred combinations are detergent compositions comprising a mixture of conventionally suitable enzymes, such as proteases, amylases, lipases, cutinases and/or cellulases, in combination with one or more plant cell wall degrading enzymes.

Cellulases useful in the present invention include bacterial or fungal cellulases. They preferably have a pH optimum between 5-12 and an activity in excess of 50 CEVU (Cellulase Viscosity Units). Suitable cellulases are described in Barbesgoard et al. US4435307, J61078384 and WO96/02653 which disclose fungal cellulases produced by Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP739982 discloses cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2075028, GB-A-2095275 and DE-OS-2247832 and WO95/26398.

Examples of such cellulases are cellulases produced by Humicola insolens strains (Humicola grisea var. thermoidea), in particular Humicola strain DSM 1800.

Other suitable cellulase is the cellulase obtained by Humicola insolens with molecular weight about 50KDa, isoelectric point 5.5 and containing 415 amino acids; about 43kD endoglucanase showing cellulase activity obtained by Humicola insolensDSM 1800 ; a preferred endoglucanase component has the amino acid sequence disclosed in PCT patent application WO91/17243. Also suitable cellulases are the EGIII cellulases from Tricho derma longibrachiatum described in WO 94/21801, Genencor, published September 29, 1994. Particularly suitable cellulases are cellulases having a color care effect. Examples of such cellulases are the cellulases described in EP patent application No. 91202879.2 (Novo) filed on 06.11.1991. Carezyme and Celluzyme (NovoNordisk A/S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases having fabric care and/or washing properties are described in WO96/34092, WO96/17994 and WO95/24471.

The cellulases are typically incorporated into detergent compositions at a level of from 0.0001% to 2% pure enzyme by weight of the composition.

Other preferred enzymes which may be included in the detergent compositions of the present invention include lipases. Suitable lipases for use in detergents 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 which show positive immunological cross-reactivity with lipase antibodies. 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 from Chromobacter viscosum, eg from Toyo Jozo Co., Tagata, Japan. Lipase from Chromobacter viscosum var.lipolyticum NRRLB 3673; obtained from US Biochemical Corp. and Chromobacterviscosum lipase from Disoynth, The Netherlands; and a lipase from Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 Lipase ^R and Lipomax ^R (Gist-Brocades) and Lipolase ^R and Lipolase Ultra ^R (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP258068, WO92/05249 and WO95/22615 to Novo Nordisk and WO94/03578, WO95/35381 and WO96/00292 to Unilever.

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

Lipases, phospholipases, cutinases and/or esterases are typically incorporated into detergent compositions at levels of 0.0001% to 2% active enzyme by weight of the detergent composition.

Suitable proteases are the subtilisins (subtilisins BPN and BPN') obtained from the particular genus Bacillus subtilis and Bacillus licheniformis. A suitable protease is obtained from a strain of Bacillus, which has maximal activity throughout the pH range of 8-12, developed by Novo Industries A/S of Denmark (hereinafter "Novo") and marketed as ESPERASE(R). The preparation of this and similar enzymes is described in British Patent 1,243,784 to Novo. Other suitable proteases include Novo's ALCALASE(R), DURAZYM(R), and SAVINASE(R), and those sold by Gist-Brocades under the tradenames MAXATASE(R), MAXACAL(R), PROPERASE(R), and MAXAPEM(R) (Maxacal for Protein Engineering). 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 the protease in EP 199404, Venegas, published October 29, 1986, which relates to a modified bacterial serine proteolytic enzyme, which is referred to herein as "Protease A". Suitable is the protease referred to herein as "Protease C", which is a variant of the alkaline serine protease obtained from Bacillus in which arginine is replaced by lysine at position 27 and tyrosine at position 104 Instead of valine, aspartic acid was replaced by serine at position 123 and threonine was replaced by alanine at position 274. Protease C is described in EP90915958.4 published on May 16, 1991, corresponding to WO91/06637. Genetically modified variants, especially of Protease C, are also included in the present invention.

A preferred protease called "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from the precursor carbonyl hydrolase by numbering according to Bacillus amyloliquefaciens subtilisin, in the corresponding At the position of +76 of the carbonyl hydrolase, it is also preferably at the position corresponding to +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128 , +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and/or +274 bits At one or more amino acid residue positions, a variety of amino acid residues are replaced with different amino acids, which is obtained in WO95/10591 and C.Ghosh et al., entitled "Bleaching Compositions Containing Proteases" on October 13, 1994 The application is described in patent application US № 08/322677.

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 WO95/23211.

See also the high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140A to Novo. Enzyme detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529A to Novo. If desired, proteases with reduced absorption and improved hydrolysis can be obtained as described in Procter & Gamble, WO95/07791. A recombinant trypsin-like protease suitable for use in the detergents of the present invention is described in WO 94/25583 to Novo. Other suitable proteases are described in EP516200 to Unilever.

Proteolytic enzymes are added to the detergent compositions of the present invention at a level of 0.0001%-2%, preferably 0.001%-0.2%, more preferably 0.005%-0.1% pure enzyme by weight of the composition.

Amylases (alpha and/or beta) may be included to remove carbohydrate based stains. WO 94/02597, Novo Nordisk A/S, published February 3, 1994, describes detergent compositions incorporating mutant amylases. See also WO 95/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases known for use in detergent compositions include alpha- and beta-amylases Alpha-amylases are known in the art, including in US5003257, EP252666, WO91/00353, FR2676456, EP285123, EP525610, EP368341 and Amylases described in British Patent Specification 1296839 (Novo). Other suitable amylases are the stability-enhanced amylases described in WO 94/18314, published 18.08.1994 and WO 96/05295, published 22.02. 1996 by Genencor and as disclosed in Apr. 95 Amylase variants obtained from Novo Nordisk A/S with additional modifications in the previous parent described in WO95/10603. Also suitable are the amylases described in EP277216, WO95/26397 and WO96/23873 (all by Novo Nordisk).

Examples of commercial alpha-amylase products are Purafect Ox Am® available from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl® all available from Novo Nordisk A/S, Denmark. WO 95/26397 describes other suitable amylases: α-amylases characterized in that they are determined by the Phadebas® α-amylase activity test in the temperature range 25°C-55°C and at a pH of 8-10 Has a specific activity at least 25% higher than that of Termamyl(R). Suitable are variants of the aforementioned amylases described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties in terms of activity level and thermostability combined with higher activity levels are described in WO 95/35382.

Amylolytic enzymes are added to the detergent compositions of the present invention at levels of 0.0001%-2%, preferably 0.00018%-0.06%, more preferably 0.00024%-0.048% pure enzyme by weight of the composition.

It is believed that enzymatic bleaching systems based on high levels of phenol oxidase and builders can cause fading of sensitive dyes on fabrics.

Peroxidases are used in combination with an oxygen source, such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used for "solution bleaching", ie to prevent the transfer of dyes or pigments that have been released from a substrate during washing operations to other substrates in the wash solution.

Peroxidases (EC 1.11.1) for use in the present invention are very suitably, for example, any peroxidases encompassed by enzyme class EC 1.11.1.7; peroxidase fragments, exhibiting peroxidase activity and synthetic or Semisynthetic peroxidase derivatives (eg with porphyrin ring systems) or microbial peroxidases (see eg US4077768, EPO537381, WO91/05858 and WO92/16634) are also relevant to the present invention. Suitable peroxidases are known from microbial, vegetable and animal sources. Other possible peroxidases can be obtained by protein engineering methods in which one or several amino acids of the native peroxidase have been replaced by other amino acids.

The peroxidase is preferably obtainable from plants (eg horseradish or soybean peroxidase) or microorganisms, eg fungi or bacteria. Certain preferred fungi include strains belonging to the subphylum Auteromycetes, class Hyphomycetes, for example, Fusarium, Humicola, Trichoderma, Myromyces, Verticillium, Arthromyces, Calnier, Ulocladium , Embellisia, Cladosporium or Dreschlera, especially Fusarium oxysporum (DSM2672), Humicola insolens, Trichodermaresii, Verticillum alalboatrum (IFO 6113), Verticillum alalboatrum, Verticillium dahlia, Arthromyces ramosus (FERM P-7754) , Ulocladium chartarum, Embellisia alli or Dreschlera halodes.

Other preferred fungi include strains belonging to the subdivision Basidiomycotina, class Basidiomycetes, such as Coprinus, Phanerochaete, Coriolus or Trametes, especially Coprinus cinereusf.microsporus (IFO8371), Coprinus macrorhizus, Phanerochaetechrysosporium (for example, NA-12) or Trametes (formerly known as Polyporus), eg T. versicolor (eg PR428-A). More preferred fungi include strains of the subdivision Zygomycetes, class Mycoraceae, such as Rhizopus or Mucor, in particular Mucor permadena.

Certain preferred bacteria include strains of the order Actinomycetes, such as Streptomyces sphaeroides (ATTC 23965), Streptomyces thermophiles (IFO 12382), or Streptomyces verticillium subsp. Verticillium. Other preferred bacteria include Bacillus pumilus (ATCC 12905), Bacillus stearothermophilus, Rhodobactersphaeroides, Rhodomonas palustri, Streptococcus lactis, Pseudomonas purrocinia (ATCC 15958) or Pseudomonas fluorescens (NRRL B-11). More preferred bacteria include strains belonging to the genus Myxococcus such as Myxococcus viridans.

Other related peroxidases are "haloperoxidases" (see e.g. US4937192), such as chloroperoxidase (EC 1.11.1.10), bromoperoxidase and iodoperoxidase (EC1.11.1.8). Other potential sources of useful peroxidases are listed in B. C. Saunders et al., Peroxidase, London, 1964, pp. 41-43.

Peroxidase can also be a kind of such peroxidase, and its preparation method comprises by cultivating the host cell transformed with recombinant DNA vector under the condition that allows expressing peroxidase in culture medium, and by culturing The peroxidase is recovered from the base, and the vector carries the DNA sequence encoding the peroxidase and the functional part encoding the DNA sequence allowing the expression of the DNA sequence encoding the peroxidase. Recombinantly produced peroxidases are especially peroxidases obtained from Coprinus po., especially C. macrorhizus or C. cinereus according to WO 92/16634.

The term peroxidase includes substances having peroxidase activity, such as peroxidase active fragments obtained from cytochrome, hemoglobin or peroxidase, and synthetic or semisynthetic derivatives thereof, such as iron porphyrin, Iron porphyrins and iron phthalocyanines and their derivatives. The peroxidase used in the preparations according to the invention is very suitably Coprinus peroxidase, Myxococcus peroxidase or horseradish peroxidase.

Detergent compositions containing peroxidases are described, for example, in PCT International Application WO 89/099813 and European Patent Application No. 91202882.6 filed November 6, 1991.

Laccases are also suitable.

The peroxidase is usually added to the detergent composition of the present invention at an active enzyme level of 0.0001%-2% by weight of the detergent composition.

Builders are generally present at levels of 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 syringates (C3-C5 substituted alkyl syringates) and phenol. Sodium percarbonate or sodium perborate are preferred sources of hydrogen peroxide.

By xylanolytic enzyme is meant any enzyme that degrades, eg hydrolyzes and/or modifies xylan-containing polymers associated with hemicellulose and other plant polysaccharides. Xylanolytic enzymes include commercially available xylanases such as Pulpzyme HB and SP431 from Novo Nordisk A/S, Lyxasan from Gist-Brocades and Optipulp and xylanase from Solvay.

Xylanase is added to the detergent compositions of the present invention at a level of 0.0001%-2%, preferably 0.0005%-0.5%, more preferably 0.001%-0.1% pure enzyme by weight of the total composition.

By chondroitinase is meant any enzyme that degrades, eg hydrolyzes and/or modifies complex polysaccharide chains found eg in chondroitin sulfate. Chondroitinases ABC, AC, B and C are also known as chondroitin ABC, AC, B and C lyases and are classified as EC4.2.2.4, EC4.2.2.5 and EC4.2.2, respectively.

Chondroitinase is added to the detergent composition of the present invention at a level of 0.0001%-2%, preferably 0.0001%-0.5%, more preferably 0.001%-0.1%, by weight of the total composition.

By cutanase is meant any enzyme that degrades, eg hydrolyzes and/or modifies complex polysaccharide chains found eg in cutan sulfate. Cutinases are also known as endo-β-galactosidases and are classified as EC 3.2.1.103.

Cutinase is added to the detergent compositions of the present invention at a level of 0.0001%-2%, preferably 0.0001%-0.5%, more preferably 0.001%-0.1% pure enzyme by weight of the total composition.

Hyaluronidase refers to any enzyme that degrades, eg hydrolyzes and/or modifies, glycoproteins and proteoglucans containing hyaluronic acid, chondroitin, chondroitin sulfate and keratan sulfate. Hyaluronidases are carbohydrases in the following classifications EC 3.2.1.35, EC 3.2.1.36 and EC 4.2.2.1, commercially available from Fluka, Sigma and Biozyme.

Hyaluronidase is added to the detergent compositions of the present invention at a level of 0.0001%-2%, preferably 0.0001%-0.5%, more preferably 0.001%-0.1% pure enzyme by weight of the total composition.

Endoglucanase refers to any enzyme that degrades, e.g. hydrolyzes and/or modifies 1,6-α-glycosidic linkages in glucan substrates; ) bond is a high molecular weight polysaccharide with a D-glucose backbone. The endoglucanase may be of fungal origin, eg of the penicillin species or may be expressed in any other suitable host organism by cloning techniques known in the art. The naturally occurring endoglucanase derived from lilacin is especially suitable for use in neutral pH or granular detergents. The endo-glucanase may be a carbohydrase of EC class EC 3.2.1.11, commercially available from Sigma Chemicals, Fluka Fine Chemicals and Novo Nordisk.

Endoglucanase is added to the detergent composition of the present invention at a content of 0.0001%-2%, preferably 0.0001%-0.5%, more preferably 0.001%-0.1%, by weight of the total composition.

The term "pectinase" is intended to include polygalacturonase (EC 3.2.1.15), exo-polygalacturonase (EC 3.2.1.67), exo-poly-alpha-galacturonase (EC3.2.1.82), pectin lyase (EC3.2.1.10), pectin esterase (EC3.2.1.11), pectate lyase (EC4.2.2.2) and exogalacturonan Acid lyase (EC 4.2.2.9). Pectinase refers to any enzyme that acts to break down pectic substances. Pectin substances are found in plant tissues and are common constituents of fruit juices such as orange, tomato, and grape juices. Pectin substances contain galacturonic acid and/or their derivatives.

Pectinases include pectin methylesterase that hydrolyzes pectin methyl ester bonds, polygalacturonase that breaks glycosidic bonds between galacturonic acid molecules, and acts on pectinic acid to cause α1→4 complexation. Pectin trans-eliminase or lyase that nonhydrolytically cleaves sugar bonds to form unsaturated derivatives of galacturonic acid.

Pectinase is added to the detergent compositions of the present invention at a level of 0.0001%-2%, preferably 0.0005%-0.5%, more preferably 0.001%-0.1% pure enzyme by weight of the total composition.

The aforementioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. The source can also be mesophilic or extreme (psychrophilic, psychrotrophic, thermophilic, barophilic, basophilic, acidophilic, halotrophic, etc.). Pure or impure forms of these enzymes can be used. Also included in the 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 enzymes in host organisms in which the genetic material responsible for enzyme production has been cloned. The enzymes are typically incorporated into detergent compositions at a level of from 0.0001% to 2% active enzyme by weight of the detergent composition. Enzymes can be added as individual components (pellet, granule, stabilized liquid, etc. containing one enzyme) or as a mixture of two or more (eg co-granulate).

Other suitable detergent ingredients which 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.

WO9307263A and WO9307260A to Genencor International, WO8908694A to Novo and US3553139 to McCarty et al., issued January 5, 1971 also describe a range of enzyme materials and their incorporation into synthetic detergent compositions. Enzymes are further described in US 4,101,457, Place et al., issued July 18, 1978, and in US 4,507,219, Hughes, issued March 26, 1985. US Patent 4,261,868, Hora et al., issued April 14, 1981, discloses enzyme materials for use in liquid laundry formulations and their incorporation into such formulations. Enzymes for use in detergents can be stabilized in a variety of ways. Enzyme stabilization techniques are described and exemplified in US3600319, Gedge et al., issued August 17, 1971, and EP199405 and EP200586, Venegas, published October 29, 1986. Enzyme stabilization systems are also described eg in US3519570. WO9401532A to Novo describes Bacillus AC13 capable of obtaining proteases, xylanases and cellulases. detergent components

The detergent compositions of the present invention may also contain other detergent ingredients. The exact nature of these additional ingredients and their level of addition will depend upon the physical form of the composition and the nature of the laundering operation employed.

The detergent compositions of the present invention may be in liquid, paste, gel, bar, tablet, powder or granular form. Granular compositions may also be in "compact" form and liquid compositions may also be in "concentrated" form.

The compositions of the present invention may be formulated, for example, as hard surface cleaners, hand and machine dishwashing compositions, hand and machine laundry detergent compositions, including laundry additive compositions and suitable for soaking and/or pretreatment of soiled fabrics. Composition, rinse-added fabric softener composition.

The compositions of the present invention may be formulated as hand and machine laundry detergent compositions comprising laundry additive compositions and compositions suitable for soaking and/or pretreatment of soiled fabrics, rinse added fabric softener compositions. The compositions provide fabric cleaning, stain removal, whiteness maintenance, softness, color appearance and dye transfer inhibition.

When formulated as compositions for use in machine laundry methods, the compositions of the present invention preferably contain both a surfactant and a builder compound and an additional one or more compounds preferably selected from organic polymers, bleaches, additional Detergent component of enzymes, suds suppressors, dispersants, lime soap dispersants, soil suspending and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents as additional detergent ingredients.

The compositions of the present invention can also be used as detergent additive products which contain enzyme-directed antibodies to be added to conventional detergent compositions containing said enzymes. Detergent additives may also contain enzymes and antibodies directed against said enzymes. The additive product is used to supplement or enhance the performance of conventional detergent compositions and preferably contains up to 50% antibody by weight of the total composition.

When formulated as a composition for use in hand dishwashing methods, the compositions of the present invention preferably contain a surfactant and preferably selected from the group consisting of organic polymers, suds boosters, Group II metal ions, solvents, hydrotropes and additional enzymes. other detergent compounds.

When formulated as compositions for use in machine laundry methods, the compositions of the present invention preferably contain both a surfactant and a builder compound and an additional one or more compounds preferably selected from organic polymers, bleaches, additional Detergent component of enzymes, suds suppressors, dispersants, lime soap dispersants, soil suspending and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents as additional detergent ingredients.

The compositions of the present invention can also be used as detergent additive products containing enzyme-directed antibodies to be added to conventional detergent compositions containing enzymes. Detergent additives may also contain enzymes and antibodies directed against said enzymes. The additive product is used to supplement or enhance the performance of conventional detergent compositions and preferably contains up to 50% antibody by weight of the total composition.

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

In the present invention, the "compact" form of granular laundry detergent compositions is best reflected by density and, for compositions, by the amount of inorganic filler salts; inorganic filler salts are conventional components of detergent compositions in powder form; In conventional detergent compositions filler salts are present in substantial amounts, typically 17-35% by weight of the total composition.

In compact compositions, the filler salt is present in an amount of not more than 15%, preferably not more than 10%, most preferably not more than 5% by weight of the composition of the total composition.

The inorganic filler salts described in the composition of the present invention are selected from alkali metal and alkaline earth metal sulfates and chlorides.

A preferred filler salt is sodium sulfate.

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

Concentrated liquid detergents generally preferably have a water content of less than 50%, more preferably less than 40%, most preferably less than 30%, by weight of the detergent composition. Surfactant system

The detergent compositions of the present invention comprise a surfactant system wherein the surfactant may be selected from nonionic and/or anionic and/or cationic and/or amphoteric and/or zwitterionic and/or semipolar surfactants.

Surfactants are typically present in amounts of 0.1% to 60% by weight. In the present invention, it is more preferably added in an amount of 1%-35% by weight of the detergent composition, most preferably 1%-30% by weight.

The surfactant is preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated so as to promote, or at least not destabilize, any enzymes in these compositions.

Preferred surfactant systems for use in the present invention contain as surfactant one or more of the nonionic and/or anionic surfactants described herein.

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

The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having alkyl groups containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with about 2 to about 10 moles of ethylene oxide per mole of alcohol. From about 2 to about 7 moles of ethylene oxide, most preferably from 2 to 5 moles of ethylene oxide, are present in the condensation product per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ^™ 15-S-9 (a condensation product of C ₁₁ -C ₁₅ linear alcohols with 9 moles of ethylene oxide), Tergitol ^™ 24-L - 6NMW (condensation product of C ₁₂ -C ₁₄ primary alcohols with narrow molecular weight distribution and 6 moles of ethylene oxide), both sold by Union Carbide; Neodol ^TM 45-9 (C ₁₄ -C ₁₅ linear alcohols with 9 moles of ethylene oxide), Neodol ^TM 23-3 (condensation product of C ₁₂ -C ₁₃ linear alcohols with 3.0 moles of ethylene oxide), Neodol ^TM 45-7 (C ₁₄ -C ₁₅ linear alcohols Condensation product with 7 moles of ethylene oxide), Neodol ^TM 45-5 (condensation product of C ₁₄ -C ₁₅ linear alcohols with 5 moles of ethylene oxide), both sold by Shell Chemical Company, Kyro ^TM EOB (C ₁₃ -C ₁₅ alcohols with 9 moles of ethylene oxide), sold by P&G; and Genapol LA 030 or 050 (condensation products of C ₁₂ -C ₁₄ alcohols with 3 or 5 moles of ethylene oxide), sold by Hoechst Sale. The preferred HLB range for these products is 8-11, most preferably 8-10.

Nonionic surfactants also useful in the surfactant system of the present invention are the alkyl polysaccharides disclosed in US4565647, Llenado, issued January 22, 1986, containing from about 6 to about 30 carbon atoms, preferably about Hydrophobic groups of 10 to about 16 carbon atoms and polysaccharides containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units, such as polyglycoside hydrophilic groups. Any reducing sugar containing 5 or 6 carbon atoms can be used, such as glucose, galactose and galactosyl can be used in place of glucosyl (hydrophobic groups are selectively attached at 2-, 3-, 4-, etc. positions, thereby to obtain glucose or galactose relative to glucoside or galactoside). An internal sugar bond may be, for example, between one position of the additional sugar unit and the 2-, 3-, 4- and/or 6-position of the previous sugar unit.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains about 10- About 18, preferably 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 - about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl polyethoxy alcohol is first formed and subsequently reacted with glucose or a source of glucose to form the glucoside (attached at the 1-position). Further glycosyl units may subsequently be attached between their 1-position and the previous glycounit 2-, 3-, 4- and/or 6-position, preferably predominantly in the 2-position.

Condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol are also suitable for use in 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. The addition of a polyoxyethylene moiety to this hydrophobic moiety will increase the overall water solubility of the molecule, and the liquid character of the product will remain until the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation of up to about 40 moles of ring Oxyethane. Examples of compounds of this type include certain of the commercially available Plurafac ^™ LF404 and Pluronic ^™ surfactants, both sold by BASF.

Nonionic surfactants which are likewise suitable for use as the nonionic surfactant system according to the invention are the condensation products of ethylene oxide with the product obtained by reacting propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and 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 certain of the commercially available Tetronic ^™ compounds, marketed by BASF.

Preferred nonionic surfactants for use in the surfactant system of the present invention are polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, Alkyl polysaccharides and their mixtures. Most preferred are C ₈ -C ₁₄ alkylphenol ethoxylates containing 3-15 ethoxy groups and C ₈ -C ₁₈ alcohol ethoxylates containing 2-10 ethoxy groups (preferably average C ₁₀ ) and their mixture.

Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

R ₂ -C(0)-N(R ¹ )-Z wherein R ¹ is H, or R ¹ is C _1-4 hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C _5-31 hydrocarbyl, and Z is a polyhydroxyl hydrocarbyl having at least 3 hydroxyl groups directly attached to the chain, or an alkoxylated derivative thereof. Preferably ^R1 is methyl, ^R2 is a straight chain _C11-15 alkyl or _C16-18 alkyl or alkenyl chain, such as coconut alkyl or mixtures thereof, and Z is formed from a reducing sugar, such as glucose, fructose , Maltose and lactose are obtained in the reductive amination reaction.

Suitable anionic surfactants that can be used are linear alkylbenzene sulfates, alkyl ester sulfonate surfactants, which include linear esters of C ₈ -C ₂₀ carboxylic acids (i.e. fatty acids) according to the "U.S. Sulfonation with gaseous sulfur trioxide by the method in Journal of Petrochemical Society", 52 (1975), pp. 323-329. Suitable materials would include natural fatty materials derived from tallow, palm oil, and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry applications, include alkyl ester sulfonate surfactants of the formula:

R ³ -CH(SO ₃ M)-C(O)OR ⁴ wherein R ³ is C ₈ -C ₂₀ hydrocarbon group, preferably alkyl or their mixture, R ⁴ is C ₁ -C ₆ hydrocarbon group, preferably alkyl or their A mixture of M is a cation which forms a water-soluble salt with an alkyl ester sulfonic acid. 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. Especially 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 hydrocarbyl, preferably containing a C ₁₀ -C ₂₀ alkyl moiety Alkyl or hydroxyalkyl, 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 trimethyl-ammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and alkylamines such as ethylamine, diethylamine, triethylamine , and their mixtures to obtain quaternary ammonium cations, etc.). _C12 - _C16 alkyl chains are generally preferred for low wash temperatures (eg _{, below about 50°C) and C16-18 alkyl} chains are preferred for higher wash temperatures (eg, above about 50°C).

Other anionic surfactants suitable for detersive use may also be included in the detergent compositions of the present invention. They may include soap salts (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 olefins Sulfonates, sulfonated polycarboxylic acids prepared by sulfonating pyrolysis products of alkaline earth metal citrates, C ₈ -C ₂₄ alkylpolyethylene glycol ether sulfates (containing poly up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oil acyl glycerol sulfates, alkylphenol oxirane ether sulfates, paraffin sulfonates, alkyl phosphates salts, isethionates, for example, acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and sulfosuccinate diesters (especially saturated and unsaturated C ₆ -C ₁₂ diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as alkyl Polyglucoside sulfates (nonionic unsulfated compounds described _below ), branched primary alkyl sulfates and alkyl polyethoxy carboxylates such as the formula RO( _CH2CH2O ) _k - _CH2 Those of COO ^- M ⁺ , wherein, R is a C ₈ -C ₂₂ alkyl group, k is an integer of 1-10, and M is a water-soluble salt-forming cation. 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, Schwartz, Perry and Berch). A variety of such surfactants are also generally described in US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 23, line 58 through column 29, line 23 (herein incorporated by reference).

If included, the laundry detergent compositions of the present invention will generally contain from about 1% to about 40%, preferably from about 3% to about 20%, by weight of such anionic surfactants.

Highly preferred anionic surfactants including alkyl alkoxylated sulfate surfactants are water soluble salts or acids of the formula RO(A) _m SO ₃ M where R is an unsubstituted C ₁₀ -C ₂₄ alkyl Or hydroxyalkyl containing 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 propoxy m is greater than zero, usually about 0.5 to about 6, more preferably about 0.5 to about 3, M is H or a cation, which can be, for example, a metal cation (such as sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or Substituted ammonium cations. The present invention contemplates both alkyl ethoxylated sulfates and alkyl propoxylated sulfates. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as ethylamine , Diethylamine, triethylamine, and cations obtained from their mixtures. 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(40)M), where M is typically selected from sodium and potassium.

The detergent compositions of the present invention may also contain cationic, amphoteric, zwitterionic and semi-polar surfactants as well as nonionic and/or anionic surfactants other than those already described above.

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

[R ² (OR ³ ) _y ][R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X ^- wherein R ² is an alkyl or alkyl benzyl having from about 8 to about 18 carbon atoms in the alkyl chain Each R ³ is selected from the group consisting of -CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )-, -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, benzyl ring structure formed by connecting two R ⁴ groups, -CH ₂ CHOH-CHOHCOR ⁶ CHOHCH ₂ OH, wherein R ⁶ is any hexose or hexose polymer having ^a molecular weight below about 1000, and when y is not 0, is hydrogen; R is the same as R or is an alkyl chain, wherein R ^{and R} have the same total number ^of carbon atoms exceeds about 18; each y is from 0 to about 10, the sum of the y values is from 0 to about 15; and X is any compatible anion.

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

Formula I wherein R ¹ is a short-chain alkyl group (C6-C10) or an alkylamidoalkyl group of formula (II):

Formula IIy is 2-4, preferably 3, wherein R2 is H or C1-C3 alkyl, wherein x is 0-4, preferably 0-2, most preferably 0, wherein R3, R4 and R5 are identical or different, can is a short-chain alkyl group (C1-C3) or an alkoxylated alkyl group of formula III, wherein ^X- is a counterion, preferably a halide such as chloride or methylsulfate.

Formula III R6 is C ₁ -C ₄ and z is 1 or 2.

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

Highly preferred cationic surfactants 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 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 is 2-5 and X is an anion. Not more than one of _R2 , _R3 or _R4 shall be benzyl. Preferred alkyl chain lengths for R ₁ are C ₁₂ -C ₁₅ , especially mixtures of chain lengths where the alkyl group is derived from coconut oil or palm kernel fat or from olefin synthesis or oxo alcohol synthesis. 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.

Examples of suitable quaternary ammonium compounds of formula (i) for use in the present invention include:

Cocotrimonium chloride or bromide;

Coco Methyldihydroxyethylammonium Chloride or Bromide;

Decyltriethylammonium chloride;

Decyldimethylhydroxyethylammonium chloride or bromide;

C _12-15 Dimethylhydroxyethylammonium chloride or bromide;

Coco Dimethyl Hydroxyethyl Ammonium Chloride or Bromide;

Tetradecyltrimethylammonium methylsulfate;

Dodecyldimethylbenzyl ammonium chloride or bromide;

Dodecyldimethyl(oxyethylene) ₄ ammonium chloride or bromide;

Choline esters (compounds of formula (i) wherein R ₁ is -CH ₂ -CH ₂ -OC(O)-C _12-14 alkyl and R ₂ , R ₃ and R ₄ are methyl); dialkylimidazoles Phenyl [compound of formula (i)].

Other cationic surfactants useful in the present invention are also described in US 4,228,044, Cambre, issued October 14, 1980, and European Patent Application EP 000224.

If included, the detergent compositions herein will generally 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 detergent 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 and tertiary amines, wherein the aliphatic group may be straight or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, usually from about 8 to about 18 carbon atoms and at least one of the aliphatic substituents contains an anionic water solubilizing group, eg, carboxy, sulfonate, sulfate. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, lines 18-35, for exemplary amphoteric surfactants.

If included, the detergent compositions herein will generally 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 the detergent compositions of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines or derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, line 38-column 22, line 48, for exemplary zwitterionic surfactants.

If included, the detergent compositions herein will generally 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 special class of nonionic surfactants that include an alkyl moiety containing about 10 to about 18 carbon atoms and two alkyl moieties selected from the group consisting of about 1 to about 3 carbon atoms Water-soluble amine oxides containing moieties of alkyl and hydroxyalkyl groups; containing one alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl and hydroxyalkyl moieties of about 1 to about 3 carbon atoms and water-soluble sulfoxides containing an alkyl moiety of about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl groups of about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include amine oxide surfactants having the formula:

0

↑R ³ (OR ⁴ )×N(R ⁵ ) ₂ wherein R ³ is alkyl, hydroxyalkyl or alkylphenyl containing about 8 to about 22 carbon atoms or a mixture thereof; R ⁴ is containing about 2- An alkylene or hydroxyalkylene group of about 3 carbon atoms or a mixture thereof; x is 0 to about 3; each ^R is an alkyl or hydroxyalkyl group of about 1 to about 3 carbon atoms or contains about 1 to about 3 polyoxyethylene groups of oxirane groups. The R ⁵ 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 C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides, among others.

If included, the detergent compositions herein will generally contain from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of such semi-polar nonionic surfactants.

The detergent compositions of the present invention 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 C ₆ -C ₁₂ alkyl chain n is 1-5, preferably 3. The R ₁ alkyl chain may be straight or branched and may be interrupted by up to 12, preferably less than 5, ethylene oxide moieties. Preferred amines of the above formula according to the invention are n-alkylamines. Suitable amines for use in the present invention are selected from 1-hexylamine, 1-octylamine, 1-decane and dodecylamine. Other preferred primary amines are C ₈ -C ₁₀ propylamine oxide, octyloxypropylamine, 2-ethylhexyloxypropylamine, dodecylamidopropylamine and amidopropylamine.

R₃是C₆-C₁₂，优选C₆-C₁₀烷基链或R₃是R₄X(CH₂)_n，而X是-O-、-C(O)NH-或-NH-,R₄是C₄-C₁₂,n是1-5，优选是2-3。R₅是H或C₁-C₂烷基和x是1-6。R₃和R₄可以是直链或支链的；R₃烷基链可被至多12个，优选少于5个环氧乙烷部分间断。Suitable tertiary amines for use in the present invention include tertiary amines having 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 , and 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 and x is 1-6. _R3 and _R4 may be linear or branched; the _R3 alkyl chain may be interrupted by up to 12, preferably less than 5, oxirane moieties.

Preferred tertiary amines are R ₁ R ₂ R ₃ N, wherein 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 methyl and 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, C ₈ -C ₁₀ propylamine oxide, N-coco 1-3 diaminopropane, coconut Oleyl dimethylamine, dodecyl dimethylamine, dodecyl di(hydroxyethyl)amine, coconut oil alkyl di(hydroxyethyl)amine, 2 moles of propoxylated dodecyl Alkylamine, 2 moles of propoxylated octylamine, dodecylamidopropyldimethylamine, C8-10 amidopropyldimethylamine, and C10 amidopropyldimethylamine.

The most preferred amines for use in the compositions of the present invention are 1-hexylamine, 1-octylamine, 1-decane, 1-dodecylamine. Particularly desirable are n-dodecyldimethylamine and dihydroxyethylcocoalkylamine and 7-fold ethoxylated oleylamine, dodecylamidopropylamine and cocoamidopropylamine. Color Care Benefits

Techniques that provide the type of color care benefits can also be included. Examples of these technologies are organometallic catalysts for color retention which are described in co-pending European patent application 92870181.2. bleach

The detergent compositions of the present invention may also include bleaching agents such as hydrogen peroxide, PB1, PB4 and percarbonate having a particle size of 400-800 microns. These bleach components may include one or more oxygen bleaches and, depending on the bleach chosen, one or more bleach activators. Oxygen bleaching compounds, if present, are typically present at levels from about 1% to about 25%.

The bleaching agent component for use in the present invention can be any bleaching agent useful in detergent compositions including oxygen bleaching agents and others known in the art. Bleaching agents suitable for use in the present invention may be activated or unactivated bleaching agents.

One type of oxygen bleach that can be used includes percarboxylic acid bleaches and salts thereof. Suitable examples of such bleaches include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid . Such bleaches are disclosed in US4483781, US patent application 740446, EP patent application 0133354 and US4412934. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid described in US4634551.

Another class of bleaches that can be used includes halogen bleaches. Examples of hypohalite bleaches include, for example, trichloroisocyanuric acid and sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulfonamides. This substance is generally added at 0.5-10% by weight of the final product, preferably 1-5% by weight.

Hydrogen peroxide releasing agents can be combined with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US4412934), 3,5,-trimethylhexanoyloxy phenylsulfonate (ISONOBS, described in EP120591) or pentaacetylglucose (PAG) or N-nonanoyl-6-aminocaproic acid phenolsulfonate (NACA-OBS, described in WO94/28106) in combination , which are perhydrolyzed to form peracids as active bleaching substances, resulting in an improved bleaching effect. Also suitable activators are the acylated citrates disclosed in co-pending European patent application 91870207.7.

Useful bleaching agents for use in the detergent compositions of the present invention, including peroxyacids and bleaching systems containing bleach activators and peroxygen bleaching compounds, are described in our co-pending application USSN 08/136626, PCT/US95 /07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775.

Hydrogen peroxide can also be present by adding an enzymatic system (ie enzymes and their substrates) capable of generating hydrogen peroxide at the beginning of the wash or during the wash and/or rinse. This enzyme system is disclosed in European Patent Application 91202655.6 filed on October 9,1991.

Metal-containing catalysts for use in bleach compositions include cobalt-containing catalysts such as cobalt(III) pentaamine acetate salts and manganese-containing catalysts such as the compounds described in EPA549271, EPA549272, EPA458397, US5246621, EPA458398, US5194416 and US5114611. Bleaching compositions containing peroxygen compounds, manganese-containing bleach catalysts and chelating agents are described in patent application No. 94870206.3.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be used in the present invention. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited on the soil carrier during the washing process. Upon exposure to light and in the presence of oxygen to dry, for example by hanging the clothes in the sun, the sulfonated zinc phthalocyanine is activated, resulting in bleaching of the soil carrier. A preferred zinc phthalocyanine and photoactivated bleaching process is described in US4033718. Detergent compositions will generally contain from about 0.025% to about 1.25% by weight of sulfonated zinc phthalocyanine. Builder system

The compositions of the present invention may further 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 ethylenediaminetetraacetate, diethylenediaminetetraacetate, Ethylenetriaminepentamethyleneacetate substances, 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 especially hydrated synthetic zeolites such as hydrated zeolite A, X, B, HS or MAP.

Other suitable inorganic builder materials are layered silicates, 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 carboxyl group include lactic acid, glycolic acid and their ether derivatives disclosed in Belgian Patents 831368, 821369 and 821370. Polycarboxylates containing two carboxyl groups include succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, Water-soluble salts and ether carboxylates of tartronic and fumaric acids, and thionyl carboxylates described in Belgian patent 840623. Polycarboxylates containing three carboxy groups include especially the water-soluble citrates, aconitates and citraconicates and succinate derivatives such as carboxymethoxysuccinates described in British Patent 1379241, in Lactoxysuccinates are described in Dutch application 7205873 and oxidized polycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylate are described in British Patent 1387447.

Polycarboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates disclosed in British Patent 1,261,829 salt and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include sulfosuccinate derivatives disclosed in British Patents 1,398,421 and 1,398,422 and US Pat. Polycarboxylates are disclosed in British Patent 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadiene pentacarboxylates, 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 polyhydric alcohols such as carboxymethyl derivatives of sorbitol, mannitol and xylitol. Aromatic polycarboxylates include pyromellitic acid, pyromellitic acid and pyromellitic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more especially citrates.

Preferred builder systems for use in the compositions of the present invention include water insoluble aluminosilicate builders such as zeolite A or layered silicate (SKS-6) and water soluble carboxylate chelating agents such as citric acid mixture. Preferred builder systems for use in the liquid detergent compositions of the present invention include soaps and polycarboxylates.

A suitable chelating agent for inclusion in the detergent compositions of the present invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or their alkali metal, alkaline earth metal, ammonium or substituted ammonium salts or mixtures thereof. Preferred EDDS compounds are the free acid forms and their sodium or magnesium salts. Examples of the preferred sodium salt of EDDS include _Na2EDDS and _Na4EDDS . Examples of the preferred magnesium salt of EDDS include MgEDDS and _Mg2EDDS . Magnesium salts are most preferred for use in the compositions of the present invention.

A preferred builder system comprises a mixture of a water-insoluble aluminosilicate builder, such as zeolite A, and a water-soluble carboxylate chelating agent, such as citric acid.

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, amino poly Alkylene phosphonates and amino polycarboxylates.

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-1596756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, the copolymers having a molecular weight of 20000-70000, especially about 40000.

Builder salts are typically present in amounts of from 5% to 80%, preferably from 10% to 70%, most usually from 30% to 60% by weight of the composition. Foam suppressor

Another optional ingredient is a suds suppressor, such as silicones and silica-polysiloxane mixtures. Polysiloxanes can generally be expressed as alkylated polysiloxane substances, while silica is usually used in finely divided forms, such as various types of silica aerosols and xerogels, and hydrophobic silica . These materials can be incorporated as granules wherein the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, non-surfactant detergent substantially impermeable carrier. Alternatively, the suds suppressor can be dissolved or dispersed in a liquid carrier and added by spraying onto one or more of the other ingredients.

Preferred silicone suds control agents are disclosed in US 3,933,672 to Bartollota et al. Other particularly suitable suds suppressors are the self-emulsifying silicone suds suppressors described in German Patent Application DTOS 2646126, published April 28,1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a polysiloxane-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 12R.

This suds suppressor system is described in co-pending European Patent Application 92870174.7, filed November 10,1992.

Particularly preferred silicone suds control agents are described in co-pending European patent application 92201649.8. The composition may contain a polysiloxane/silica mixture in combination with fumed non-porous silica, such as Aerosil ^R.

The aforementioned suds suppressors are generally used at a level of 0.001% to 2% by weight of the composition, preferably 0.01% to 1% by weight. other

Other ingredients used in detergent compositions may be used, such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, colorants and/or encapsulated or unencapsulated perfumes .

Particularly suitable encapsulating materials are water soluble capsules, as described in GB1464616, which consist of a matrix of polysaccharides and polyols.

Other suitable water-soluble encapsulating materials include dextrins derived from ungelatinized starch esters of substituted dicarboxylic acids as described in US3455838. These ester dextrins are preferably prepared from starches such as soft corn, soft sorghum, sago, tapioca and potato. Suitable examples of such encapsulating materials include N-Lok manufactured by National Starch. N-Lok encapsulating material consists of modified corn starch and dextrose. Starches are modified by adding monofunctional substituent groups such as octenyl succinic anhydride.

Suitable antiredeposition and soil suspension agents herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose and homo- or copolymers of polycarboxylic acids or salts thereof. Polymers of this type include the previously mentioned polyacrylates and maleic anhydride-acrylic acid copolymers as builders, and copolymers of maleic anhydride with 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 0.5% to 10% by weight, more preferably 0.75% to 8%, most preferably 1% to 6% by weight of the composition.

Preferred optical brighteners are anionic in character, an example of which is 4,4'-bis-(2-ethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'disulfo disodium 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"-sodium sulfonate and 4,4'-bis(2-sulfostyryl)biphenyl. Highly preferred brighteners are the specific brighteners of co-pending European patent application 95201943.8.

Other useful polymers are polyethylene glycols, especially polymers having a molecular weight of 1000-10000, more preferably 2000-8000, most preferably about 4000. They are used in amounts of 0.20% to 5%, more preferably 0.25% to 2.5% by weight. These polymers and the homo- or co-polymeric polycarboxylates mentioned above are useful in improving whiteness retention, fabric dust deposition and detergency performance on clay, protein and oxidizable soils in the presence of transition metal impurities .

Soil release agents useful in the compositions of the present invention are conventional copolymers or terpolymers of terephthalic acid and ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are described in commonly assigned US4116885 and 4711730 and EP published patent application 0272033. According to EP-A-0272033, a particularly preferred polymer has the following 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 mainly consisting of sulfobenzyl Esters and minors consist of monoesters of ethylene glycol and/or propylene glycol. The goal is to have polymers capped at both ends with sulfobenzoate, in the present invention the majority of said copolymers of the invention are "predominantly" sulfobenzoate capped. However, some copolymers will not be fully end-capped, and as such, their end groups may consist of ethylene glycol and/or propane 1-2 diol which "secondarily" makes up the species.

The polyester selected for the present invention contains about 46% by weight dimethyl terephthalate, about 16% by weight propane-1,2 diol, about 10% by weight ethylene glycol, about 13% by weight % dimethyl sulfobenzoate and about 15% by weight sulfoisophthalic acid having a molecular weight of about 3000. Polyesters and their preparation are described in detail in EPA311342.

It is known in the art that free chlorine present in tap water rapidly deactivates enzymes contained in detergent compositions. Therefore, the use of chlorine scavengers such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine in the formulation at levels above 0.1% by weight of the total composition will provide improved stabilization of the detergent enzymes during the wash process. sex. Compositions containing chlorine scavengers are described in European Patent Application 92870018.6 filed 31 January 1992.

Alkoxylated polycarboxylates prepared from polyacrylates are useful herein to provide additional grease removal performance. This material is described in WO91/08281 and PCT90/01815, page 4 et seq., incorporated herein by reference. Chemically these materials contain polyacrylates with 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. Side chain esters are attached to the polyacrylate "backbone" to provide a "comb" polymer type structure. Molecular weights can vary, but typically range from about 2,000 to about 50,000. The alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the compositions herein. softener

Fabric softening agents can also be incorporated into the laundry detergent compositions of the present invention. These reagents can be of inorganic or organic type. Inorganic softeners are, for example, smectite clays as described in GB-A-1400898 and USP5019292. Organic fabric softeners include water-insoluble tertiary amines as described in GB-A1514276 and EP-B0011340, their mixtures with mono-C12-C14 quaternary ammonium salts are disclosed in EP-B-0026527 and EP-B-0026528, and as described in EP-B-0026528 - Dilong chain amides disclosed in B-0242919. Other useful organic components for fabric softening systems include the high molecular weight polyethylene oxide materials disclosed in EP-A 0299575 and 0313146.

The amount of smectite clay typically ranges from 2% to 20%, more preferably 5% to 15% by weight, the material being added as a dry blend component to the remainder of the formulation. Organic fabric softeners, such as water-insoluble tertiary amines or dilong-chain amide substances, are added in an amount of 0.5%-5% by weight, usually 1%-3%, while high-molecular-weight polyethylene oxide substances and water-soluble cationic substances It is added in an amount of 0.1%-2%, usually 0.15%-1.5% by weight. These materials are usually added to the spray-dried portion of the composition, although in some cases they may more conveniently be added as dry blended granules or sprayed as a molten liquid onto the other solid components of the composition. Dispersant

The detergent compositions of the present invention may also contain dispersants: 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-1596756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, the copolymers having a molecular weight of 1000-100000.

In particular, copolymers of acrylate and methacrylate having a molecular weight of 4000, eg 480N, may be included in the detergent compositions of the present invention at levels of 0.5-20% by weight of the composition.

The compositions of the present invention may contain a lime soap peptizer compound having a lime soap dispersing power (LSDP) of not more than 8, preferably not more than 7, most preferably not more than 6, as defined below. Lime soap peptizers are preferably present in an amount of 0% to 20% by weight.

Various measures of the peptizing effect of lime soaps are given by the peptizing power of lime soaps (LSDP), which is described in the article H.C. Borghetty and C.A. Bergman, J.Am.Oil.Chem.Soc. Vol. 27, pp. 88-90 Determined by the calcium soap dispersant test described in . This calcium soap dispersion test method is widely used by practitioners in the field and is relevant for example to the following review articles: W.N. Linfield, Surfactant science Series, Vol. 7, p. 3; W.N. Linfield, Tenside surf.det. Vol. 27, pp. 159-163 (1990) and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Vol. 104, pp. 71-73 (1989). LSDP is the weight percent ratio of dispersant to sodium oleate required to disperse by precipitation of a calcium soap formed from 0.025 g of sodium oleate in 30 ml of 333 ppm calcium carbonate (calcium: magnesium = 3: 2) equivalent hardness water.

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 a LSDP of not more than 8 include C ₁₆ -C ₁₈ dimethylamine 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 with an average degree of ethoxylation of 3 (LSDP=4) and C with an average degree of ethoxylation of 12 (LSDP=6) or 30 ₁₄ -C ₁₅ ethoxylated alcohols sold under the trade names Lutensol AO12 and Lutensol AO30, respectively, by BASF GmbH.

Polymeric calcium soap peptizers suitable for use in the present invention are described in the article by M.K. Nagarajan, W.F. Masler in Cosmetics 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 are also useful as lime soap peptizing compounds together with hydrophilic/hydrophobic bleaching agents. dye transfer inhibition

The detergent compositions of the present invention may also include compounds which inhibit the transfer of dissolved and suspended dyes from one fabric to another encountered in fabric laundering operations involving colored fabrics. polymeric dye transfer inhibitor

The detergent compositions of the present invention also contain from 0.001% to 10%, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are typically added to detergent compositions to inhibit the transfer of dyes from colored fabrics to fabrics washed therewith. These polymers have the ability to complex or adsorb fugitive dyes washed out of dyed fabrics during laundering before the dyes have a chance to attach to other items.

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 this polymer also improves the performance of the enzymes of the invention.

a) Polyamine N-oxide polymers

其中P是可聚合的单元，R-N-O基团可与其相连或其中R-N-O基团构成部分可聚合的单元或两者的结合。A是NC,CO,

-O-, x是O或1；R是脂族、乙氧基化脂族、芳香族、杂环或脂环基团或其任何组合，N-O基团的氮可与其相连或其中N-O基团的氮是这些基团的一部分。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 or a combination of both. A is NC, CO,

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

其中R1、R2和R3是脂族基团、芳香族、杂环或脂环基团或它们的组合，x或/和y或/和z是0或1，其中N-O基团的氮可与其连接或其中N-O基团的氮构成这些基团的部分。The NO group can be represented by the following general structural formula:

wherein R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z are 0 or 1, wherein the nitrogen of the NO group can be attached to it or wherein the nitrogen of the NO group forms part of these groups.

The N-O groups may be part of the polymerizable unit (P) or may be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein 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 the group of polyamine N-oxides in which the nitrogen 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 comprises a group of polyamine N-oxides in which the nitrogen of the N-O group is attached to the R group.

Other suitable polyamine N-oxides are polyamine oxides in which the N—O groups are attached to the polymerisable units.

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 of the N-O functional group is the R group part.

Examples of such compounds 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 of the N-O functional group is attached to said R group .

Examples of such compounds are polyamine oxides, where the R group may be aromatic, eg 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 polyethylenes, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.

The amine N-oxide polymers of the present invention typically have a ratio of amine to amine N-oxide of 10:1 to 1:1,000,000. However, the amount 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 or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an amine N-oxide or not. The amine oxide units of the polyamine N-oxides have a PKa<10, preferably a PKa<7, more preferably a PKa<6.

Polyamine oxides are available in almost any degree of polymerization. The degree of polymerisation is not critical so long as the material has the desired water solubility and dye suspending power.

The average molecular weight is usually 500-1,000,000; preferably 1,000-50,000, more preferably 2,000-30,000, most preferably 3,000-20,000.

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 polymer has a An average molecular weight of 10,000-20,000 is most preferred.

The average molecular weight range is determined by, for example, Barth H.G. and by light scattering as described in Mays J.W. Chemical Analysis Vol. 113, "Modern Approaches to the Characterization of Polymers".

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

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

The molar ratio of N-vinylimidazole to N-vinylpyrrolidone in the N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention is 1-0.2, more preferably 0.8-0.3, most preferably 0.6-0.4.

c) Polyvinylpyrrolidone

The detergent composition of the present invention can also use 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 names PVPK-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVPK-60 (average molecular weight 160,000 ) and PVP K-90 (average molecular weight 360000) obtained. Other suitable polyvinylpyrrolidones commercially available from BASF Cooperation include Sokalan HP165 and Sokalan HP 12; polyvinylpyrrolidones known to those skilled in the detergent field (see e.g. EP-A-262897 and EP-A- 256696).

d) Polyvinyloxazolidinone:

The detergent compositions of the present invention may also employ polyvinyloxazolidinones as polymeric dye transfer inhibiting agents. The polyvinyloxazolidinone 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.

e) Polyvinylimidazole:

The detergent compositions of the present invention may also employ polyvinylimidazoles as polymeric dye transfer inhibiting agents. 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:

Cross-linked polymers are polymers in which the backbone is interconnected to some extent; these linkages can be chemical or physical in nature, possibly with reactive groups on the backbone or branches; cross-linked polymers are described in Journal of Polymer Science Described in 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 swelling.

This crosslinked polymer is described in co-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 having a rinse step to which a separate rinse aid composition may be added.

The method of the present invention involves contacting the fabrics with a wash solution in the usual manner and as hereinafter described.

The method of the invention is generally carried out during a wash. The washing method is preferably carried out at 5°C-95°C, especially at 10°C-60°C. The pH of the treatment solution is preferably 7-11.

A preferred machine dishwashing method comprises treating soiled items with an aqueous solution of a machine dishwashing or rinsing composition. A conventionally effective amount for machine dishwashing compositions refers to 8-60 grams of product dissolved or dispersed in a wash volume of 3-10 liters.

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

The compositions of the present invention may also be formulated as hard surface cleaner compositions.

The following examples serve to illustrate the compositions of the present invention without limiting or otherwise defining the scope of the invention.

In the detergent composition, the content of enzyme is represented by pure enzyme based on total composition weight, and the abbreviated component symbols have the following meanings: LAS: linear C ₁₂ sodium alkylbenzene sulfonate TAS: animal oil alkyl sodium sulfate CXYAS: Sodium C _1X - _{C 1Y} Alkyl Sulfate 25EY: Condensed with average Y moles of ethylene oxide, mainly C12-C15 straight chain

Primary Alcohol CXYEZ: Condensed with average Z moles of ethylene oxide is mainly C _1X -C _1Y straight chain

Primary alcohol XYEZS: _C1X - _C1Y alkyl condensed with average Z moles of ethylene oxide per mole

Sodium Sulfate QAS: R ² N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), where R ₂ =C ₁₂ -C ₁₄ Soap: Linear alkanes obtained from 80/20 mixture of animal oil and coconut oil

Sodium carboxylate nonionic surfactant: C ₁₃ -C ₁₅ mixed ethoxylated/propoxylated fatty alcohols, average degree of ethoxylation 3.8, average degree of propoxylation 4.5, by BASF

GmbH sells under the trade name Plurafac LF404 CFAA: C ₁₂ -C ₁₄ Alkyl N-Methyl Glucamide TFAA: C ₁₆ -C ₁₈ Alkyl N-Methyl Glucamide TPKFA: C ₁₂ -C ₁₄ Topped Whole Fraction Fatty acid DEQA: Di(tallow-oxy-ethyl)dimethylammonium chloride SDASA: 1:2 stearyl dimethylamine: tri-compressed stearic acid Neodo1 45-13: C14-C15 straight Alcohol Ethoxylates, by Shell Chemicals

Selling Silicate: Amorphous Sodium Silicate (SiO ₂ : Na ₂ O Ratio = 2.0) NaSKS-6: Crystalline Layered Silicate of Formula δ-Na ₂ Si ₂ O ₅ Carbonate: Anhydrous Sodium Carbonate, Particle size 200 micron-900 micron bicarbonate: anhydrous sodium bicarbonate, particle size 400 micron-1200 micron STPP: anhydrous sodium tripolyphosphate MA/AA: 1:4 maleic acid/acrylic acid copolymer, average molecular weight approx. 80000PA30: polyacrylic acid terpolymer with an average molecular weight of about 8000: a terpolymer with an average molecular weight of about 7000, by weight

60:20:20 random copolymer containing acrylic acid:maleic acid:ethacrylic acid monomer 480N:3:7 acrylic acid/methacrylic acid, average molecular weight

Amount of about 3500 Polyacrylate: Polyacrylate homopolymer with an average molecular weight of 8000, manufactured by BASF

GmbH sells Zeolite A under the trade name PA30: hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) 12.27H ₂ O, primary

           Particle size 0.1-10 microns Citrate: Trisodium citrate dihydrate, 86.4% active, particle size fraction

Cloth 425 microns-850 microns Citric acid: Anhydrous citric acid PB1: Anhydrous sodium perborate monohydrate bleach, empirical formula: NaBO ₂ .H ₂ O ₂ PB4: Anhydrous sodium perborate tetrahydrate percarbonate : Anhydrous sodium percarbonate bleach, empirical formula: 2Na2CO3.3H2O2TAED: Tetraacetylethylenediamine NOBS: Sodium nonanoylphenol benzene sulfonate Photoactivated bleach: Sulfonated zinc phthalocyanine, encapsulated in dextrin-soluble PAAC in polymers: Cobalt(III) pentaamine acetate Salt Paraffin: Paraffin oil, sold under the tradename Winog 70 by Wintershall

Sold BzP : Benzoyl Peroxide Antibody : Antibody to the Enzyme of the Invention Protease : Proteolytic Enzyme, marketed by Novo Nordisk A/S under the trade name

         Savinase, Alcalase, Durazym by Gist-Brocades

Sold under the trade names Maxacal, Maxapem, and Properase

and patents WO91/06637 and/or WO95/10591 and/or

Protease amylase described in EP251446: Genencor as described in WO94/18314, WO96/05295

Amylolytic enzymes sold under the trade name Purafact Ox Am ^R ,

by Novo Industries A/S under the trade name Termamyl®,

Fungamyl® and Duramyl® are marketed and as described in WO95/26397

Those lipases mentioned: marketed by Novo Nordisk A/S under the trade names Lipolase,

The lipolytic enzyme cellulase marketed by Lipolase Ultra: by Novo Nordisk A/S under the trade name Carezymea,

Cellulolytic enzyme carbohydrase sold by Celluzyme and/or Endolase: Xylanase: Pulpzyme obtained from Novo Nordisk A/S

HB and SP431, Lyxasan from Gist-Brocades,

Optipulp and xylanase obtained from Solvay;

          Chondroitinase: C2905, C3667, C2262,

C2780, C8058 and C0954 and 27038 commercialized by Fluka

and 27040;

Cutinase: K2876 from Sigma; from Fluka, Sigma

and Biozyme commercialized hyaluronidase; supplied by Sigma

Chemicals, Fluka Fine Chemicals and Novo

Endoglucanase commercially available from Nordisk A/S; pectinase:

Sold under the trade name Pectinex AR by Novo Nordisk A/S

Pectinolytic enzyme peroxidase sold: Guardzyme synergist from Novo Nordisk A/S: phenothiazine 10-propionate and/or butyl syringate as in Novo

In WO96/12846 and WO96/12845 of Nordisk A/S

CMC described: sodium carboxymethylcellulose HEDP: 1,1-hydroxyethanediphosphonic acid DETPMP: diethylenetriaminepenta (methylenephosphonic acid), commercialized by Monsanto

Name Dequest 2060 Sales PVNO : Poly(4-vinylpyridine)-N-oxide PVPVI : Poly(4-vinylpyridine)-N-oxide/vinylimidazole and ethylene

Pyrrolidone copolymer brightener 1 : 4,4'-bis(2-sulfostyrene)biphenyl disodium brightener 2 : 4,4'-bis(4-anilino-6-morpholino -1,3,5-triazin-2-yl)

Stilbene-2:2'-disodium disulfonate polysiloxane suds suppressor: polydimethylsiloxane foam control agent with silicone as dispersant

Alkane-oxyalkylene copolymer, the foam control agent and the dispersed

The ratio of the agent is 10:1-100:1 Granular antifoam agent: 12% polysiloxane/silicon dioxide, 18% stearyl alcohol, 70% starch

Powder, particle form SRP1: Sulfenzozozozozozozozozozozozozozoh in oxygenyl oxygenyl and phenylmethyl skeleton skeleton

Acyl-terminated ester SRP2 : Short blocks of diethoxylated poly(1,2-propylene terephthalate)

Polymer sulfate: Sodium -free sodium sulfate HMWPEO: Polymer polyetracular ethylene PEG: polyethylene glycol BTA: benzene and triazole nitrate: nitrate salt NADCC: scent of sodium dichlorocyanuric acid pad Zeolite 13x, fragrance and glucose/glycerol agglomerated binder material particles Insoluble fragrance delivery technology KOH: 100% active solution of potassium hydroxide pH: Measured at 20°C as 1% distilled aqueous solution Example 1 Antibody preparation:

1 ml of 1 mg/ml Lipolase® emulsion was injected into the breast muscle of the chicks. Lipase emulsions were prepared using Freunds complete adjuvant (Freund and McDermott, 1942; Freund 1956) by vigorously mixing equal amounts of Lipolase(R) solution (2 mg/ml) and Freunds complete adjuvant.

The immunization process was completed by injection with Freunds incomplete adjuvant, and eggs were collected over a period of 1 week after 4 weeks. Antibodies were extracted from egg yolk according to the Polson extraction method described in Immunological Investigation 19, 1990, pp. 253-258. Lipase inactivation:

Lipolase® stock solutions were prepared at a concentration of 0.3% active enzyme in Tris buffer (5×10 ⁻² Tris, 25 mM NaCl, pH=7 and 10). Phosphate buffer (0.05M KH2PO4, pH 6.8) contained antibody (0.18mg/ml). Tris buffer and a commercially available detergent solution containing Ariel liquid (0.8%, in city water, pH 8.5) and Ariel ColorFutur (0.8%, in city water, pH 9.5) within 5 minutes at 40°C A lipase (0.08% final concentration)/antibody interaction was performed.

Lipase residual activity was measured according to a method based on the hydrolysis of 4-nitrophenol butyrate. As shown in the table below, the enzymatic activity of lipase was successfully blocked within 5 minutes.

Residual lipolytic activity (% after 5 minutes) Tris pH=7 Tris pH=10 Ariel liquid Ariel Color Futur 2 5 3 4 Example 2

Laundry detergent compositions of the present invention were prepared as follows:

Ⅰ Ⅱ Ⅲ ⅴ ⅵLas 8.0 8.0 8.0 8.0 8.0C25E3 3.4 3.4 3.4 3.4 3.4 QAS-0.8 0.8 0.8 0.8 Burlestone A 18.1 18.1 18.1 18.1 18.1 Carbonic 13.0 13.0 27.0 27.0 Siliconic acid 3.0      3.0硫酸盐            26.1     26.1     26.1     26.1     26.1     26.1PB4               9.0      9.0      9.0      9.0      9.0      9.0TAED              1.5      1.5      1.5      1.5      1.5      1.5DETPMP            0.25     0.25     0.25     0.25     0.25     0.25HEDP              0.3      0.3      0.3      0.3      0.3      0.3蛋白酶            0.0026   0.0026   0.0026   0.0026   0.0026   0.0026淀粉酶            -        0.0009   0.0009 -0.0009 0.0009 antibody 10e-1-4 10E-2E-2E-10E-3 10E-2 lipase 0.003 0.003 0.003-cellulose enzyme 0.0006 0.0006-0.0006 agonase-0.005-0.01-peroxides Enzyme-0.005-0.01 Efficiency Efficiency-0.5-1.0MA/AA 0.3 0.3 0.3 0.3 0.3cmc 0.2 0.2 0.2 0.2 0.2 Light activation bleach (PPM) 15 15 15 15 15 15.09 agent 1 0.09 0.09 0.09 0.09 0.09 0.09 spice 0.3 0.3 0.3 0.3 0.3 0.3 polysiloxane bubbles 0.5 0.5 0.5 0.5 0.5 components/trace components to 100 % density, G/L 850 850 850 850 850 embodiment 3

The following granular laundry detergent compositions according to the invention having a bulk density of 750 g/l were prepared:

Ⅰ Ⅱ ⅢLAS 5.25 5.61 4.76TAS 1.25 1.86 1.57C45AS-2.24 3.89C25AE3S-0.76 1.18C45E7 3.25-5.0C25E3-5.8 2.0stpp 19.7-19.5 19.5NASKS-6/iltyle : 21) Carbonate 6.1 21.4 21.4 Barcarbonate-2.0 2.0 Silicate 6.8-sodium sulfate 39.8-14.3pb4 5.0 12.7-TAED 0.5 3.1 -DetPMP 0.25 0.2Hedp-0.3 0.3 antibody 10E-1-4 10E-4 10E-4 10E-4 10E-4 10E-4 10E-4 10E-4 10E-4 10E-4 10E-4 10E -2 protease 0.0026 0.0085 0.045 lipase 0.003 0.003 0.003 cellulose enzyme-0.0006 0.0006 amylase 0.0009-0.0009 deotase-0.01 0.01 peroxidase 0.5-0.5mA/AA 0.8.6cmc 0.2 0.4 0.4 0.4 0.4 0.2 0.6 cmc Light activation bleach (PPM) 15PPM 27ppm 27PPM whitening agent 1 0.08 0.19 0.19 whitening agent 2-0.04 0.04 packet capsule granules 0.3 0.3 0.3 polysiloxane elixids 0.5 2.4 trace components/small amount components to a small amount 100% Example 4

Detergent formulations according to the invention were prepared wherein I was a phosphorus-containing detergent composition, II was a zeolite-containing detergent composition and III was a compact detergent composition.

                                                                      

STPP 24.0 - 24.0

Zeolite A - 24.0 -

C45AS 9.0 6.0 13.0

MA/AA 2.0 4.0 2.0

LAS 6.0 8.0 11.0

TAS 2.0 - -

Silicate 7.0 3.0 3.0

CMC 1.0 1.0 0.5

Brightener 2 0.2 0.2 0.2

Soap 1.0 1.0 1.0

DTPMP 0.4 0.4 0.2 spray

C45E7 2.5 2.5 2.0

C25E3 2.5 2.5 2.0

Polysiloxane defoamer 0.3 0.3 0.3

Spices 0.3 0.3 0.3 dry additives

Carbonate 6.0 13.0 15.0

PB4 18.0 18.0 10.0

PB1 4.0 4.0 0

TAED 3.0 3.0 1.0

Photoactivated Bleach 0.02 0.02 0.02

Synergist 0.5 - 0.5

Peroxidase 0.0075 - 0.075

Carbohydrase - 0.01 0.01

Protease 0.01 0.01 0.01

Lipase 0.009 0.009 -

Amylase 0.002 - 0.001

Antibody 10E-1 10E-4 10E-2

Sodium Sulfate Dry Mix 3.0 3.0 5.0

Balance (moisture and trace components) 100.0 100.0 100.0

Density (g/l) 630 670 670Example 5

A bleach-free detergent granule formulation for washing colored laundry according to the invention was prepared as follows:

                                               

Zeolite A 15.0 15.0 -

Sodium sulfate 0.0 5.0 -

LAS 3.0 3.0 -

DTPMP 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

Spices 0.3 0.3 0.5

C45E7 4.0 4.0 4.0

C25E3 2.0 2.0 2.0 dry additive

MA/AA - - - - 3.0

NaSKS-6 - - - - 12.0

Citrate 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

Protease 0.026 0.016 0.047

Lipase - 0.009 0.009

Amylase - 0.005 0.005

Cellulase - 0.006 0.006

Carbohydrase 0.005 0.01 0.02

Antibody 10E-1 10E-1 10E-3

Polysiloxane defoamer 5.0 5.0 5.0 dry additive

Sodium sulfate 0.0 9.0 0.0 Balance (moisture and trace components) 100.0 100.0 100.0 Density (g/l) 700 700 700 Example 6 The detergent formulation of the invention was prepared as follows:

                                                

LAS 20.0 14.0 24.0 22.0

QAS 0.7 1.0 - 0.7

TFAA - 1.0 -

C25E5/C45E7 - 2.0 - 0.5

C45E3S - 2.5 - -

STPP 30.0 18.0 30.0 22.0

Silicate 9.0 5.0 10.0 8.0

Carbonate 13.0 7.5 - 5.0

Bicarbonate - 7.5 - -

DETPMP 0.7 1.0 - -

SRP1 0.3 0.2 - 0.1

MA/AA 2.0 1.5 2.0 1.0

CMC 0.8 0.4 0.4 0.2

Synergist 0.5 - 0.5

Peroxidase 0.01 - 0.01

Carbohydrase - 0.005 - 0.005

Protease 0.008 0.01 0.026 0.026

Amylase 0.007 0.004 - 0.002

Lipase 0.004 0.002 0.004 0.002

Cellulase 0.0015 0.0005 - -

Antibody 10E-1 10E-1 10E-3 10E-2

Photoactivated Bleach (ppm) 70ppm 45ppm - 10ppm

Brightener 1 0.2 0.2 0.08 0.2

PB1 6.0 2.0 - -

NOBS 2.0 1.0 - -

Balance (moisture and trace components) 100 100 100 100 Example 7

Detergent formulations according to the invention were prepared as follows:

                                                                                                             

Zeolite A 30.0 22.0 6.0 6.7

Na SkS-6 - - - - - 3.3

Polycarboxylates - - - - - 7.1

Sodium sulfate 19.0 5.0 7.0 -

MA/AA 3.0 3.0 6.0 -

LAS 14.0 12.0 22.0 21.5

C45AS 8.0 7.0 7.0 5.5

Cationic Surfactant - - - - - 1.0

Silicate - 1.0 5.0 11.4

Soap - - - - 2.0 -

Brightener 1 0.2 0.2 0.2 -

Carbonate 8.0 16.0 20.0 10.0

DETPMP - 0.4 0.4 - Spray

C45E7 1.0 1.0 1.0 3.2 dry additive

PVPVI/PVNO 0.5 0.5 0.5 -

Antibody 10E-1 10E-4 10E-2 10E-2

Protease 0.052 0.01 0.01 0.01

Lipase 0.009 0.009 0.009 0.009

Amylase 0.001 0.001 0.001 0.001

Cellulase 0.0002 0.0002 0.0002 0.0002

Carbohydrase - 0.005 0.01 -

Peroxidase - - - - - - 0.0075

Synergist - - - - - 1.0

NOBS - 6.1 4.5 3.2

PB1 1.0 5.0 6.0 3.9

Sodium Sulfate - 6.0 - - Balance Balance (Moisture and Minor Components) 100 100 100 Example 8 A high density and bleach-containing detergent formulation according to the invention was prepared as follows:

                                                   

Zeolite A 15.0 15.0 15.0

Sodium sulfate 0.0 5.0 0.0

LAS 3.0 3.0 3.0

QAS - 1.5 1.5

DETPMP 0.4 0.4 0.4

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

Spices 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

C25E3 2.0 - - Dry Additive

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

Polyethylene oxide of MW5000000 - - - 0.2

Bentonite - - - 10.0

Antibody 10E-4 10E-1 10E-3

Protease 0.01 0.01 0.01

Lipase 0.009 0.009 0.009

Amylase 0.005 0.005 0.005

Cellulase 0.002 0.002 0.002

Carbohydrase 0.002 0.002 0.002

Polysiloxane defoamer 5.0 5.0 5.0 dry additive

Sodium sulfate 0.0 3.0 0.0

Balance (moisture and trace components) 100.0 100.0 100.0

Density (g/l) 850 850 850Example 9

A high density detergent formulation according to the invention was prepared as follows:

                               

Agglomerates

C45AS 11.0 14.0

Zeolite A 15.0 6.0

Carbonate 4.0 8.0

MA/AA 4.0 2.0

CMC 0.5 0.5

DETPMP 0.4 0.4 spray

C25E5 5.0 5.0

Spices 0.5 0.5 dry additives

HEDP 0.5 0.3

SKS 6 13.0 10.0

Citrate 3.0 1.0

TAED 5.0 7.0

Percarbonate 20.0 20.0

SRP1 0.3 0.3

Antibody 10E-2 10E0

Protease 0.014 0.014

Lipase 0.009 0.009

Cellulase 0.001 0.001

Amylase 0.005 0.005

Carbohydrase 0.005 0.005

Peroxidase - 0.001

Synergist - 0.1

Polysiloxane defoamer 5.0 5.0

Brightener 1 0.2 0.2

Brightener 2 0.2 -

Balance (moisture and trace components) 100 100

Density (g/l) 850 850Example 10

A granular detergent formulation according to the invention was prepared as follows:

Ⅰ Ⅱ III ⅴ aLAS 21.0 25.0 18.0 18.0-Coconut C12-14AS---21.9AE3S-1.5 1.5 2.3 Puja dihydroxyl-based ammonium chloride-0.4 0.7 0.8 non-ion surface activity agent 1.2-0.9 0.5 -Cococa C12-14 fat alcohol---1.0stpp 44.0 25.0 22.5 22.5 22.5 Biite A 7.0 10.0-8.0mA/AA-0.9 -SRP1 0.3 0.15 0.2cmc 0.3 2.0 0.75 0.0 carbonate 17.5 29.3 5.0 13.0 15.0 silicate 2.0-7.6 7.9-antibody 10E-2 10E-2E-10E-3 10E+1 protease 0.007 0.007 0.007 0.007 amylase-0.004 0.004 0.004 lipidase 0.003-0.003-fibol enzymease -0.001 0.001 0.001-Agly-0.003 0.006 peroxidase 0.005 0.005 0.01--0.7 1.0 -NOBS--1.2 1.2 1.0pb1-2.4 1.2 Trinhoethalidine- --0.7 1.0 Tradyle Trone Ayramine-0.6-Magnesium Sulfate-0.8-Light Activating Bleach 45PPM 15PPM 45PPM 42PPM Plasticizer 0.3 0.05 0.13 0.13 water and minor components up to 100% Example 11

A liquid detergent formulation according to the invention was prepared as follows:

Ⅰ Ⅱ Ⅲ ⅴ ⅵ ⅵ ⅷLAS 10.0 13.0 9.0-25.0--C25AS 4.0 1.0 1.0-13.0 18.0 15.0C25E3S 1.0-3.0-2.0 4.0C25E7 6.0 1.5-4.0 4.0tfaa-4.5-6.0 8.0 8.0QAS---3.0 1.0--TPKFA 2.0-13.0 2.0-15.0 7.0 7.0 Rapeseed fatty acids--5.0-4.0 4.0 citrate 2.0 1.0 1.5 1.0 1.0 1.0 1.0 Twelve carboninel/14.0 12.0 10.0-15.0--carbonine-based amber hydrotic acid 4.0 2.0 1.0-1.0--ethanol 4.0 7.0 2.0 7.0 2.0 2.01,2 propane 2.0 4.0 7.0 6.0 10.0 13.0 Single ethanyamine--5.0-- 9.0 9.0 triple ethanlamine--8---------------8.0 7.0 7.7 8.0 7.5 8.0 8.2 ethyl oxidized quadrathytes 0.5-0.5 0.2-0.4 0.3 Panamine DETPMP 1.0 1.0 0.5 1.0 2.0 2.0 1.0 -SRP2 0.3-0.3 0.1-0.2 0.1pvno ------0.10 antibody 10E-2 10E+10E-5 10E-2 10E-3 10E-10E-2 protease .005. 005.004.003 0.08.005.003 .006 lipase-.002-. 0002- .003 .003 amylase .002 .002.004 .002 .008 .005 .0055 fiber enzymes-- .0001-.0004.0004 Agly-.005 .005 0.05 0.0 0.1 peroxidase 0.05 0.01 — 0.01 0.1-0.1 Efficiency Efficiency 1.0 0.1 5-5 Hydrogenation 1.0-1.0 1.0 1.0 1.0-1.0 boric acid 0.1 0.2-2.0 1.0 1.5 1.5 2.5 2.5 sodium methampite--1.0------0.015-0.01-----4.0 4.0-suspended clay SD3--0.6 0.3 - -

Balanced amounts of moisture and minor components: up to 100% Example 12

A granular fabric washing composition according to the invention having an "in-wash softening" effect is prepared as follows:

                                 

45AS - 10.0

LAS 7.6 -

68AS 1.3 -

45E7 4.0 -

25E3 - 5.0

Cocoalkyl-dimethyl-hydroxyethylammonium chloride 1.4 1.0

Citrate 5.0 3.0

NaSKS-6 - 11.0

Zeolite A 15.0 15.0

MA/AA 4.0 4.0

DETPMP 0.4 0.4

PB1 15.0 -

Percarbonate - 15.0

TAED 5.0 5.0

Green Soil 10.0 10.0

HMWPEO - 0.1

Antibody 10E-1 10E-3

Protease 0.02 0.01

Lipase 0.02 0.01

Amylase 0.03 0.005

Cellulase 0.001 -

Carbohydrase 0.001 -

Peroxidase 0.005 0.01

Synergist 0.5 1.0

Silicate 3.0 5.0

Carbonate 10.0 10.0

Granular antifoam 1.0 4.0

CMC 0.2 0.1

Water/Minor Components Up to 100% Example 13

A rinse-in fabric softener composition of the present invention was prepared as follows:

Softener Active 20.0

Antibody 10E-2

Amylase 0.001

Cellulase 0.001

Carbohydrase 0.01

HCl 0.03

Antifoaming agent 0.01

Blue dye 25ppm

Calcium chloride 0.20

Spice 0.90

Water/Minor Components up to 100% Example 14

Fabric softener compositions of the present invention were prepared as follows:

                                 

DEQA 2.60 19.00 -

SDASA - - - 70.00

Stearic acid, Ⅳ=0 0.30 - -

Neodol 45-13 - - - 13.00

Hydrochloric acid 0.02 0.02 -

Ethanol - - - - 1.00

PEG - 0.60 -

Antibody 10E-1 10E-4 10E-2

Cellulase 0.001 - 0.004

Carbohydrase 0.005 0.005 0.005

Spices 1.00 1.00 0.75

Digeranyl succinate - - - 0.38

Polysiloxane defoamer 0.01 0.01 -

Electrolyte - 600ppm -

Dye 100ppm 50ppm 0.01

Water and minor components 100% 100% - Example 15

A synthetic detergent bar washing composition of the present invention was prepared as follows:

                                                        

C26AS 20.00 20.00 20.00 20.00

CFAA 5.0 5.0 5.0 5.0

LAS(C11-13) 10.0 10.0 10.0 10.0

Sodium Carbonate 25.0 25.0 25.0 25.0

Sodium pyrophosphate 7.0 7.0 7.0 7.0

STPP 7.0 7.0 7.0 7.0

Zeolite A 5.0 5.0 5.0 5.0

CMC 0.2 0.2 0.2 0.2

Polyacrylate (MW1400) 0.2 0.2 0.2 0.2

Coconut Monoethanolamide 5.0 5.0 5.0 5.0

Antibody 10E-2 10E-2 10E-1 10E-3

Amylase 0.01 0.02 0.01 0.01

Protease 0.3 - 0.5 0.05

Lipase 0.003 0.05 0.1 0.005

Carbohydrase 0.01 0.02 0.005 -

Whitening agent, fragrance 0.2 0.2 0.2 0.2

Calcium Sulfate 1.0 1.0 1.0 1.0

Magnesium Sulfate 1.0 1.0 1.0 1.0

Water 4.0 4.0 4.0 4.0

       Fillers*: balance to 100%* may be selected from conventional substances such as calcium carbonate, talc, clays (kaolin, smectite), silicates, etc. Example 16

The following compact high density (0.96Kg/l) dishwashing detergent compositions I-VI of the present invention were prepared:

Ⅰ Ⅱ III ⅴ ⅵ ⅵStpp-49.0 38.0-citrate 33.0 17.5-54.0 25.4 carbonate-17.5-20.0 14.0 25.4 silicate 33.0 14.8 20.4 14.8-Polarate-2.5 2.5 -PB11 1.9 9.7 7.8 14.3 7.8 -PB4 8.6-----6.7-6.7 Non-ion surface active agent 1.5 2.0 1.5 1.5 1.5 2.6TAed 4.8 2.4-2.4 4.0Hedp 0.8 1.0 0.5 -DetPMP 0.6 0.6 0.6---PAAC--0.2--BZP--4.4--0.5 0.5 0.5 0.5 0.2 antibody 10E-2 10E0 10E-1 10E-6 10E-3 protease 0.075 0.10 0.08 0.01 0.01 0.01 0.01 Lipidase 0.001 0.001 0.002 0.005 0.01 0.005 amylase 0.05 0.015 0.015 0.01 0.0025 agonase 0.005 0.01-0.05 0.1 Portaidase-0.01 0.05--0.5-BTA 0.3 0.3 0.3 0.3- Nitrate-0.3---PA30 4.0------Sanyuan sync-4.0 -480n-6.0 2.8--sulfate 7.1 20.8 8.4-0.5 1.0PH (1 % solution) 10.8 11.0 10.9 10.8 10.9 9.6 Example 17

Preparation of the following bulk density of the present invention is the granular detergent composition embodiment I-VI of 1.02Kg/L:

Ⅰ Ⅱ III ⅴ ⅵ ⅵStpp 30.0 30.0 30.0 27.9 34.5 26.7 carbonate 30.5 30.5 30.0 30.5 2.80 silicate 7.4 7.4 12.0 8.0 20.3pb1 4.4 4.4-4.4 -NADDC--2.0-1.5 non-ion surface activated agent 0.755555555 0.75 0.75 1.9 1.2 0.5TAed 1.0 1.0-1.0-PAAC-0.004- -BZP-----Paraffin 0.25 0.25--Antibody 10E-1 10E-3 10E-2 10E 10E -3蛋白酶            0.05   0.05   0.05    -      0.1     -脂酶              0.005  0.005  0.001   0.01   0.002   0.002淀粉酶            0.003  0.001  0.01    0.02   0.01    0.015糖酶              0.005  0.007  0.01    0.05   0.005   -过氧化物酶        -      -      -       -      0.001   0.05增效剂            -      -      -       - 0.1 1.0BTA 0.15-0.5---sulfate 23.9 23.9 23.9 31.4 17.4-PH (1 % solution) 10.8 10.8 10.7 10.7 10.3 Example 18

The following 259 weight tablets of the detergent composition of the present invention were prepared by compressing the granular dishwashing detergent composition using a standard 12-head rotary press at ^a pressure of 13 KN/cm:

                                                  

STPP - 48.8 47.5

Citrate 26.4 - -

Carbonate - - 5.0 -

Silicate 26.4 14.8 25.0

Antibody 10E-2 10E-3 10E-1

Protease 0.03 0.075 0.01

Lipase 0.005 0.005 0.005

Amylase 0.01 0.005 0.001

Carbohydrase 0.01 0.005 0.01

Peroxidase - - - 0.001

Synergist - - - - 1.0

PB1 1.6 7.8 -

PB4 6.9 - 11.4

Non-ionic surfactant 1.2 2.0 1.1

TAED 4.3 2.4 0.8

HEDP 0.7 -

DETPMP 0.65 - -

Paraffin 0.4 0.5 -

BTA 0.2 0.3 -

PA30 3.2 - -

Sulphate 25.0 14.7 3.2

pH (1% solution) 10.6 10.6 11.0 Example 19

Prepare the liquid dishwashing detergent composition I-II of the present invention whose density is 1.40Kg/L as follows:

                       

STPP 33.3 20.0

Carbonate 2.7 2.0

Silicate - 4.4

NaDCC 1.1 1.15

Non-ionic surfactant 2.5 1.0

Paraffin 2.2 -

Antibody 10E-1 10E-2

Lipase 0.003 0.003

Protease 0.03 0.02

Amylase 0.005 0.0025

Carbohydrase 0.005 0.005

480N 0.50 4.00

KOH - 6.00

Sulphate 1.6 -

pH (1% solution) 9.1 10.0 Example 20

A liquid dishwashing composition according to the invention was prepared as follows:

                                                          

C17ES 28.5 27.4 19.2 34.1 34.1

Amine oxide 2.6 5.0 2.0 3.0 3.0

C12 Glucosamide - - - 6.0 - -

Betaine 0.9 - - - 2.0 2.0

Xylenesulfonate 2.0 4.0 - 2.0 -

Neodol C11E9 - - - 5.0 - -

Polyhydroxy fatty acid amides - - - - - 6.5 6.5

Sodium diethylene pentaacetate (40%) - - - 0.03 - -

TAED - - - - - 0.06 0.06

Sucrose - - - - - 1.5 1.5

Ethanol 4.0 5.5 5.5 9.1 9.1

Alkyl diphenyl ether disulfonates - - - - - - - 2.3

Calcium formate - - - - - 0.5 1.1

Ammonium citrate 0.06 0.1 - - - -

Sodium Chloride - 1.0 - - - -

Magnesium chloride 3.3 - 0.7 -

Calcium chloride - - - - 0.4 - -

Sodium Sulfate - - - 0.06 - -

Magnesium Sulfate 0.08 - - - - -

Magnesium Hydroxide - - - - - 2.2 2.2

Sodium Hydroxide - - - - - 1.1 1.1

Hydrogen peroxide 200ppm 0.16 0.006 - -

Antibody 10E-3 10E-2 10E-1 10E-2 10E-4

Protease 0.017 0.005 0.0035 0.003 0.002

Spices 0.18 0.09 0.09 0.2 0.2

Water and minor components up to 100% Example 21

A liquid hard surface cleaning composition of the present invention was prepared as follows:

Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ Ⅵ Ⅵ

Antibody 10E-3 10E-4 10E-2 10E-1 10E-2 10E-1

Lipase 0.003 0.005 0.005 0.001 0.01 0.001

Amylase 0.01 0.002 0.005 0.02 0.001 0.005

Protease 0.05 0.01 0.02 0.03 0.005 0.005

Carbohydrase 0.01 0.002 0.005 0.02 0.001 0.005

EDTA* - - - 2.90 2.90 - -

Citrate - - - - - - - 2.90 2.90

LAS 1.95 - 1.95 - 1.95 -

Cl2AS - 2.20 - 2.20 - 2.20

Sodium Sulfate C12(Ethoxy)** - 2.20 - 2.20 - 2.20

C12 Dimethylamine Oxide - 0.50 - 0.50 - 0.50

SCS 1.30 - 1.30 - 1.30 -

Hexyl Carbitol** 6.30 6.30 6.30 6.30 6.30 6.30

Water balance to 100%

*Tetrasodium EDTA

**Diethylene glycol monohexyl ether

***All formulations adjusted to pH 7 Example 22

A spray composition for cleaning hard surfaces and removing household mildew according to the present invention was prepared as follows:

           

Antibody 10E-2

Lipase 0.003

Amylase 0.01

Protease 0.01

Carbohydrase 0.05

Sodium octyl sulfate 2.00

Sodium Lauryl Sulfate 4.00

Sodium hydroxide 0.80

Silicate (sodium) 0.04

Spices 0.35

Water/Minor Components up to 100% Example 23

Preparation of the detergent additive of the present invention:

                       

LAS - - - 5

STPP 30 30 -

Zeolite A - - - 35

PB1 20 20 15

TAED 10 10 8

Protease - - - 0.3

Amylase 0.4 - 0.2

Carbohydrase 0.1 - 0.2

Antibody 10E+1 10E+1 10E0

Claims (13)

1. A detergent composition comprising an enzyme and an antibody directed by the enzyme. 2. A detergent composition according to claim 1, wherein said enzyme-directed antibody is present in an amount of 10E-6% to 10E+1% by weight of the total composition. 3. A detergent composition according to any preceding claim, wherein said enzyme-directed antibody is incorporated into a release agent. 4. A detergent composition according to claims 1-3, wherein the enzyme is present at a level of 0.0001% to 2%, preferably 0.0001% to 0.5%, more preferably 0.001% to 0.1% pure enzyme by weight of the total composition. 5. A detergent composition according to claims 1-4, wherein the molecular ratio of antibody to enzyme is equal to or less than 100:1, preferably equal to or less than 50:1. 6. A detergent composition according to claims 1-5, wherein said antibody is a monoclonal antibody, preferably a fragment thereof. 7. A detergent composition according to claim 6, wherein the molecular ratio of antibody to enzyme is equal to or less than 50:1, preferably equal to or less than 20:1. 8. The detergent composition according to claims 1-7, wherein said enzyme is selected from the group consisting of protease, lipase, cellulase, amylase, xylanase, cutinase, chondroitinase, hyaluronidase, glucan Endoglycosidases, pectinases, peroxidases, and mixtures thereof, said enzyme-directed antibodies being proteases, lipases, cellulases, amylases, xylanases, cutinases, chondroitinases, Antibodies directed against hyaluronidase, endoglucanase, pectinase, peroxidase and/or mixtures thereof. 9. A detergent composition according to any preceding claim, further comprising one or more selected from the group consisting of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, builders, bleaching systems, suds suppressors, detergency Components of polymers, lime soap dispersants, soil suspending and anti-redeposition agents, smectite clays and/or mixtures thereof. 10. A detergent composition according to any preceding claim which is in the form of a liquid, granule, powder, gel, paste or bar. 11. A detergent additive containing an enzyme-directed antibody. 12. A detergent additive according to claim 11, further comprising an enzyme directing the antibody. 13. Use of enzyme-directed antibodies to control enzyme activity in detergent compositions.