MXPA01009927A - A detergent composition containing a metallo-protease - Google Patents

Abstract

A detergent composition of the present invention contains a protease. More particularly, the present invention relates to laundry detergent compositions, dishwashing detergent compositions, hard surface cleaning compositions and personal cleansing compositions which contain a metallo-protease. Further more particularly, the detergent composition of the present invention contains a detersive surfactant and a metallo-protease which has more than 15AU/mg activity caseinolytic activity.

Description

COMPOSITION DETERGENT CONTAINING A METAL-PROTEASE FIELD OF THE INVENTION The present invention relates to detergent compositions comprising a protease. More particularly, the present invention relates to laundry detergent compositions, dishwashing detergent compositions, hard surface cleaning compositions and personal cleansing compositions comprising a metalloprotease.

BACKGROUND OF THE INVENTION Several types of enzymes have been used for a long time in laundry detergents to assist in the removal of certain stains from fabrics. Each class of enzyme (amylase, protease, lipase, cellulase, etc.) generally catalyzes a different chemical reaction. For example, protease enzymes are known for their ability to hydrolyze (break a compound into two or more simpler compounds) other proteins. Many food products and other organic materials contain proteins that dye fabric materials, such as clothing. Protease enzymes can help remove these spots by breaking down proteins. For this reason, naturally occurring or bioengineered protease enzymes have been added to laundry detergent compositions. The protease enzymes are divided into four groups, serine proteases, cysteine proteases, proteases of aspartic acid and metalloprotease. Although the use of serine protease has been investigated for use in detergent compositions for several years, metalloprotease has not been used in detergent compositions for many reasons. Specifically, the stability and activity of the metalloprotease in a detergent solution, and the effect of chelating agents on the metalloprotease were unknown. In addition, the effect of the metallo-protease on various fabric materials was unknown. Therefore, there are many unknown parameters to ensure satisfactory performance. However, there is a continuing need for proteases that provide improved and improved cleaning capacity when used in detergents and cleaning compositions. It has now been found that a detergent composition containing a metallo-protease is effective in removing dirt, especially protein-based stains.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions comprising a protease (s). More particularly, the present invention relates to laundry detergent compositions, dishwashing detergent compositions, hard surface cleaning compositions and personal cleansing compositions comprising a metalloprotease. Specifically, in one aspect of the present invention there is provided a detergent composition comprising: (1) a detersive surfactant; and (2) a metallo-protease. In addition, the metalloprotease has more than 15AU / mg of caseinolytic activity. Preferably, 80% of the metallo-protease activity is inhibited by at least 1 mM of metallo-protease inhibitor. In another aspect of the present invention there is provided a detergent composition comprising: a) from about 1% to about 60% by weight of a detersive surfactant; b) from about 0% to about 80% by weight of a builder; and c) from about 0.0001% to about 5% by weight of a metallo-protease where the metalloprotease has more than 15AU / mg of caseinolytic activity. Current proteases are mainly serine proteases (serine as the active / binding site of the enzyme) that have an optimum pH in the alkaline range, however, metallo-proteases (which have metal ions as the active site / binding site). enzyme) are normally neutral proteases. The detergent compositions of the present invention contain metallo-protease enzymes, where the metallo-protease shows substantially better performance in terms of benefits against protein spots on common proteases. Usually a pH of the detergent composition solution is neutral to alkaline (pH 7-11). Although the metalloprotease has an optimum pH in the neutral range (6-8), the metallo-protease shows a better cleaning performance than other proteases even in the detergent composition of pH 9. Although it is not desired to be limited by theory, the metallo-protease has a greater specific activity and a broad specific breakdown compared to other proteases. Therefore, even in alkaline solutions, the metallo-protease may show a better cleaning performance than other proteases. These and other features, aspects, and advantages of the present invention will be apparent to those skilled in the art from a reading of the present disclosure.

DETAILED DESCRIPTION OF THE INVENTION While the specification concludes with claims that particularly point to the distinctive claim of the invention, it is believed that the present invention will be better understood from the following description.

All percentages are by weight of the total composition unless otherwise specified. All relationships are weight ratios unless otherwise specified.

Definitions As used herein, "comprising" means that other steps and other ingredients that affect the final result may be added. This term encompasses the terms "consisting of" and "consisting essentially of". All references cited are incorporated herein by reference in their entirety. The citation of any reference is not an assertion with respect to any determination of the availability of a prior art to the claimed invention. As used herein, the term "detergent composition" or "Detergent" is intended to designate any of the conventionally used agents for removing dirt, such as general household detergents or laundry detergents of synthetic or soap type.

Detergent compositions containing a metalloprotease The detergent composition of the present invention contains a metalloprotease. The metalloprotease in the detergent composition of the present invention have at least more than 15 AU / mg of caseinolytic activity by the caseinolytic test method described in detail below. The metallo-protease in the detergent composition of the present invention preferably has a characteristic of more than 80% of the metallo-protease activity inhibited by at least 1 mM of metallo-protease inhibitors. Preferably the metalloprotease inhibitor is selected from the group consisting of 1.10 phenanthroline, phosphoramidon, or EDTA. The metalloprotease in the detergent composition of the present invention further preferably has more than 70% activity under a pH condition of about 4.5 to about 9.0 to 20 ° C, preferably, about pH 5 to about 8. and more than 70% activity under a temperature condition of about 50 ° C to about 60 ° C, preferably, about 50 ° C to about 55 ° C. The metalloprotease in the detergent composition of the present invention optionally has these characteristics: a) a molecular weight of from about 28 KDa to about 40 KDa, preferably, from about 30 KDa to about 36 KDa; b) Zn, Co, Mn or Cu as an active center, preferably, Zn (Zinc) as an active center. A calcium ion can be added to the formulation in any way, but preferably it is added as a salt. Preferably it is selected from the group consisting of calcium chloride, calcium sulfate, calcium nitrate, calcium citrate, formate, acetate, tartrate, and mixtures thereof, more preferably, the salt is calcium acetate or calcium. Most current serine alkaline proteases possess a primary breakthrough site in the insulin B chain, whereas, the metalloprotease in the detergent composition of the present invention possesses at least 4 major break sites, in accordance with the proof of the fermentation pattern of the insulin beta chain described below. Although not wishing to be bound by theory, the metalloprotease is inhibited by metalloprotease inhibitors because the metalloprotease has a metal ion in the active center and some metalloproteases need calcium ion for stability. The metalloprotease inhibitors can be combined with metal ions and / or calcium ions and as a result, the metalloprotease is inhibited by the inhibitors. A metalloprotease inhibitor is not limited, but for example, o-phenanthroline, ethylenediaminetetraacetic acid (EDTA) or phosphoramidon is used. The metalloprotease in the detergent composition of the present invention can be derived from a natural or recombinant source. If the metallo-protease is derived from a natural source, the natural source is a bacterium preferably Bacillus subtilis (D. Tsuru & amp; amp;; T. Yoshimoto, 'Microbial Proteases', Handbook of Microbiology. 2nd Edition by A.l. Laskin & HE HAS. Lechevalier, 239-283. The metalloprotease can also be derived from commercially available products such as Protease N ™ by Amano Seiyaku Co., Ltd (Tokyo, Japan), such as Orientase 90N ™ from Hankyu Bio-industries Corp. Ltd (Osaka, Japan). The preferred metalloprotease is, for example, the metalloprotease described in Kobayashi, et al, Agricultural and Biological Chemistry 53 (10), page 2737-2750 (1989), or Kobayashi et al, Journal of Biochemistry 106, page 1110 -1113.

Metallo-protease performance tests The metallo-proteases of the present invention can be characterized by the following description. Although not wishing to be limited by theory, the performance of a protease can be decided by two parameters, one is specific activity (hydrolysis rate) and the other is broad specificity of breakdown. The specific activity means how fast the protease can break a protein substrate. One of the methods for measuring specific activity is the caseinolytic activity test. This method uses casein as a protein substrate and measures the hydrolysis rate of casein (dimethyl casein, DMC) by the protease and evaluates the specific activity. For example, the caseinolytic activity assay method is carried out as follows: 5.5 mg / m of dimethyl casein (DMD, Sigma) were prepared in buffer of 0.1 M tris-HCl pH 7.0 and 0.1 ml of protease solution was mixed with 0.9 ml of this casein solution and the hydrolysis was carried out at 20 ° C. Just after 10 min, 4 ml of TCA solution (0.12 M CCI3COOH + 0.22 M CH3COONa.3H2O + 0.33 M CH3COOH) was added to this enzyme-casein mixture and incubated at 30 minutes at 20 ° C. Then, the white mixture was centrifuged at 12000 rpm for 8-10 min. 0.5 ml of the supernatant was transferred to a disposable tray and 2.5 ml of 0.5 M Na2C03 was added. After 5-10 min, 0.5 ml of phenol reagent (1 ml Folin Ciocalteu's phenol reagent, Sigma, was added with 5 ml of water milli-Q) and incubated at room temperature for 40 min. And then, the absorbance at 660 nm was measured against water. An Anson unit (AU) of enzymatic activity is defined as the amount of enzyme that increases the absorbance corresponding to a micromol of tyrosine in one minute under the aforementioned measurement conditions. According to this test, the metalloprotease in the detergent composition herein has more than 15 AU / mg, preferably more than 30 AU / mg. The broad specificity of breaking means the ability of a protease to break the peptide bond after different types of amino acids. For example, if a protease breaks the peptide bond between Leu-Tyr. In this case, the breaking specificity is Leu. Some proteases can break several bonds after several different amino acids on different proteins. One of the methods to measure the specificity of the break is the fragmentation pattern test of the B chain of insulin. This method uses the beta chain of insulin as a protein substrate and measures the number of protease hydrolysis sites. For example, the method of testing the fermentation pattern of the B chain of insulin is carried out as follows: The major break sites are defined as the break sites in the early stages of hydrolysis of the B chain of insulin ( before hydrolysis less than 50% of chain B insulin). To identify the main break sites, the following method was used. 1 mg / ml of beta chain of oxidized insulin was prepared in 0.1 M Tris-HCl buffer pH 7.0 and incubated at 35 ° C for 10 min. Then, 10 microliters of enzyme solution were mixed with the insulin solution at a final concentration of 0.1-0.2 ppm. After only 3 minutes of hydrolysis, the reaction was stopped by adding a volume of 0.1 M HCl. Then, the reaction mixture was analyzed by HPLC to measure the fragmented peptides. The identification of the fragmented peptides was carried out when measuring the PM by LC / MS. Most current serine alkaline proteases possess a major cleavage site (Leu 15-Tyr16) in the B chain of insulin, whereas these metallo-proteases possess at least 3 major break sites. The detergent composition of the present invention contains from about 0.0001% to about 5%, preferably, from about 0.002% to about 1% by weight of mertalo-protease.

Detersive Surfactant The detergent compositions of the present invention include surfactants wherein the surfactant may be selected from the group consisting of nonionic and / or anionic and / or cationic and / or ampholytic and / or zwitterionic and / or semi-surface active agents. -polars. The surfactant is typically present at a level of about 0.01% to about 60% by weight. The most preferred levels of incorporation are from about 1% to about 35% by weight, more preferably from about 1% to about 30% by weight of detergent compositions according to the invention. The surfactant is preferably formulated to be compatible with enzymatic components present in the composition. In liquid gel compositions the surfactant is more preferably formulated so as to promote, or at least not degrade, the stability of any enzyme in this composition. Preferred surfactants when used in accordance with the present invention comprise a surfactant of one or more nonionic and / or anionic surfactants described herein. Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactants of the present invention, with condensate polyethylene oxide being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in any straight chain configuration or branched with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal ™ CO-630, marketed by GAF Corporation; and Triton ™ X-45, X-114, X-100 and X-102, all marketed by Rohm & Haas Company. These surfactants are commonly referred to as alkoxylated alkyl phenols (eg, alkyl phenol ethoxylates). The condensation products of the primary and secondary aliphatic alcohols with from about one to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactants of the present invention. The alkyl chain of the aliphatic alcohol may be either linear or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. The preferred condensation products are alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and more preferably about 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products. Examples of commercially available nonionic surfactants of this type include Tergitol ™ 15-S-9 (the condensation product of the linear alcohol of C 11 -C 15 with 9 moles of ethylene oxide), Tergitol ™ 24-L-6 NMW (the condensation product of the C12-C14 primary alcohol with 6 moles of ethylene oxide with a narrow molecular weight distribution), both marketed by Union Caribe Corporation; NeodolTM 45-9 (the condensation product of the linear alcohol of C14-C15 with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of the linear alcohol of C12-C13 with 3.0 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of the linear alcohol of C14-C15 with 7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of the linear alcohol of C14-C15 with 5 moles of ethylene oxide) marketed by Shell Chemical Company, KyroTM EOB (the condensation product of C13-C15 alcohol with 9 moles of ethylene oxide), marketed by The Procter & amp;; Gamble Company, and Genapol LA O30 or 050 (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. A preferred range of HLB in these products is 8-11 and more preferably 8-10. The nonionic surfactants also useful of the present invention are the alkyl polysaccharides described in US Pat. No. 4,565,647, to Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, for example a polyglucoside, a hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7 units of saccharide. Any reduced saccharide containing from 5 to 6 carbon atoms can be used, for example glucose, galactose and portions of galactosyl that can be substituted by the glucosyl portions (optionally the hydrophobic group is attached in the 2-, 3-, 4- positions, etc. thus giving a glucose or galactose as opposed to a glycoside or galactoside). The intersaccharide bonds can be, for example, between a position of the additional saccharide unit and positions 2-, 3-, 4-, and / or 6- of the preceding saccharide unit. Preferred alkyl polyglycosides have the formula R2O (CnH2r? O) t (glycosyl)? wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3 preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7. The glucosyl is preferably derived from glucose. To prepare these compounds, the alcohol or polyethoxyalkyl alcohol is first formed and then reacted with glucose, or with a glucose source, to form the glucosyl (attached at position 1). The additional glucosyl units can then be linked between position 1 and the preceding glucosyl units in the 2-, 3-, 4-, and / or 6- positions, preferably with position 2 predominating. The condensation products of ethylene oxide with a Hydrophobic bases formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic detersive surfactant of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of between about 1500 to about 1800 and will exhibit insolubility in water. The addition of polyoxyethylene portions to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained to the point where the polyoxyethylene content is about 50 of the total product weight. of condensation which corresponds to condensation with more than about 40 moles of ethylene oxide. Examples of compounds of this type include certain commercially available surfactants such as Plurafac ™ LF404 and Pluronic ™, marketed by BASF. Also suitable for use as nonionic surfactants of the present invention, are the condensation products of ethylene oxide with the resulting product from the reaction of propylene oxide and ethylene diamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and an excess of propylene oxide, and generally has a molecular weight of between about 2,500 to about 3,000. This hydrophobic portion is counteracted with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of about 5%., 000 to around 11, 000. Examples of this type of nonionic surfactants include certain compounds commercially available as Tetronic ™, marketed by BASF. Preferably for use, as surfactants of the present invention are the condensates of polyethylene oxide of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkyl polysaccharides, and mixtures thereof. More preferred are the alkylphenol ethoxylates of Cs-C having from 3 to 15 ethoxy ethoxylated alcohol groups of Cs-C-is (preferably with a Cio average) having from 2 to 10 ethoxy groups, and mixtures thereof. The highly preferred nonionic surfactants are polyhydroxy fatty acid amine surfactants of the formula where R1 is H, or R1 is C-, 2-hydroxyethyl, 2-hydroxypropyl hydrocarbyl or a mixture thereof, R2 is C5.31 hydrocarbyl and Z is a polyhydroxycarbyl having a straight hydrocarbyl chain with at least three hydroxyl 7 directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight Cn-15 alkyl or an alkyl or alkenyl chain of C-iß-iß such as coconut alkyl or mixtures thereof, and Z is derived from a reduced sugar such as glucose, fructose, maltose, lactose, in a reduction of reductive amination. Anionic surfactants suitable for use as linear alkylbenzene sulfonates, alkyl ester sulfonate, branched alkyl sulfonate, alkyl sulfonate surfactants with medium branching include linear esters of Cs-C20 carboxylic acids (ie fatty acids) ) which are sulfonated with gaseous SO3 in accordance with "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials may include natural fatty substances such as derived from tallow, palm oil, etc. Preferred alkyl ester sulphonated surfactants, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula: wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a Ci-Cβ hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a salt soluble in water with the alkyl ester sulfonate. 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, R3 is C10-C16 alkyl and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates where R3 is C10-C16 alkyl. Other suitable anionic surfactants include the alkyl sulfate surfactants which are salts or water soluble acids of the formula ROSO3M wherein R is preferably a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having an alkyl component of C10- C20. more preferably an alkyl or a C12-C18 hydroxyalkyl, and M is H or a cation, for example, an alkali metal cation (for example, sodium, potassium, lithium), or ammonium or substituted ammonium (for example methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine diethylamine, triethylamine, and mixtures thereof, and the like., Typically, the C12 alkyl chains -C16 are preferably for low wash temperatures (for example below about 50 ° C) and C16-18 alkyl chains are preferred for higher wash temperatures (for example, greater than about 50 ° C.) Other surfactants Anionic agents useful for detersive purposes can also be included in the detergent composition of the present invention, which may include salts (including, for example, sodium, potassium, nio, and substituted ammonium salts such as mono-, di- and triethanolamine salts) soap, C8-G22 primary or secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of pyrolyzed product of alkali metal citrates For example, as described in British Patent Specification No. 1, 082,179, C8-C24 alkyl polyglycol ether sulfonates (containing more than 10 moles of ethylene oxide); alkyl glycerol sulfonates, glycerol fatty acid sulphonates, fatty oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulphates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfocycinates, mono-esters of sulfocycnates (especially saturated and unsaturated C12-C-18 monoesters) and diesters of sulfocycinates ( especially saturated and unsaturated C6-C12 diesters), acyl sarcocinates, alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (the nonionic non-sulfate compounds are described below), primary and branched alkyl sulfates, and polyethoxyalkyl carboxylates such as those of the formula RO (CH2CH2?) k-CH2COO-M + where R is a C8-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as resin, hydrogenated resin, and hydrogenated resin acids and resin acids present in or derived from wood oil.

Additional examples are described in "Surface Active Agents and Detergents" (Vol. 1 and II by Schwartz, Perry and Berch). A variety of such surfactants are generally described in the US patent. A. 3,929,678, issued December 30, 1975 to Laughiin, et al. in column 25, line 58 to column 29, line 23 (incorporated herein by reference). When included herein, the detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 3% to about 20% by weight of said anionic surfactants. Highly preferred anionic surfactants include alkoxylated alkyl sulfate surfactants themselves which are water soluble salts or acids of the formula RO (A) mS03M where R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having one component C10-C24 alkyl, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a cation with substituted ammonium. The alkyl ethoxylated sulfates as well as the propoxylated alkyl sulphates are contemplated herein. Specific examples of the substituted ammonium cations include methyl-, dimethyl-, trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures of the same, and similar. Exemplary surfactants are polyethoxylated sulfate (1.0) of C12-C18 alkyl (Ci2-CidE (1.0) M), polyethoxylated sulfate (2.25) of C12-C18 alkyl (C? 2-C18E (2.25) M), sulfate polyethoxylated (3.0) C12-C18 alkyl (Ci2-C? eE (3.0) M), and polyethoxylated sulfate (4.0) C12-C18 alkyl (Ci2-CidE (4.0) M), where M is conveniently selected from sodium and potassium The detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as nonionic and / or anionic surfactants other than those described herein. Detersive surfactants suitable for use in the detergent compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants such as alkyltrimethylammonium halides, and those surfactants having the formula: [R2 (OR3) and] [R4 (OR3) and] 2R5N + X- where R2 is a alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH (CH3) -, - CH2CH (CH2OH ) -, -CH2CH2CH2-, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by the joining of two groups R 4, -CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH where R 6 is any hexose or hexose polymer which has a molecular weight of less than about 1000, and hydrogen where y is not 0; R5 is the same as R4 or is an alkyl chain where the total number of carbon atoms of R2 plus R5 is not greater than about 18, each y is from 0 to about 10 and the sum of the values of y is from 0 to around 15; and X is any compatible anion. The quaternary ammonium surfactants suitable for the present invention have the formula (I): Formula I wherein R1 is a short chain alkyl (C6-C10) or alkylamidoalkyl of the formula (II): CrCl0? Or Formula II and is 2-4, preferably 3. Where R2 is H or a C1-C3 alkyl, where X is 0-4, preferably 0-2, more preferably 0, where R3, R4 and R5 are either the same or different and they can be either a short alkyl chain (C1-C3) or an alkoxylated alkyl of the formula III, wherein X- is a counterion, preferably a halide, for example chloride or methylisulfate.

R6 is C C4 and z is 1 or 2. Preferred quaternary ammonium surfactants are those defined in formula I where Ri is Ce, C10 or mixtures thereof, x = 0, R3, R4 = CH3 and R5 = -CH2CH2OH . The highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula: wherein R 1 is C 1 -C 6 alkyl, each R 2, R 3 and R 4 is independently C 1 -C 4 alkyl, hydroxyalkyl of C1-C4, benzyl, and - (C2H4o)? H where x has a value of 2 to 5, and X is an anion. No more than one of R2, R3 or R must be benzyl. The preferred alkyl chain length for R1 is C12-C15 particularly when the alkyl group is a mixture of long chains derived from coconut or palm kernel fat or synthetically derived by olefin products or alcohol synthesis OXO Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X can be selected from halide, methosulfate, acetate and phosphate ions. Examples of suitable quaternary ammonium compounds of formula (i) for use herein are: Ammonium chloride or trimethylcoccus bromide; ammonium chloride or ammonium dihydroethylmethylcoccus; triethyldecyl ammonium chloride; Ammonium chloride or ammonium hydroxyethyldimethyldecyl; C12-C15 hydroxyethyldimethyl ammonium chloride or bromide; Ammonium chloride or ammonium hydroxyethyldimethyl coconut; ammonium methylisulfate trimethylmiristyl; Ammonium benzyl chloride or dimethylurauryl bromide; ammonium chloride (ethenoxy) 4-dimethyl-lauryl; Hill esters (compounds of formula (i) wherein R1 is alkyl of CH2-CH2-O-C-C12-14 and R2R3R4 are methyl). II O Dialkylimidazolines [compounds of formula (i)]. Other useful cationic surfactants here also are described in the patent of E. U. A. 4,228,044, Cambre, issued on October 14, 1980 and in the European patent application EP 000,224.

Typical cationic fabric softening components include the water-insoluble quaternary ammonium fabric softening actives of the corresponding amine precursor, the most commonly used having a di-long alkyl chain of ammonium chloride or methyl sulfate. Preferred cationic softeners among these include the following: 1) dimethylammonium ditallow chloride (DTDMAC); 2) Dihydrogenated tallow dimethyl ammonium chloride; 3) Dihydrogenated tallow dimethyl ammonium methylisulfate; 4) distearyl dimethyl ammonium chloride; 5) dimethylammonium dioleyl chloride; 6) Methylammonium hydroxyethyl dipalmityl chloride; 7) dimethyl ammonium benzyl stearyl chloride; 8) tallow dimethyl ammonium chloride; 9) hydrogenated tallow trimethylammonium chloride; 10) C12-14 alkyl hydroxyethyl dimethyl ammonium chloride; 11) C12-18 alkyl hydroxyethyl methylammonium chloride; 12) dimethylammonium chloride di (stearoyloxyethyl) (DSOEDMAC); 13) dimethylammonium chloride di (tallowoxyethyl); 14) imidazolinium methylisulfate disebo; 15) imidazolinium methylisulfate 1- (2-de-salam-amidoethyl) -2-seboyl. Biodegradable quaternary ammonium compounds have been presented as traditionally used alternatives to di-long alkyl chain ammonium dimethisulphate chlorides. Said quaternary ammonium compounds contain long chain alkyl (en) yl groups interrupted by functional groups such as carboxyl groups. Such materials and fabric softening compositions containing them are described in numerous publications such as EP-A-0,040,562, and EP-A-0,239,910. The quaternary ammonium compounds and the amine precursors herein have the formula (I) or (II), below: ((II) where Q is selected from -O-C (O) -, -C (O) -O-, -0-C (0) -O-, -NR4-C (O) -, -C (O) -NR4-; R is (CH2) n-Q-T2 or T3; R2 is (CH) m-Q-T4 or T5 or R3; R3 is C1-C4 alkyl or C1-C4 hydroxyalkyl or H; R 4 is H or C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl; T1, T2, T3, T4, T5 are independently C11-C22 alkyl or alkenyl; n and m are integers from 1 to 4; and X- is an anion compatible with softener. Non-limiting examples of anions compatible with softeners include chloride or methylsubate. The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain can be straight or branched. Sebum is a convenient source of long chain alkyl and alkenyl material. Particularly preferred are the compounds wherein T1, T2, T3, T4, T5 represents the mixture of long chain materials typical for tallow. Specific examples of the quaternary ammonium compounds suitable for use in the aqueous fabric softener compositions include: 1) N, N-di (tallowyl-oxy-ethyl) -N, N-dimethylammonium chloride; 2) N, N-di (tallowyl-oxy-ethyl) -N-methyl, N- (2-hydroxyethyl) methylammonium sulfate; 3) N, N-di (2-tallowyl-oxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; 4) N, N-di (tallowyl-oxy-ethylcarbonyl-oxy-ethyl) -N, N-dimethylammonium chloride; 5) N- (2-tallowyl-oxy-2-ethyl) -N- (2-tallowyloxy-2-oxo-ethyl) -N, N-dimethylammonium; 6) N, N, N-tri (tallowyl-oxy-ethyl) -N-methylammonium chloride; 7) N- (2-tallowyl-oxy-2-ethyl) -N- (tallow-N, N-dimethylammonium chloride, and 8) 1,2-diisobutyloxy-3-trimethylaminopropionate chloride; and mixtures of any of the above materials. When included herein, the detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from 1% to about 5% by weight of said cationic surfactants. The ampholytic surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic secondary or tertiary amine derivatives, or aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic radical can be straight or branched chain. One of the aliphatic substituents containing at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one contains a water-soluble anionic group, for example carboxy, sulfonate, sulfate. See in the patent of E.U.A. No. 3,929,678 to Laughiin et al., Issued December 30, 1975 in column 19, lines 18-35, for examples of ampholytic surfactants. When included herein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of said ampholytic surfactants. Zwitterionic surfactants are also suitable for use in detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derived from quaternary ammonium, quaternary phosphonium or quaternary sulfonium compounds. See the patent of E.U.A. No. 3,929,678 to Laughiin et al., Issued December 30, 1975 in column 19, line 38 to column 22, line 48, for examples of zwitterionic surfactants. When included herein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of said zwitterionic surfactants. The semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxide containing an alkyl portion of from about 10 to about 18 carbon atoms and 2 portions selected from the group that it consists of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing an alkyl portion of from about 10 to about 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 about 3 carbon atoms; and water-soluble sulfoxides containing an alkyl portion of from about 10 to about 18 carbon atoms and a portion selected from the group consisting of alkyl portions and hdroxyalkyl of about 1 to about 3 carbon atoms. The semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula: O t R3 (OR4) xN (R5) 2 where R3 is an alkyl, hydroxyalkyl, or phenyl alkyl group or mixtures thereof containing from about 8 to about 22 carbon atoms. carbon; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The groups R5 can be linked together, for example, through an oxygen atom or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular include dimethyl alkyl amine oxides of C-io-C-iß and amine oxides of ethyl dihydroxyethyl C8-C12 alkoxy. When included, the cleaning compositions of the present invention typically comprise from about 0.2% to about 15%, preferably from about 1% to about 10% by weight of said semi-polar nonionic surfactants. The detergent composition of the present invention may further comprise a co-surfactant selected from the group of primary or tertiary amines. Primary amines suitable for use herein include amines according to the formula R1NH2 wherein R1 is an alkyl chain of C-C12, preferably of C6-C? O or R4X (CH2) n, X is -O-, -C (0) NH- or -NH-, R4 is an alkyl chain of C6-C12 n is between 1 to 5, preferably 3. The alkyl chains R1 can be straight or branched and can be interrupted with more than 12, preferably less than 5 portions of ethylene oxide.

Preferred amines according to the aforementioned formula are N-alkyl amines. Amines suitable for use herein may be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include Cß-C -io oxypropylamine, octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl aminopropylamine and amino propylamine. Tertiary amines suitable for use herein include tertiary amines having the formula R 1 R 2 R 3 N wherein R 1 and R 2 are C 8 C alkyl chains or - (CH2- CH-0) xH R3 is either an alkyl chain of C6-C12, preferably Ce-Cio or R3 is R4X (CH2) n, where X is -O-, -C (0) NH- or -NH-, R4 is a C4-C12, n is between 1 to 5, preferably 2-3. R5 is H or C1-C2 alkyl and x is between 1 to 6.

R3 and R4 can be linear or branched; the alkyl chains R3 can be interrupted with more than 12, preferably less than 5, portions of ethylene oxide. Preferred tertiary amines are R1R2R3N where R1 is a alkyl chain of C6-C12, R2 and R3 are C1-C3 alkyl or where R5 is H or CH3 and x = 1-2. Also preferred are amido amines of the formula: O R1-C-Nr + - (CH2) ñ-N- (R2) 2 where R1 is C6-Ci2 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C1-C4. More preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C-10-oxypropylamine, N-coconut 1-3 diaminopropane, cocoalkyldimethylamine, lauryldimethylamine, lauryl bis (hydroxyethyl) amine , coco bis (hydroxyethyl) amine, 2 moles of propoxylated lauryl amine, 2 moles of propoxylated octylamine, lauryl amidopropyldimethylamine, amidopropylamine dimethylamine of C 10 -io and amidopropyldimethylamine of C 10.

Most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine.

Especially desirable are the n-dodecyldimethylamine and bishydroxyethylcocoalkylamine and 7-fold ethoxylated oleylamine, lauryl amido propylamine and cocoamido propylamine.

Additional ingredients Detergency builders The compositions according to the present invention may further comprise a builder. Any conventional builder agent is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, fatty acids and succinic, alkyl or alkenyl acids, materials such as ethylenediamine tetraacetate, diethylene triamine pentamethylene acetate, metal ion sequestrants such as amino polyphosphonates, particularly acid ethylene diamine tetra methylene phosphonic acid and diethylene triamine pentamethylene phosphonic acid. The phosphate builder agents can also be used here. Suitable builder agents can be inorganic ion exchange materials, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B HS or MAP. 3 Other suitable inorganic builder materials are the layered silicate, for example SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na 2 Si 2 s). Suitable polycarboxylates containing a carboxy group include lactic acid, glycolic acid and ether derivatives thereof as described in Belgian Patents Nos. 831, 368, 821, 369 and 821, 370. The polycarboxylates contain two carboxyl groups including water-soluble succinic acid salts, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates described in German Offenlegenschrift 2,446,686 and 2,446,687 and in the US patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as carboxymethyloxysuccinates described in British Patent No. 1, 379,241, Lactoxysuccinates described in the application of the Netherlands 7205873 and oxipolycarbonate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1, 387,447. Polycarboxylates containing 4 carboxyl groups include oxydisuccinates described in British Patent No. 1, 261, 829, 1, 1, 2,2-ethane tetracarboxylates, 1, 1,3,3-propane tetracarboxylates and 1, 1, 2, 3, propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patents Nos. 1, 398,421 and 1, 398,422 and in the patent of E.U.A. No. 3,936,448, and in the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are described in British Patent No. 1, 439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydro-furan-cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan-cis- dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1, 2,3,4,5,6-hexane-hexacarboxylates and a carboxymethyl derivative of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melific acid, pyromellitic acid and phthalic acid derivatives described in British Patent No. 1, 425,343. Of the above, the preferred polycarboxylates are hydroxycarboxylates containing more than three carboxy groups per molecule, more particularly citrates. Preferred builders for use in the present composition include a mixture of water insoluble aluminosilicate builder agents such as zeolite A or a layered silicate (SKS-6), and a water soluble chelating carboxylate agent such as acid citric. Other preferred builders include a mixture of water insoluble aluminosilicate builders such as zeolite A, and a water soluble water soluble chelating carboxylate agent such as citric acid. Preferred builders for use in liquid detergent compositions of the present invention are soaps and polycarboxylates.

Other detergent-improving materials that can form Part of the detergency builders for use in granular compositions include inorganic materials such as alkali metal carbonates such as citrate, bicarbonates, silicates, and organic materials such as organic phosphonates, amino polyalkylene! Phosphonates and amino polycarboxylates. Other suitable water-soluble organic salts are the salts homo- or co-polymeric acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are described in GB-A-1596,756. Examples of such salts are polyacrylates of MW 2000-500 and their copolymers with maleic anhydride, said copolymers having a molecular weight of between 20,000 to 70,000, especially 40,000. The salts of builder agents are usually included in amounts of from 0% to 80% by weight of the composition preferably from about 5% to 80%, more preferably from about 10% to 70%, more preferably, from around 30% and more usually i 60% by weight.

Detergent Enzymes The detergent compositions may further comprise one or more enzymes that provide cleaning performance, fabric care and / or sanitation benefits. Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, serin-proteases, glyco-amylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanasas, pentosanasas, malánasas, ß-glucanasas, arabinosidasas, hialuronidasas, chondroitanasa, lacasa or mixtures of the same. A preferred combination is a detergent composition having a cocktail of the conventional enzymes applicable as serine protease, amylase, lipase, cutinase and / or cellulose in conjunction with one or more cell wall degrading enzymes. Cellulases usable in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimum pH between 5 and 12 and in activity greater than 50 CEVU (cellulose viscosity unit). Suitable celluloses are described in the US patent. 4,435,307, Barbesgoard et al, J61078384 and WO96 / 02653 which describes fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes isolated cellulases from novel species of Bacillus. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275; DE-OS-2,247,832 and W095 / 26398. Examples of said cellulases and cellulases produced by a strain of Humicola insolens (Humicola grísea variety Thermoidea), particularly Humicola DSM 1800. Other suitable cellulases are cellulases originated from Humicola having a molecular weight of about 50 KDa, a point isoelectric of 5.5 and containing 415 amino acids; and a -43 kD endoglucanase derived from Humicola insolens, DSM 1800, which exhibits cellulase activity; a preferred endoglucanase component has the amino acid sequence described in PCT patent application number WO 91/17243. Also suitable cellulases are the cellulases EGII from Trichoderma longibrachiatum described in WO94 / 21801, Genencor, published on September 29, 1994. Particularly suitable cellulases are cellulases having color care benefits. Examples of said cellulases are cellulases described in the European patent application, filed on November 6, 1991 (Novo). Carezyme and Celluzime (Novo Nordisk A / S) are especially useful. See also W091 / 17244 and WO91 / 21801. Other cellulases suitable for fabric care and / or cleaning properties are described in WO96 / 34092, W096 / 17994 and W095 / 24471.

Said cellulases are normally incorporated in the detergent composition at levels from 0.0001% to 2% pure enzyme per weight of the detergent composition. The peroxidase enzymes are used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. and with a phenolic substrate as a bleach improving molecule. They are used for "bleaching in solution", that is, to avoid the transfer of dyes or pigments removed from substrates during washing operations, to other substrates in the washing solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO89 / 099813, WO89 / 09813 and European Patent Application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, presented on February 20, 1996. Also suitable is the laccase enzyme. The improvers are generally comprised at a level of 0.1% to 5% by weight of the total composition. Preferred enhancers are substituted phenoxyzine and phenoxyzine, 10-phenothiazinopropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinopropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (substituted C3-C5 alkylarykates) ) and phenols. Percarbonate or sodium perborate are preferred sources of hydrogen peroxide. Said peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% pure enzyme by weight of the detergent composition. Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, such as those described in British Patent 1,372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the tradename Lipase P " Amano ", hereinafter referred to as" Amano-P ". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, for example Chromobacter viscosum var. lipolyticum NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are the ® ® ® lipases such as M1 Lipase and Lipomax (Gist-Brocades) and Lipolase and ® Lipolase Ultra (Novo), which have been found to be very effective when used in combination with the compositions of the present invention .

Also suitable are the lipolytic enzymes described in EP 258 068, WO92 / 05249, W095 / 22615 by Novo Nordisk, and in WO94 / 03578, W095 / 35381 and WO 96/00292 by Unilever. Also suitable are cutinases [EC 3.1.1.50] that can be considered as a special type of lipase, namely lipases that do not require interfacial activation. The addition of cutinases to detergent compositions has been described in for example, WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic) and W094 / 14963 and WO 94/14964 (Unilever). The lipases and / or cutinases are normally incorporated in the detergent composition at levels of 0.0001% to 2% pure enzyme by weight of the detergent composition. Suitable serine proteases are the subtilisins that are obtained from particular strains of B. subtilis and β. licheniformis (subtilisin BPN and BPN '). A suitable serine protease is obtained from a Bacillus strain, having a maximum activity across the pH range of 8 to 12, ® developed and sold as ESPERASE by Novo Industries A / S Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784, by Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Maxacal manited with proteins) from Gist-Brocades. The proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application No. 87303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98) and which is referred to herein as "Protease B". ", and in the European patent application 199 404, Venegas, published on October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme that is called in the present" Protease A ". The protease called "Protease C" is suitable, which is a variant of a Bacillus alkaline serine protease in which lysine replaces arginine in position 27, tyrosine replaces valine in position 104, serine replaces asparagine in position 123 and alanine replace threonine at position 274. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published May 16, 1991. Variants are also included herein genetically modified, particularly from Protease C. A preferred serine protease referred to as "Protease D", is a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived from a precursor carbonyl hydrolase substituting a different amino acid by a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also n in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126 , +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or + 274 according to the numeration of the subtilisin of Bacillus amyloliquefaciens as described in WO95 / 10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes", which has the serial number US 08 / 322,677, issued October 13, 1994. A carbonylhydrolase variant of the protease described in WO95 / 10591, having an amino acid sequence derived by replacing a plurality of amino acid residues replaced in the corresponding precursor enzyme, is also suitable. to position +210 in combination with one or more of the following residuals: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, + 130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the numbered position corresponds to subtilisina of Bacillus amyloliquefaciens occurring naturally or to equivalent amino acid residues in other carbonylhydrolases or subtilisins, such as Bacillus lentus subtilisin (co-pending US patent application Serial No. 60 / 048,550, filed June 4, 1997). Also suitable for the present invention are the serine proteases described in patent applications EP 251 446 and WO 91/06637 and the BLAP® protease described in WO91 / 02792 and its variants described in WO 95/23221. See also a high pH serine protease from Bacillus sp.

NCIMB 40338 described in WO93 / 18140 A to Novo. Enzymatic detergents comprising serine protease, one or more other different enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a serine protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable serine proteases are described in EP 516200 by Unilever. The proteolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, most preferably from 0.005% to 0.1% pure enzyme by weight of the composition. Amylases (a and / or ß) can be included for the removal of carbohydrate-based stains. WO94 / 02597, Novo Nordisk A / S published on February 3, 1994 discloses detergent compositions that incorporate mutant amylases. See also WO95 / 10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in detergent compositions include α and β-amylases. A-amylases are known in the art and include those described in the U.S.A. No. 5,003,257; EP 252,666; WO / 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and in the specification of British Patent No. 1, 296,839 (Novo). Other suitable amylases are the amylases of improved stability described in W094 / 18314, published August 18, 1994 and WO96 / 05295, Genencor, published on February 22, 1996 and the amylase variants having additional modification in the immediate parent, available from Novo Nordisk A / S described in WO95 / 10603, published April 1995. Also suitable are the amylases described in EP 277 216, W095 / 26397 and WO 96/23873 (all by Novo Nordisk). Examples of commercial a-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S Denmark. W095 / 26397 describes other suitable amylases: α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and a value of ® pH on the scale of 8 to 10, measured by the Phadebas test of a-amylase activity. Suitable are the variants of the above enzymes, described in W096 / 23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and higher activity level are described in W095 / 35382. The amylolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, most preferably from 0.00024% to 0.048% pure enzyme by weight of the composition. The aforementioned enzymes may have any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. The origin can also be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidic, halophilic, etc.). The purified or non-purified forms of these enzymes can be used. At present, it is common practice to modify wild-type enzymes by means of protein / genetic manipulation techniques in order to optimize their efficiency of performance in the detergent compositions of the invention. For example, the variants can be designed in such a way that the compatibility of the enzyme with commonly found ingredients of such compositions is increased. Alternatively, the variant can be designed such that the optimum pH, bleach or chelator stability, catalytic activity and the like, of the enzyme variant is adjusted to suit the particular cleaning application. In particular, attention must be focused on amino acids sensitive to oxidation in case of bleaching stability and surface loads for compatibility with surfactant. The isoelectric point of such enzymes can be modified by the replacement of some charged amino acids, for example, an increase in the isoelectric point can help improve compatibility with anionic surfactants. The stability of the enzymes can be further enhanced by the creation of, for example, additional salt bridges and by reinforcing the calcium binding sites to increase the chelator stability. Special attention should be paid to cellulases, since most cellulases have separate binding domains (CBD). The properties of such enzymes can be altered by modifications in these domains. Said enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% pure enzyme by weight of the detergent composition. Enzymes can be added as separate individual ingredients (pellets, granules, stabilized liquids, etc. containing an enzyme) or as mixtures of two or more enzymes (eg cogranulated materials). Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in European co-pending patent application 92870018.6 filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylenepolyamines. A range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and US Patent 3,553,139, January 5, 1971. to McCarty et al. In the patent of E.U.A. 4,101, 457, Place et al, July 18, 1978, and in the patent of E.U.A. 4,507,219, Hughes, March 26, 1985, enzymes are also described. Useful enzyme materials for liquid detergent formulations, and their incorporation into such formulations, are described in the US patent. 4,261, 868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in the US patent. 3,600,319, August 17, 1971, to Gedge, et al, EP 199 405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in the U.S. patent. 3,519,570. A Bacillus sp. AC13 useful and which gives proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.

Benefits of color care and fabric care Technologies that provide a type of color care benefit can also be included. Examples of these technologies are metallocatalysts for color maintenance. Said metallocatalysts are also described in copending European patent application No. 92870181.2. Dye fixative, polyolefin dispersion agents for anti-wrinkle and improved water absorbency, perfume and amino-functional polymer for color care treatment and perfume substantivity are additional examples of color care / fabric care technologies and described in co-pending patent application No. 96870140.9, filed on November 7, 1996. Fabric softening agents can also be incorporated into the detergent compositions according to the present invention. These agents may be of inorganic or organic type. Inorganic softening agents are illustrated by the smectite clays described in GB-A-1 400 898 and USP 5,019,292. Organic fabric softening agents include water-insoluble tertiary amines as described in GB-A1 514 276 and EP-BO 011 340 and their combination with C12-C14 quaternary ammonium monosols as described in EP-B-0 026 527 and EP-B-0 026 528 and the di-long chain amides described in EP-B-0 242 919. Other useful organic ingredients of fabric softener systems include high molecular weight polyethylene oxide materials as described in EP-A-0 299 575 and 0 313 146. Smectite clay levels are normally in the range of 2% to 20%, more preferably 5% to 15% by weight, with the material being added as a dry mixed component to the rest of the formulation. Organic fabric softening agents such as water insoluble tertiary amines or dilarga chain amide materials are incorporated at levels of 0.5% to 5% by weight, normally from 1% to 3% by weight while polyethylene oxide materials High molecular weight and water soluble cationic materials are added at levels of 0.1% to 2%, usually from 0.15% to 1.5% by weight. These materials are normally added to the spray-dried portion of the composition, although in some cases it may be more convenient to add them as a dry mixed material in particles or sprinkle them as molten liquid over the other solid components of the composition.

Bleaching agent Additional optional detergent ingredients that may be included in the detergent compositions of the present invention include bleaching agents.

Preferred peroxygen bleaching agents include those peroxygen bleach compounds that are capable of producing hydrogen peroxide in an aqueous solution. These compounds are well known in the art and include hydrogen peroxide and alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and bleaching compounds of inorganic persalts, such as alkali metal perborates, percarbonates, perfosphates. , and similar. Preferred peroxygen bleaching agents include peroxygen bleach selected from the group consisting of perborates, percarbonates, peroxyhydrates, peroxides, persulfates, and mixtures thereof. Specific preferred examples include: sodium perborate, commercially available in the form of mono and tetrahydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Particularly preferred are sodium perborate tetrahydrate, and especially sodium perborate monohydrate. Sodium perborate monohydrate is especially preferred since it is very stable during storage and still dissolves very rapidly in the bleaching solution. These bleaching agent components may include one or more oxygen bleaching agents and, depending on the bleaching agent chosen, one or more bleach activators. When oxygen bleaching compounds are present, they will typically be present at levels of from about 1% to about 25%. The component of the bleaching agent for use herein may be any bleaching agent useful for detergent compositions including oxygen bleaching as well as others known in the art. The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent. A category of oxygen bleaching agent that can be used comprises percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutric acid and diperoxydecanedioic acid. Said bleaching agents are described in the patent of E.U.A. 4,483,781, patent application of E.U.A. 740,446, European patent application 0,133,354 and US patent. 4,412,934. The most preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in the US patent. 4,634,551. Another category of bleaching agents that can be used encompass halogen bleaching agents. Examples of hypohalite bleaching agents, for example, include trichloroisocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro- and N-bromo-alcansulfonamides. Said materials are normally added to 0.5-10% by weight of the finished product, preferably 1-5% by weight.

Hydrogen peroxide release agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose ( PAG) or N-nonanoyl-6-aminocaproic acid phenolsulfonate ester (NACA-OBS, described in WO94 / 28106), which are perhydrolyzed to form a peracid as the active bleaching species, leading to the improved bleaching effect. Also suitable activators are acylated citrate esters such as those described in co-pending European Patent Application No. 91870207.7 and the non-symmetric acyclic imide bleach activator of the following formula as described in the co-pending patent applications Procter &; Gamble of E.U.A. Serial No. 60 / 022,786 (issued July 30, 1996) and No. 60 / 028,122 (issued October 15, 1996): wherein Ri is a saturated or unsaturated branched straight chain alkyl group of C7-C13, R2 is a saturated or unsaturated straight or branched chain alkyl group of C? -C8 and R3 is a saturated or unsaturated alkyl group of linear or branched chain of C1-C4. Useful bleaching agents, including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleach compounds for use in detergent compositions in accordance with the present invention are described in co-pending applications USSN 08 / 136,626, PCT / US95 / 07823, W095 / 27772, W095 / 27773, W095 / 27774 and W095 / 27775. Hydrogen peroxide may also be present by adding an enzymatic system (i.e., an enzyme and a substrate thereof) that is capable of generating hydrogen peroxide at the start or during the washing and / or rinsing process. Said enzymatic systems are described in patent application EP 91202655.6 filed on October 9, 1991. Metal-containing catalysts for use in bleaching compositions include cobalt-containing catalysts such as cobalt (lll) salts of pentamine acetate and manganese-containing catalysts such as those described in EPA 549 271; EPA 549 272; EPA 458 397; US 5,246,621; EPA 458 398; US 5,194,416 and US 5,114,611. The bleaching composition comprising a peroxide compound, a manganese-containing bleach catalyst and a chelating agent is disclosed in Patent Application No. 94870206.3. Bleaching agents other than oxygen bleaching agents are also well known in the art and can be used therein. Another type of oxygen-free bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines. These materials can be deposited on the substrate during the washing process. At the time of irradiation with light, in the presence of oxygen, such as when hanging clothes in the sun, sulfonated zinc phthalocyanine is activated and, as a consequence, the substrate is bleached. The preferred zinc phthalocyanine and a photoactivated bleaching process are described in the U.S.A. 4,033,718. Typically, the detergent compositions will have from about 0.025% to about 1.25% by weight, of the sulfonated zinc phthalocyanine.

Chelating Agents The detergent compositions of the present invention may also optionally contain one or more iron and / or manganese chelating agents. Said chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below. Without wishing to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from wash solutions by the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates and ethanoldiglicines, alkali metal, ammonium and substituted ammonium salts thereof and mixtures thereof. The aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in the detergent compositions, and include ethylene diamine tetrakis (methylene phosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. No. 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate ("EDDS"), especially the [S, S] isomer as described in the U.S.A. No. 4,704,233, November 3, 1987, to Hartman and Perkins. The compositions herein may also contain salts (or acid form) of methylglycliciacetic acid (MGDA) as a useful chelator or co-builder with, for example, insoluble builders such as zeolites, layered silicates and the like.

If used, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if used, the chelating agents will comprise from about 0.1% to about 3.0% by weight of said compositions.

Foam suppressor Another optional ingredient is a foam suppressor, illustrated by silicones and silica / silicone blends. Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms polished by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulate materials in which the foam suppressant is usefully incorporated in a releasable manner in a detergent-impermeable, water-soluble or water-dispersible, substantially non-active surface carrier. Alternatively, the foam suppressant can be dissolved or dispersed in a liquid carrier and applied by spraying on one or more of the other components. A preferred silicone foam controlling agent is described in Bartollota et al, U.S. No. 3,933,672. Other particularly useful foam suppressors are self-emulsifiable silicone foam suppressors, which are described in the German patent application DTOS 2 646 126 published on April 28, 1977. An example of such a compound is DC- 544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. The especially preferred foam controlling agent is the foam suppressant comprising a mixture of silicone oil and 2-alkyl-alkanols. Suitable 2-alkyl-alkanols are 2-butyloctanol which are commercially available under the trade name Isofol 12 R. Said suds suppressor is described in co-pending European Patent Application No. 92870174.7, filed on November 10, 1992. Particularly preferred silicone foam control agents are described in co-pending European patent application No. 92201649.8. Said compositions may comprise a mixture of silicone / silica in combination with fumed non-porous silica such as Aerosll®. The foam suppressors described above are normally used at levels of 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.

Other Other components that are used in detergent compositions may be used, such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, rust inhibitors, coloring agents, and / or encapsulated or unencapsulated perfumes.

Especially suitable encapsulation materials are water-soluble capsules consisting of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1,464,616. Other suitable water-soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid esters of substituted dicarboxylic acids as described in the U.S.A. No. 3,455,838. These acid-ester dextrins are preferably prepared from starches such as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of such encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consists of a modified corn starch and glucose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride. Preferred optical brighteners are of anionic character, examples of which are 4,4'-bis- (2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2: 2'-disulfonate of disodium, 4, -4, -bis- (2-morpholino-4-anilino-s-triazin-6-ylamino-stilbene-2: 2'-disulfonate of disodium, 4,4'-bis- (2 , 4-dianilino-s-triazin-6-ylamino) estylben-2: 2, -disodium disulfonate, 4 \ 4"-bis- (2,4-dianilino-s-triazin-6-ylammon) stilbene-2-sulphonate monosodium, 4,4'-bis- (2-anilino- 4- (N-methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino) -stilbene-2,2'-disulfonate of disodium, 4,4'-b-s- (4-phenyl- Disodium 2,1,4-triazol-2-yl) -stilbene-2,2'-disulfonate, 4,4'bis (2-anilino-4- (1-methyl-2-hydroxyethylamino) -s-triazine- 6-ylamino) -stilbene-2,2'-disulfonate of disodium, 2 (stilbene-4"- (naphtho-1,, 2,: 4,5) -1, 2,3-triazole-2" -sulfonate of sodium and 4,4'-bis (2-sulfostyril) biphenyl The highly preferred brighteners are the specific brighteners of co-pending European patent application No. 95201943.8 Other useful polymeric materials are polyethylene glycols, particularly those of molecular weight of 1,000. -10,000, more particularly from 2,000 to 8,000 and more preferably from about 4,000.These are used at levels of 0.20% to 5%, more preferably from 0.25% to 2.5% by weight.These polymers and the polycarbox salts homo- or co-polymeric ions mentioned above are valuable for improving the maintenance of whiteness, the deposition of ash in the fabric, and the cleaning performance on clay, protein and oxidizable soils in the presence of transition metal impurities. The soil release agents useful in the compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and / or propylene glycol units in various arrangements. Examples of such polymers are described in the patents of E.U.A. Nos. 4116885 and 4711730, commonly assigned, and published European Patent Application No. 0 272 033. A particularly preferred polymer according to EP-A-0 272 033 has the formula: (CH3 (PEG) 43) 0 75 ( POH) 025 [T-PO) 2 8 (T-PEG) 04) T (PO-) 0.25 ((PEG) 43C 3)? 75 where PEG is - (OC2H4) 0-, PO is (OC3H60) and T is (pcOC6H4CO).

Modified polyesters are also very useful as random copolymers of dimethylterephthalate, dimethylsulfoisophthalate, ethylene glycol and 1,2-propanediol, the end groups consisting first of all of their benzoate Ifon and secondly of monoesters of ethylene glycol and / or propanediol. The objective is to obtain a polymer blocked at both ends by sulfobenzoate groups; "in the first place", in the present context most of said copolymers herein will be blocked at the ends by sulfobenzoate groups. However, some copolymers will be less than completely blocked and therefore their end groups may consist of monoesters of ethylene glycol and / or popane-1,2-diol, therefore consisting of "second" of such species. The polyesters selected herein contain about 46% by weight of dimethylterephthalic acid, about 16% by weight of propane-1,2-diol, about 10% by weight of ethylene glycol, about 13% by weight of dimethisulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and have a molecular weight of about 3,000. The polyesters and their method of preparation are described in detail in EPA 311 342. The enzyme stabilizer useful herein depends on characteristics such as the enzyme used, and the active ingredient. However, preferred examples of an enzyme stabilizer useful herein include calcium ion, borates, borate diols, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof.

It is well known in the art that free chlorine in tap water rapidly deactivates enzymes comprised in detergent compositions. Therefore, the use of a chlorine scrubber such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine at a level above 0.1% by weight of the total composition, in the formulas, will provide improved stability through washing , of detergent enzymes. Compositions comprising chlorine scrubber are described in European patent application 92870018.6 filed on January 31, 1992. Alkoxylated polycarboxylates, such as those prepared from polyacrylates are useful herein to provide additional removal performance of grease. Such materials are described in WO 91/08281 and PCT 90/01815 on page 4 et seq., Incorporated herein by reference. Chemically, these materials comprise polyacrylates having an ethoxy side chain for every 7-8 acrylate units. The side chains are of the formula - (CH2CH20) m (CH2) nCH3 where m is 2-3 and n is 6-12. The side chains are linked with esters to the "base structure" of the polyacrylate to provide a "comb" type polymer structure. The molecular weight may vary, but is typically in the range of about 2,000 to about 50,000. Such alkoxylated polycarboxylates may comprise from about 0.05% to about 10%, by weight, of the compositions herein.

The following examples serve to exemplify compositions of the present invention, but do not necessarily intend to limit it, or otherwise define the scope of the invention. In detergent compositions, the enzyme levels are expressed by a pure enzyme by weight of the total composition and unless otherwise specified, the detergent ingredients are expressed by weight of the total compositions.

EXAMPLES The following examples further describe and demonstrate the preferred embodiments within the scope of the present invention. The examples are given by way of illustration only, and are not intended to be construed as limitations of the present invention since many variations thereof are possible without departing from the spirit and scope.

EXAMPLE 1 Liquid compositions for cleaning hard surfaces Example No.

Component A B C D E F G Metallo-protease 0.001 0.005 0.01 0.02 0.03 0.01 0.02 Serin-Protease - - - - - 0.02 0.01 EDA * - - - 2.90 2.90 - - Citrate - - - - - 2.90 2.90 Alkylbenzenesulfonat - 1.95 - 1.95 - 1.95 - or linear C13 (LAS) Alkylsulfate (AS) 2.00 - 2.20 - 2.20 - 2.20 Alkylpolyoxyethylene sulf 2.00 - 2.20 - 2.20 - 2.20 ato (AES) Amine oxide 0.40 - 0.50 - 0.50 - 0.50 Hydrotrope - 1.30 - 1.30 - 1.30 - Solvent ** - 6.30 6.30 6.30 6.30 6.30 6.30 Ca ++ (as CaCI2) - - 0.40 0.40 0.40 - - Water and components the rest at 100% lower * Ethylenediamine diacetic acid Na4 ** Diethylene glycol monohexyl ether In examples 1-F- and 1-G, any combination of the protease enzymes useful in the present invention which are mentioned herein, inter alia, is replaced by metallo-protease and serine. -protease, with substantially similar results. 2. Compositions for dishwashing EXAMPLE 2 Dishwashing composition Example No.

Component A B C D E F Metallo-protease 0.001 0.005 0.01 0.05 0.01 0.003 Serin-Protease - - - - 0.04 0.01 TFAA * 0.90 0.90 0.90 0.90 0.90 0.90 AES 12.00 12.00 12.00 12.00 12.00 12.00 Acid 2- 4.50 4.50 - 4.50 4.50 - methylundecanoic Ethoxylated alcohol 3.00 3.00 3.00 3.00 3.00 3.00 C12 (4) Amine oxide 3.00 3.00 3.00 3.00 3.00 3.00 Hidrótropo 2.00 2.00 2.00 2.00 2.00 2.00 Ethanol 4.00 4.00 4.00 4.00 4.00 4.00 Mg ++ - (as MgCI2) Ca ++ (as CaCI2) 0.40 0.40 0.40 0.40 0.40 0.40 Water and components the rest at 100% lower * Ci-Ciß alkyl N-methyl glucamide In Examples 2-E and 2-F, any combination of the protease enzymes useful in the present invention mentioned herein, inter alia, is replaced by metallo-protease and serine. -protease with substantially similar results. 3. Cleaning compositions for fabrics Granular composition for cleaning fabrics Granular compositions for cleaning fabrics of the present invention contain an effective amount of one or more protease enzymes, preferably from about 0.001% to about 10%, more preferably from about 0.005% to about 5%, more preferably from about 0.01% to about 1% by weight of the active protease enzyme of the composition (see U.S. Patent No. 5,679,630 in the examples).

EXAMPLE 3 Granulated composition for fabric cleaning Example No.

Component ABCD Metallo-protease 0.01 0.02 0.02 0.02 Serin-Protease - - 0.01 0.02 Alkyl benzenesulfonate 22.00 22.00 22.00 22.00 linear C13 Phosphate (as 23.00 23.00 23.00 23.00 sodium tripolyphosphates) Sodium carbonate 23.00 23.00 23.00 23.00 Silicate sodium 14.00 14.00 14.00 14.00 Zeolite 8.20 8.20 8.20 8.20 DTPA * 0.40 - 0.40 - Ca ++ (as CaCI2) 0.40 0.40 0.40 0.40 Sodium sulphate 5.50 5.50 5.50 5.50 Water the rest at 100% * Diethylenetriaminpentaacetic acid.

In Examples 3-C and 3-D, any combination of the protease enzymes useful in the present invention mentioned herein, inter alia, is replaced by metallo-protease and serine protease, with substantially similar results.

EXAMPLE 4 Granulated composition for cleaning fabrics Example No. Component A B C D Metallo-protease 0.01 0.02 0.007 0.005 Serin-protease - - 0.003 0.005 C12 alkylbenzene sulfonate 12.00 12.00 12.00 12.00 Zeolite A (1-10 micrometer) * 26.00 26.00 26.00 26.00 Sodium salt of (2,3) alkylsulfate 5.00 5.00 5.00 5.00 secondary of C12-C14 Sodium citrate 5.00 5.00 5.00 5.00 Optical brightener 0.10 0.10 0.10 0.10 Sodium sulphate 17.00 17.00 17.00 17.00 Ca ++ (as CaCI2) 0.40 0.40 0.40 0.40 Fillers, water, minor components the rest at 100% * A hydrated sodium aluminosilicate of formula Nai2 (A102Si? 2) i2-27H20 has a primary particle size on the scale of about 0.1 to 10 micrometers (weight expressed on an anhydrous basis) In examples 4-C and 4-D, any combination of the protease enzymes useful in the present invention mentioned herein, inter alia, is replaced by metallo-protease and serine protease, with substantially similar results.

EXAMPLE 5 Liquid compositions for fabric cleaning Example No. Component A B DI H2o 38.63 - MEA (monoethanolamine) 0.48 9.00 NaOH 4.40 1.00 Pdiol 4.00 10.0 Citric acid 2.50 2.00 Sodium sulphate 1.75 - DTPA 0.50 1.00 Premix of FWA (Br 15 / MEA / NI 23- 0.15 0.15 9) Na C25E1.80S 23.50 - AE3S (H) - 4.00 C11.8HLAS * 3.00 14.00 Neodol 2.00 6.00 EtOH 0.50 2.00 Ca ++ (as CaCI2) 0.10 0.10 Borax premix 2.50 - (Borax / MEA / Pdiol / citric acid) Boric acid - 1.00 Amidopropyldimethylamine of C10 1.50 - TEPA 105 ** 1.20 - Colorant 0.0040 0.0015 Cellulase 0.053 0.20 Amylase 0.15 0.20 Metallo-protease 0.05 0.05 Water and minor components the rest at 100% * HLAS: Acid form of linear alkylbenzene sulfonate (an anionic synthetic surfactant) ** TEPA: tetraethylenepentamine EXAMPLE 6 Bar compositions for fabric cleaning Ahem | alo No. Component B C D Metallo-protease 0.01 0.03 0.01 0.02 Serin-protease - 0.01 0.01 Ci2-C? 6 alkyl hydrosulfate from Na 20.0 20.0 20.0 20.0 N-methyl glucamide of C12-C14 5.0 5.0 5.0 5.00 C11-C13 alkylbenzene sulphonate of Na 10.0 10.0 10.0 10.00 Sodium pyrophosphate 7.0 7.0 7.0 7.00 Sodium tripolyphosphate 7.0 7.0 7.0 7.00 Zeolite A (0.1 -.10 μ) 5.0 5.0 5.0 5.0 Carboxymethylcellulose 0.2 0.2 0.2 0.20 Polyacrylate (MW 1400) 0.2 0.2 0.2 0.20 Coconut monoethanolamide 5.0 5.0 5.0 5.00 Brightener, perfume 0.2 0.2 0.2 0.20 CaS04 1.0 1.0 1.0 1.00 MgS04 1.0 1.0 1.0 1.00 Water 4.0 4.0 4.0 4.00 Filler * the rest at 100% * Can be selected from convenient materials such as CaC03, talc, clay, silicates, and the like In Examples 6-C and 6-D, any combination of the protease enzymes useful in the present invention mentioned herein, inter alia, is replaced by metallo-protease and serine protease, with substantially similar results. The compositions of the present invention can be prepared in a suitable manner by any method chosen by the formulator, non-limiting examples of which are described in U.S. 5,691,297 Nassano et al., Issued November 11, 1997; U.S. 5,574,005 Welch et al., Issued November 12, 1996; U.S. 5,569,645 Dinniwell et al., Issued October 29, 1996; U.S. 5,565,422 Del Greco et al., Issued October 15, 1996; U.S. 5,516,448 Capeci et al., Issued May 14, 1996; U.S. 5,489,392 Capeci et al., Issued February 6, 1996; U.S. 5,486,303 Capeci et al., Issued January 23, 1996, which are hereby incorporated by reference in their entirety. In addition to the above examples, the cleaning compositions of the present invention can be formulated in any suitable laundry detergent composition, non-limiting examples of which are described in U.S. 5,679,630 Baeck et al., Issued October 21, 1997; U.S. 5,565,145 Watson et al., Issued October 15, 1996, U.S. 5,478,489 Fredj et al., Issued December 26, 1995; U.S. 5,470,507 Fredj et al., Issued November 28, 1995; U.S. 5,466,802 Panandiker et al., Issued November 14, 1995; U.S. 5,460,752 Fredj et al., Issued October 24, 1995; U.S. 5,458,810 Fredj et al., Issued October 17, 1995; U.S. 5,458,809 Fredj et al., Issued October 17, 1995; U.S. 5,288,431 Huber et al., Issued February 22, 1994, which are hereby incorporated by reference in their entirety. It is understood that the examples and embodiments described herein are for the purpose of illustrating only and that various modifications or changes will be suggested in the light thereof by those skilled in the art without departing from the scope of the present invention.

Claims (8)

1. NOVELTY OF THE INVENTION CLAIMS 5 1. A detergent composition comprising: (1) an agent , detersive surfactant; and (2) a metallo-protease wherein the metallo-protease < f has at least more than 15AU / mg of caseinolytic activity.
2. 2. The detergent composition according to claim 1, further characterized in that at least 80% of the activity 10 of the metalloprotease is inhibited by 1 mM of a metalloprotease inhibitor.
3. 3. The detergent composition according to claim 1, further characterized in that the metallo-protease has more than 70% activity under a pH condition of about 4.5 to about 9.0; and more than 70% stability under a temperature condition of about 50 ° C to about 60 ° C for 15 minutes.
4. 4. The detergent composition according to claim 1, further characterized in that the metallo-protease has more than 3 primary break sites by tests of insulin beta chain fragmentation patterns.
5. 5. The detergent composition according to claim 1, further characterized in that the detergent composition 7 comprises from about 0.0001% to about 5% by weight of the metallo-protease.
6. 6. A detergent composition comprising: (a) from about 0.01% to about 60% by weight of an agent 5 detersive surfactant; (b) from about 0% to about 80% in m weight of a builder; and (c) of around 0.0001% a «T about 5% by weight of a metalloprotease according to claim 1.
7. 7. The detergent composition according to claim 6, further characterized in that the surfactant is selected from the group consisting of surfactants. anionic, cationic, amphoteric, nonionic and mixtures thereof.
8. 8. The detergent composition according to claim 6, further characterized in that it comprises a bleach. 15 9.- The detergent composition in accordance with the 1 claim 7, further characterized in that the bleach is selected from the group consisting of peroxygen, perborates, percarbonates, perfosphates and mixtures thereof. 10. The detergent composition according to claim 6, further characterized in that it comprises an enzyme that is selected from the group consisting of amylase, lipase, peroxidase, serine protease, cellulase and mixtures thereof.