CN1375000A - A detergent composition containing a protease - Google Patents

Abstract

A detergent composition comprising a protease that is screened by a process comprising the steps of measuring the primary Cleavage Rate and measuring the Second Cleavage Rate. the ratio of the Primary Cleavage Ratio to the Second Cleavage Rate of the protease is calculated. Proteases are selected that have a Primary Cleavage Rate higher than 1000 mu g/min/mug and a ratio of the Primary Cleavage Rate to the Secondary Cleavage Rate lower than 150:1.

Description

Detergent composition containing protease

Field of Invention

The present invention relates to detergent compositions containing proteases, more particularly, the present invention relates to laundry detergent compositions, dishwashing detergent compositions, hard surface cleaning compositions and personal cleansing compositions containing proteases.

Background of the Invention

Various types of enzymes have long been used in laundry detergents to help remove certain stains from fabrics. Each enzyme (amylase, protease, lipase, cellulase, etc.) typically catalyzes a different chemical reaction. For example proteases are known to hydrolyze (break down a compound into two or more simpler compounds) other proteins. Many foods and other organic substances contain proteins that stain textile materials such as clothing. Proteases can help remove these stains by breaking down proteins, for which reason naturally occurring or artificial proteases are added to laundry detergent compositions.

Proteins are generally composed of 20 types of amino acids that form long polypeptide chains. In a polypeptide chain, each amino acid forms a peptide bond with other amino acids, and proteases hydrolyze the peptide bonds as substrates. However, each protease has different substrate specificity, for example, some proteases prefer insulin β chain, hydrolyze the peptide bond between valine (Val) and cystine (Cys) of insulin β chain, but other proteases Hydrolyzes the peptide bond between proline (Pro) and lysine (Lys) of the insulin beta chain. Therefore, since substrate specificity of protease is one of the most important factors when protease is applied to detergent compositions, we need to select the most suitable protease from many types of protease.

There has now been discovered detergent compositions comprising proteases effective in removing soils, especially protein-based stains, and detergent compositions wherein the proteases are screened by a method.

Summary of Invention

The present invention relates to detergent compositions containing proteases, more particularly, the present invention relates to laundry detergent compositions, dishwashing detergent compositions, hard surface cleaning compositions and personal cleansing compositions containing proteases.

In particular, in one aspect of the present invention, there is provided a detergent composition containing a protease, wherein the protease is screened by a method comprising the steps of: measuring the primary cleavage rate (Primary Cleavage Rate), measuring the secondary cleavage rate (Second Cleavage Rate) and calculating The ratio of the primary cleavage rate to the secondary cleavage rate of the protease; select a protease with a primary cleavage rate higher than 1000 μg/min/μg and a ratio of the primary cleavage rate to the secondary cleavage rate lower than 150:1. Preferred proteases have a primary cleavage rate greater than 1200 μg/min/μg, and a ratio of primary cleavage rate to secondary cleavage rate of about 50:1 to about 130:1. Furthermore, the protease is preferably obtained from Bacillus subtilis.

In other aspects of the present invention, there are provided detergent compositions comprising: a) from about 0.01% to about 60% by weight of a detersive surfactant; b) from about 5% to about 80% by weight of a detergent builder; and c) from about 0.0001% to about 5% by weight of a protease having a primary cleavage rate above 1000 μg/min/μg and a ratio of primary to secondary cleavage rates below 150:1.

In another aspect of the present invention, there is provided a method for screening comprising the steps of: a. measuring the primary cleavage rate; b. measuring the secondary cleavage rate; c. calculating the ratio of the primary cleavage rate to the secondary cleavage rate; d . Select a protease with a primary cleavage rate higher than 1000 μg/min/μg and a ratio of primary cleavage rate to secondary cleavage rate lower than 150:1.

Detailed description of the invention

While the specification includes specific description and claims that clearly claim the invention, it is believed that the invention will be better understood from the following description.

All percentages are by weight of the total composition unless otherwise indicated.

All ratios are by weight unless otherwise indicated. definition

"Contains" as used herein means that other steps and other components that do not affect the end result may be added. This term includes the terms "consisting of" and "consisting essentially of".

All cited references are incorporated herein by reference in their entirety. Citation of any reference is not an admission of any admission as to the availability of prior art as prior art to the claimed invention.

The term "detergent composition" or "detergent" as used herein is used to designate any agent conventionally used for removing soils, such as general household or laundry detergents of the synthetic or soap type. protease selection process

Proteases are screened by a method comprising: measuring the primary cleavage rate; measuring the secondary cleavage rate and calculating the ratio of the primary cleavage rate to the secondary cleavage rate. Proteases of choice are proteases with a primary cleavage rate above 1000 μg/min/μg and a ratio of primary cleavage rate to secondary cleavage rate below 150:1.

The protease in the detergent compositions of the present invention may be obtained from natural or recombinant sources, and if the protease is obtained from a natural source, the protease is preferably obtained from Bacillus subtilis.

Fragmentation rate

For evaluating the properties of proteases for use in detergent compositions of the present invention, two main properties of proteases are important, one being hydrolysis kinetics (which corresponds to the primary cleavage rate) and the other being broad cleavage specificity ( It corresponds to the secondary cleavage rate). Either the detergent of the invention cleans better, or it is not the invention. Again, you have to correlate these properties with cleavage rates.

The cleavage rate measures how rapidly the protease hydrolyzes the insulin B-chain polypeptide. Insulin B-chain polypeptide consists of 30 amino acids. First, the protease hydrolyzes the peptide bond between No. 15 leucine (Leu) and No. 16 tyrosine (Tyr) to obtain two short polypeptides. The primary cleavage rate of the present invention indicates how rapidly the protease hydrolyzes the insulin beta chain polypeptide, resulting in two short polypeptides. If the protease's primary cleavage rate is high, the protease is able to hydrolyze more rapidly and yield two shorter polypeptides. Thus, the primary cleavage rate of the present invention represents the kinetics of protease hydrolysis. Therefore, a protease is able to hydrolyze a protein more rapidly if its primary cleavage rate is high.

As explained above, the insulin beta chain polypeptide is hydrolyzed by proteases into two short polypeptides. These two polypeptides do not contain Leu-Tyr peptide bonds, as available bonds are cleaved as described above. To hydrolyze short polypeptides, proteases must hydrolyze other peptide bonds than Leu-Tyr. One way to quantify the cleavage of other bonds by a protease is defined as cleavage specificity. Cleavage specificity is the ability of a protease to cleave peptide bonds linking different amino acids. For example, if a protease cleaves a peptide bond between Leu-Tyr, the cleavage specificity is Leu. Certain proteases are able to cleave several bonds of different amino acids attached to different proteins, and if the protease has a broad cleavage specificity, the protease can hydrolyze the peptide more rapidly.

The secondary cleavage rate indicates how quickly a protease hydrolyzes short peptides produced after the primary cleavage rate as discussed above. Proteases are able to hydrolyze short polypeptides more rapidly if the secondary cleavage rate is high, which means that the protease has broader cleavage specificity.

While not intending to be bound by theory, we believe that the primary cleavage rate and the ratio of the primary cleavage rate to the secondary cleavage rate are important for hydrolyzing proteinaceous soils. The ratio of primary cleavage rate to secondary cleavage rate represents the balance between hydrolysis kinetics and broad cleavage specificity. If the ratio is higher than 150:1, the protease exhibits a relatively narrow cleavage specificity, which results in some protein stains remaining on the fabric and thus less efficient cleaning.

Protease Screening Methods

In another aspect of the present invention there is provided a detergent composition comprising a protease, wherein the protease is screened by a method comprising the steps of: a) measuring the primary cleavage rate, measuring the secondary cleavage rate and calculating the protease primary cleavage rate and the secondary cleavage rate and b) select the primary cleavage rate to be higher than 1000 μg/min/μg, preferably higher than 1200 μg/min/μg and the ratio of the primary cleavage rate to the secondary cleavage rate to be lower than 150:1, preferably about 50:1 to about 130:1 protease.

According to this method, certain proteases are screened, these proteases are described in WO9920769, WO9920770, WO9920771.

To measure primary and secondary cleavage rates we use an insulin β(B) chain break type assay. The insulin-B chain break type test method is performed as follows:

Insulin B-chain break type test

The primary cleavage site is defined as the site of cleavage in the early stages of insulin B-chain hydrolysis (before less than 50% of the insulin B-chain is hydrolyzed). To determine the location of primary cleavage and determine the rate of primary cleavage, the following methods were used. Prepare 1 mg/ml oxidized insulin B-chain in 0.1 M tris-HCl buffer at pH 7.0 and incubate at 35°C for 10 min. 10 microliters of the enzyme solution was then mixed with the insulin solution to a final enzyme concentration of 0.1-0.2 ppm. After 3 minutes of hydrolysis, an equal volume of 0.1M HCl was added to stop the reaction. The reaction mixture was then analyzed by HPLC to measure cleaved peptides, which were identified by measuring molecular weight (MW) by LC/MS. The peak value was quantified from the peak area and the primary cleavage rate was calculated from the disappearance of the insulin B chain within 3 minutes.

To determine the secondary cleavage rate, the following method was used. Prepare 1 mg/ml oxidized insulin B-chain in 0.1 M tris-HCl buffer at pH 7.0 and incubate at 35°C for 10 min. 10 microliters of the enzyme solution was then mixed with the insulin solution to a final enzyme concentration of 0.1-0.2 ppm. After 2 hours of hydrolysis, an equal volume of 0.1M HCl was added to stop the reaction. The reaction mixture was then analyzed by HPLC to measure cleaved peptides. The peak value was calculated quantitatively from the peak area and the secondary cleavage rate was calculated from the disappearance of the peptides generated by the primary hydrolysis, ie peptides 1-15 and peptides 16-30 within 2 hours.

detergent composition

The detergent compositions of the present invention contain from about 0.0001% to about 5% by weight protease. Focusing on the primary cleavage rate (kinetics of hydrolysis) and secondary cleavage rate (broad cleavage specificity) of proteases, the present invention provides detergent compositions containing from about 0.0001% to about 5% by weight of proteases, wherein the proteases have a higher than The primary cleavage rate at 1000 μg/min/μg and the ratio of the primary cleavage rate to the secondary cleavage rate was less than 150:1. Since the primary cleavage rate is higher than 1000 μg/min/μg, the protease in the detergent composition of the present invention can more rapidly hydrolyze protein soils, and since the ratio of the primary cleavage rate to the secondary cleavage rate is lower than 150:1, the Proteases rapidly hydrolyze protein stains and protein stain residues.

Detergent compositions containing proteases screened by the above method show better cleaning performance.

The detergent compositions of the present invention contain from about 0.0001% to about 5%, preferably from about 0.002% to about 1%, by weight, of protease. detergent surfactant

The detergent compositions of the present invention comprise a surfactant, 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 from about 0.01% to about 60% by weight. More preferably, in accordance with the present invention, they are incorporated at levels of from about 1% to about 35% by weight, most preferably from about 1% to about 30% by weight of the detergent compositions.

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

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

Polyoxyethylene, polyoxypropylene and polyoxybutylene condensates of alkylphenols are suitable for use as nonionic surfactants in the present invention, among which polyoxyethylene condensates are 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, 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 ^(TM) CO-630 sold by GAF Corporation, Triton ^(TM) X-45, X-114, X-100 and X-102 sold by 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 in the nonionic surfactants 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 (condensation product of C ₁₁ -C ₁₅ linear alcohols with 9 moles of ethylene oxide), Tergitol ^™ 24-L-6NMW (condensation products 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 cyclic Condensation product of ethylene oxide), Neodol ^TM 23-3 (condensation product of C ₁₂ -C ₁₃ straight chain alcohol and 3.0 moles of ethylene oxide), Neodol ^TM 45-7 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol and 7 Condensation product of 5 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 - Condensation product of C ₁₅ alcohol with 9 moles of ethylene oxide), sold by Procter &Gamble; and Genapol LA 030 or 050 (condensation product of C ₁₂ -C ₁₄ alcohol with 3 or 5 moles of ethylene oxide), sold by Hoechst Sales. The preferred HLB range for these products is 8-11, most preferably 8-10.

Nonionic surfactants also useful in the present invention are the alkyl polysaccharides disclosed in USP 4,565,647, Llenado, issued January 21, 1986, containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms Hydrophobic groups and polysaccharides containing about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7 saccharide units, such as polyglycoside hydrophilic groups. Any reducing sugars containing 5 or 6 carbon atoms can be used, such as glucose, galactose and galactosyl instead of sugar groups (hydrophobic groups are selectively attached at 2-, 3-, 4-, etc. positions to obtain relative glucoside or galactoside (glucose or galactose). An internal sugar bond may be, for example, between one position of the added 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 alkylpolyethoxylated 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 groups may subsequently be attached between their 1-position and the 2-, 3-, 4- and/or 6-position of the preceding saccharide unit, preferably predominantly in the 2-position.

Condensation products of ethylene oxide with hydrophobic groups formed by condensation of propylene oxide with propylene glycol are also suitable for use as additional nonionic detersive surfactants herein. 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 polyoxyethylene groups to this hydrophobic portion will increase the overall water solubility of the molecule and the liquid character of the product will be maintained until the polyoxyethylene content is about 50% of the total weight of the condensation product, which is equivalent to condensing up to about 40 moles of epoxy ethane. Examples of such compounds include certain commercially available Plurafac ^™ LF404 and Pluronic ^™ surfactants, marketed by BASF.

Also suitable for use herein as nonionic surfactants are the condensation products of ethylene oxide with the product obtained by the reaction of propylene oxide and ethylenediamine. The hydrophobic groups of these products consist of the reaction product of ethylenediamine and excess propylene oxide and generally have a molecular weight of from about 2500 to about 3000. The hydrophobic group 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 such nonionic surfactants include certain of the commercially available Tetronic ^(TM) compounds, sold by BASF.

Preferred nonionic surfactants for use herein 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 mixture. 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.

其中R¹是H，或R¹是C_1-4烃基、2-羟基乙基、2-羟基丙基或它们的混合物，R²是C_5-31烃基，和Z是具有至少3个与链直接连接的羟基的多羟基烃基，或它们的烷氧基化衍生物。优选R¹是甲基，R²是直链C_11-15烷基或C_16-18烷基或链烯基链，例如椰子烷基或它们的混合物，和Z通过在还原胺化反应中还原糖，例如葡萄糖、果糖、麦芽糖、乳糖得到。More preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

wherein R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, R ² is C _5-31 hydrocarbyl, and Z is a chain having at least 3 Polyhydroxyl hydrocarbon radicals with directly attached hydroxyl groups, or their alkoxylated derivatives. Preferably ^R is methyl, ^R is a straight chain C _11-15 alkyl or C _16-18 alkyl or alkenyl chain, such as coconut alkyl or mixtures thereof, and Z is reduced by Sugars such as glucose, fructose, maltose, lactose are obtained.

Suitable anionic surfactants that can be used are linear alkylbenzene sulfonate, alkyl ester sulfonate, branched chain alkyl sulfonate, medium chain alkyl sulfonate surfactants including C ₈ -C ₂₀ Linear esters of carboxylic acids (ie, fatty acids) sulfonated with gaseous sulfur trioxide according to the method in "The Journal of the American Oil Chemists Society", 52 (1975) pp. 323-329. Suitable materials include natural fatty materials derived from tallow, palm oil, and the like.

其中R³是C₈-C₂₀烃基，优选烷基或它们的混合物，R⁴是C₁-C₆烃基，优选烷基或它们的混合物，M是阳离子，它与烷基酯磺酸酯形成水溶性盐。合适的成盐阳离子包括金属，例如钠、钾和锂，和取代或未取代的铵阳离子，例如单乙醇胺、二乙醇胺和三乙醇胺。优选R³是C₁₀-C₁₆烷基，和R⁴是甲基、乙基或异丙基。尤其优选的是其中R³是C₁₀-C₁₆烷基的甲基酯磺酸盐。Preferred alkyl ester sulfonate surfactants, especially for laundry applications, include alkyl ester sulfonate surfactants of the formula:

wherein R ³ is a C ₈ -C ₂₀ hydrocarbon group, preferably an alkyl group or a mixture thereof, R ⁴ is a C ₁ -C ₆ hydrocarbon group, preferably an alkyl group or a mixture thereof, M is a cation, which forms with an alkyl ester sulfonate water soluble salt. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably R ³ is C ₁₀ -C ₁₆ alkyl, and R ⁴ is methyl, ethyl or isopropyl. 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 (methyl -, dimethyl- and trimethyl-ammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and derived from alkylamines, such as ethylamine, diethylamine, triethylamine quaternary ammonium cations and their mixtures, etc.). Typically, _C12 - _C16 alkyl chains are 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 Olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonating cleavage products of alkaline earth metal citrates, C ₈ -C ₂₄ alkyl polyglycol ether sulfates (containing up to 10 moles of ring ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkylphenol oxirane ether sulfates, paraffin sulfonates, alkyl phosphates, hydroxyethyl Sulfonates, for example, acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated _C12 -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 salts (nonionic unsulfated compounds described below ₎ , branched primary alkyl sulfates and alkyl polyethoxy carboxylates, such as the formula RO( _CH2CH2O ) _k - _CH2COO ^- 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.

Further 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 to column 29, line 23 (incorporated herein by reference).

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

More preferred anionic surfactants including alkyl alkoxy sulfate surfactants are water soluble salts or acids of formula RO(A) _m SO ₃ M wherein R is 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 unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, M is H or a cation, which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium etc.), ammonium or substituted ammonium cations. The present invention contemplates alkyl ethoxy sulfates and alkyl propoxy 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, cations obtained from their mixture, etc. Exemplary surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylated (1.0) sulfates (C ₁₂ -C ₁₈ E(1.0)M), C ₁₂ -C ₁₈ alkyl polyethoxylated ( 2.25) Sulfate (C ₁₂ -C ₁₈ E(2.25)M), C ₁₂ -C ₁₈ Alkyl Polyethoxylated (3.0) Sulfate (C ₁₂ -C ₁₈ E(3.0)M) and C ₁₂ - C ₁₈ alkyl polyethoxylated (4.0) sulfates (C ₁₂ -C ₁₈ E(4.0)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 mentioned 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 ^R6 is any hexose sugar or a hexose sugar polymer with a molecular weight below about 1000, and when y is other than 0, hydrogen; ^R5 is the same as ^R4 or an alkyl chain, wherein ^R2 adds the total number of carbon atoms of ^R5 not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

式I其中R₁是短链烷基(C₆-C₁₀)或如下式(II)的烷基酰氨基烷基：

式IIThe quaternary ammonium surfactant suitable for use in the present invention has the following formula (I):

Formula I wherein R ₁ is a short-chain alkyl group (C ₆ -C ₁₀ ) or an alkylamidoalkyl group of the following formula (II):

Formula II

y is 2-4, preferably 3,

and R ₂ is H or C ₁ -C ₃ alkyl,

while x is 0-4, preferably 0-2, most preferably 0,

And R ₃ , R ₄ and R ₅ are the same or different, and can be short-chain alkyl (C ₁ -C ₃ ) or alkoxylated alkyl of the following formula III,

while X ^- is a counterion, preferably a halide, such as chloride or methylsulfate,

Formula III

R ₆ 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 their mixture, x=0,

R ₃ , R ₄ =CH ₃ and R ₅ =CH ₂ CH ₂ OH.

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

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 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;

Chlorinated or brominated coconut oil methyl dihydroxyethyl ammonium;

Decyltriethylammonium chloride;

Decyldimethylhydroxyethylammonium chloride or bromide;

C _12-15 dimethylhydroxyethylammonium chloride or bromide;

Chlorinated or Brominated Coco Dimethyl Hydroxyethyl Ammonium;

Myristyltrimethylammonium methylsulfate;

Lauryldimethylbenzylammonium chloride or bromide;

Lauryldimethyl(oxirane) 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);

Dialkylimidazolines [compounds 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 EP 000224.

Typical cationic fabric softening ingredients include water insoluble quaternary ammonium fabric softening actives or their corresponding amine precursors, most commonly ammonium chloride or methylsulfate containing two long chain alkyl chains.

Wherein preferred cationic softener includes as follows:

1) ditallow dimethyl ammonium chloride (DTDMAC);

2) dihydrogenated tallow dimethyl ammonium chloride;

3) dihydrogenated tallow dimethyl ammonium methyl sulfate;

4) distearyl dimethyl ammonium chloride;

5) dioleyl dimethyl ammonium chloride;

6) dipalmityl hydroxyethyl methyl ammonium chloride;

7) stearyl benzyl dimethyl ammonium chloride;

8) tallow trimethyl ammonium chloride;

9) hydrogenated tallow trimethyl ammonium chloride;

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

11) C _12-18 alkyl dihydroxy ethyl methyl ammonium chloride;

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

13) Di(tallowoxyethyl)dimethylammonium chloride;

14) Ditallow imidazolium methyl sulfate;

15) 1-(2-tallowamidoethyl)-2-tallow imidazolium methylsulfate.

Biodegradable quaternary ammonium compounds exist as alternatives to the traditionally used dilong alkyl chain ammonium chloride and methyl sulfate. The quaternary ammonium compounds contain long chain alk(en)yl groups which are cleaved by functional groups such as carboxyl groups, said materials and fabric softening compositions containing them are disclosed in a number of publications such as EP-A-0040562 and EP-A-0239910 .

其中Q选自-O-C(O)-、-C(O)-O-、-O-C(O)-O-、-NR⁴-C(O)-、-C(O)-NR⁴-；The quaternary ammonium compounds and amine precursors of the present invention have the following formula (I) or (II):

Wherein Q is selected from -OC(O)-, -C(O)-O-, -OC(O)-O-, -NR ⁴ -C(O)-, -C(O)-NR ⁴ -;

R ¹ is (CH ₂ ) _n -QT ² or T ³ ;

R ² is (CH ₂ ) _m -QT ⁴ or T ⁵ or R ³ ;

R ³ is C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl or H;

R ⁴ is H or C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl;

T ¹ , T ² , T ³ , T ⁴ and T ⁵ are independently C ₁₁ -C ₂₂ alkyl or alkenyl;

n and m are integers from 1 to 4; and

X ^- is a softener compatible anion. Non-limiting examples of softener compatible anions include chloride or methylsulfate.

The alkyl or alkenyl group, the chains ^T1 , ^T2 , ^T3 , ^T4 and ^T5 must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. Chains can be straight or branched. Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl species. Compounds wherein T ¹ , T ² , T ³ , T ⁴ and T ⁵ represent a mixture of generally tallow long chain species are especially preferred.

Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions of the present invention include:

1) N, N-di(tallowyloxyethyl)-N, N-dimethyl ammonium chloride;

2) N, N-di(tallowyloxyethyl) N-methyl, N-(2-hydroxyethyl) ammonium methylsulfate;

3) N,N-bis(2-tallowyloxy-2-oxoethyl)-N,N-dimethylammonium chloride;

4) N,N-bis(2-tallowyloxy-ethylcarbonyl-oxyethyl)-N,N-dimethylammonium chloride;

5) N-(2-tallowyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxoethyl)-N,N-dimethylammonium chloride;

6) N,N,N-tris(tallowyl-oxyl-ethyl)-N-methylammonium chloride;

7) N-(2-tallowyl-oxyl-2-oxoethyl)-N-(tallowyl)-N,N-dimethylammonium chloride; and

8) 1,2-Ditallowoxy-3-trimethylammonium propane chloride; and mixtures of any of the foregoing.

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 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 examples of 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 detergent compositions. 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 3,929,678, Laughlin et al., issued December 30, 1975, column 19, line 38-column 22, line 48, for 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 comprising one alkyl group containing from about 10 to about 18 carbon atoms and two selected from the group consisting of alkyl groups containing from about 1 to about 3 carbon atoms Water-soluble amine oxides of groups containing from about 10 to about 18 carbon atoms and two groups selected from the group consisting of alkyl and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms and water-soluble sulfoxides containing an alkyl group of about 10 to about 18 carbon atoms and a group 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: wherein ^R3 is alkyl, hydroxyalkyl or alkylphenyl or mixtures thereof containing about 8 to about 22 carbon atoms; ^R4 is alkylene or hydroxyalkylene containing about 2 to about 3 carbon atoms or mixtures thereof; x is 0 to about 3; each ^R is an alkyl or hydroxyalkyl group containing about 1 to about 3 carbon atoms or a polyalkylene group containing about 1 to about 3 oxirane groups oxyethylene group. 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 semi-polar nonionic surfactants.

The laundry 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 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 , X is - O-, -C(O)NH- or -NH-, R ₄ is a C ₆ -C ₁₂ alkyl chain, n is 1 to 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 laurylamine. Other preferred primary amines are C ₈ -C ₁₀ oxypropylamine, octyloxypropylamine, 2-ethylhexyloxypropylamine, laurylamidopropylamine and amidopropylamine.

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 a 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 to 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.

其中R₅是H或甲基和x＝1-2。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 oxypropylamine, N-coconut 1,3 diaminopropane, coconut Alkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coconut alkylbis(hydroxyethyl)amine, 2 moles propoxylated laurylamine, 2 moles propoxylated octylamine, lauryl amidopropyl dimethylamine, C _8-10 amidopropyl dimethylamine and C ₁₀ amidopropyl dimethylamine.

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

                              

The compositions herein may also contain a builder, any conventional builder suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl or alkenyl succinic acids and fatty acids , substances such as ethylenediaminetetraacetate, diethylenetriaminepentamethyleneacetate, metal ion sequestrants such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and di Ethylenetriamine Pentamethylene Phosphonic 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 zeolites 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 carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, and fumaric acid and ether carboxylates described in DE2446686 and 2446687 and US3935257 and thionyl carboxylates described in Belgian patent 840623. Polycarboxylates containing three carboxy groups include especially water-soluble citrate, itaconate and citraconate and succinate derivatives, such as carboxymethoxysuccinate described in GB1379241, application in the Netherlands Lactoxysuccinates described in 7205873 and oxypolycarboxylate materials described in GB1387447, eg 2-oxa-1,1,3-propanetricarboxylate.

Polycarboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates disclosed in GB1261829 and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include sulfosuccinate derivatives disclosed in GB1398421 and 1398422 and US3936448 and sulfocleaved citrates described in GB1082179, while polycarboxylic acids containing phosphono substituents Salts are disclosed in GB1439000.

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 phthalic acid derivatives disclosed in GB1425343.

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

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

Other builder materials which may form part of the builders for granular compositions include inorganic materials such as alkali metal carbonates, bicarbonates, silicates and organic materials such as organic phosphonates, aminopolyalkylenes base 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. Such polymers are disclosed in GB-A-1596756. Examples of such salts are polyacrylates having a molecular weight of 2000-5000 and their copolymers with maleic anhydride having a molecular weight of 20000-70000, especially about 40000.

Detergent builder salts are generally present in amounts of from 5% to about 80%, preferably from about 10% to 70%, most usually from about 30% to about 60%, by weight of the composition. detergent enzyme

Detergent compositions may also contain one or more enzymes which provide cleaning performance, fabric care and/or hygiene benefits.

Said enzyme comprises cellulase, hemicellulase, peroxidase, glucoamylase, amylase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, cutinase Protease, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malic enzyme, β-glucanase, arabinosidase, Enzymes of hyaluronase, chondroitinase, laccase, or mixtures thereof. Other conventional proteases besides the proteases of the present invention may also be used.

Preferred combinations are detergent compositions comprising a mixture of commonly used enzymes, such as 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 about 50 CEVU (cellulose 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, respectively. EP739982 describes cellulases isolated from new Bacillus species. Suitable cellulases are also disclosed in GB-A-2075028, GB-A-2095275, DE-OS-2247832 and WO95/26398.

Examples of such cellulases are cellulases produced by strains of Humicola insolens (Humicola griseavar. thermoi dea), especially Humicola strain DSM 1800.

Other suitable cellulases are cellulases obtained ^from Humicola insolens having a molecular weight of about 50 kDa, an isoelectric point of 5.5 and containing 415 amino acids; Glucanase; a preferred endoglucanase component has the amino acid sequence disclosed in PCT patent application WO 91/17243. Also suitable are the EGIII cellulases from Trichoderma 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 for fabric care and/or washing performance are described in WO96/34092, WO96/17994 and WO95/24471.

The cellulase is usually added to the detergent composition at a level of 0.0001% to 2% by weight of pure enzyme of the detergent composition.

Peroxidases are used in combination with an oxygen source, such as percarbonate, perborate, persulfate, hydrogen peroxide, etc., and a phenolic substrate as a bleach booster molecule. They serve as "solution bleaching", ie to avoid the transfer of dyes or pigments removed from the substrate during washing operations to other substrates in the wash solution. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases, such as chloro- and bromo-peroxidases. Detergent compositions containing peroxidase are disclosed, for example, in PCT International Applications WO 89/099813, WO 89/09813 and European Patent Applications EP No. 91202882.6 filed on November 6, 1991 and EP No. 96870013.8 filed on February 20, 1996 . Also suitable are laccases.

Builders are typically present at levels of 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 WO 94/12621) and substituted syringates (C ₃ -C ₅ substituted alkyl syringates) and phenols. Sodium percarbonate or sodium perborate are preferred sources of hydrogen peroxide.

The above-mentioned peroxidases are usually added to the detergent composition at a level of 0.0001% to 2% pure enzyme by weight of the detergent composition.

Other preferred enzymes that may be included in the detergent compositions of the present invention include lipases, as described in GB1372034, suitable lipases for detergent use include microorganisms of the genus Pseudomonas, such as Pseudomonas stutzeri Lipase derived from ATCC 19.154. Suitable lipases include those produced by the microorganism Pseudomonas fluorescens IAM 1057 which show positive immunological cross-reactivity with lipase antibodies. This lipase is available from Amano Pharmaceutical Co. Ltd. (Nagoya, Japan) under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, a lipase from Chromobacter viscosum such as Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co. (Tagata, Japan); commercially available from USBiochemical Corp. (US) and Disoynth Co. (Netherlands) The resulting Chromobacter viscosum lipase; and the lipase from Pseudomonas gladioli. Particularly suitable lipases are lipases such as M1 Lipase ^R and Lipomax ^R (Gist-Brocades) and Lipolase ^R and Lipolase Ultra ^R (Novo), which have been found to be very effective when used in combination with the compositions of the 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, i.e. lipases that 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) and WO94/14963 and WO94/14964 (Unilever).

Lipase and/or cutinase are typically incorporated into detergent compositions at levels of 0.0001% to 2% pure enzyme by weight of the detergent 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 variant 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 and include those described in US5003257, EP252666, WO91/00353, FR2676456, EP285123, EP525610, EP368341 and GB1296839 (Novo). Other suitable amylases are the stability-improved 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 described in WO 95/10603 with additional modifications in the intermediate parent. Likewise suitable amylases are described in EP277216, WO95/26397 and WO96/23873 (all Novo Nordisk).

Examples of commercial alpha-amylase products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all 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 above amylases described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties in terms of activity level and combination of thermostability and higher activity level are described in WO95/35382.

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

The aforementioned enzymes may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin, and may also be of mesophilic or extreme conditions (psychrophilic, cryotrophic, thermophilic, barophilic, basophilic, acidophilic, halogenophilic, etc.). Pure or impure forms of these enzymes can be used. Currently, it is common practice to modify wild-type enzymes via protein/gene engineering techniques to optimize their performance efficiency in the detergent compositions of the present invention. For example, variants can be designed to increase the compatibility of the enzyme with commonly encountered components of the composition. In addition, variants can be designed such that the optimal pH, bleach or chelator stability, catalytic activity etc. of the enzyme variant can be tailored to a specific wash application.

Particular attention should be paid to the susceptibility of amino acids to oxidation in the case of bleach stability, and to the surface charge with respect to surfactant compatibility. The isoelectric point of this enzyme can be modified by the substitution of some charged amino acids, for example, increasing the isoelectric point will help to improve the compatibility with anionic surfactants. Enzyme stability can be further improved by creating eg additional salt bridges, enforcing calcium binding sites to increase chelator stability. Particular attention must be paid to cellulases, since most cellulases have separate binding domains (CBDs) and the properties of such enzymes can be altered by modifications in these domains.

The enzymes are incorporated into the detergent compositions of the present invention at a level of 0.0001% to 2% pure enzyme by weight of the laundry detergent composition. Enzymes can be added as individual components (pellets, granules, stabilized liquids, etc. containing one enzyme) or as a mixture of two or more enzymes (eg agglomerated granules).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers described in unexamined European patent application 92870018.6 filed on January 31, 1992, examples of which are ethoxylated tetraethylene base polyamine.

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 disclosed in US Pat. 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 disclosed and listed in US3600319 issued August 17, 1971 by Gedge et al. and EP199405 and EP200586 issued October 29, 1986 by Venegas. Enzyme stabilization systems are also described eg in US3519570. WO9401532A to Novo describes useful Bacillus sp. AC13 for deriving proteases, xylanases and cellulases. Color Care and Fabric Care Effects

Technologies of the type that provide color care effects may also be included, examples of which are organometallic catalysts for color retention which are described in co-pending European patent application 92870181.2. Dye fixatives, polyolefin dispersants for anti-wrinkle and improved water absorption, perfumes and amino-functional polymers for color care Described in unexamined patent application №96870140.9 filed on 7th.

Fabric softening agents can also be incorporated into the detergent compositions of the present invention. These substances 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-soluble tertiary amines as described in GB-A-1514276 and EP-B-0011340, their mixtures with mono-C ₁₂ -C ₁₄ quaternary ammonium salts in EP-B-0026527 and EP-B-0026528 Disclosed in, and dilong chain amides as disclosed in EP-B-0242919. Other useful organic components for fabric softeners include the high molecular weight polyethylene oxide materials disclosed in EP-A-0299575 and 0313146.

The amount of smectite clay generally ranges from 2% to 20% by weight, more preferably from 5% to 15% by weight, the material being added as a dry blend component to the remainder of the formulation. Organic fabric softener, such as water-soluble tertiary amine or two long-chain amide substances are added in an amount of 0.5%-5% by weight, usually 1%-3% by weight, while high-molecular polyethylene oxide substances and water-soluble cationic substances are added in an amount of 0.1%-2% by weight, 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. bleach

Other optional detergent ingredients that can be included in the detergent compositions of the present invention include bleaching agents.

Preferred peroxygen bleaches include those peroxygen bleaching compounds capable of generating hydrogen peroxide in aqueous solution, such compounds are known in the art, including hydrogen peroxide and alkali metal peroxides, organic peroxide bleaches Compounds such as urea peroxide and inorganic persalt bleaching compounds such as alkali metal perborates, percarbonates, perphosphates and the like.

Preferred peroxygen bleaches include peroxygen bleaches selected from the group consisting of perborates, percarbonates, peroxyhydrates, peroxides, persulfates and mixtures thereof. Specific preferred examples include: sodium perborate, commercially available as mono- and tetrahydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Especially preferred is sodium perborate tetrahydrate, especially sodium perborate monohydrate. Sodium perborate monohydrate is especially preferred because it is very stable during storage and dissolves very rapidly in bleach solutions.

These bleach components may include one or more oxygen bleaches and, depending on the bleach selected, one or more bleach activators. If present, oxygen bleaching compounds are typically present at levels from about 1% to about 25%.

The bleaching agent used in the present invention can be any bleaching agent used in detergent compositions, including oxygen bleaching agents as well as others known in the art. Bleaching agents suitable for use herein are activated or unactivated bleaches.

One type of oxygen bleach that can be used includes percarboxylic acid bleaches and salts thereof. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, 4-nonylamino-4-oxyperoxybutyric acid and diperoxydodecanedioic acid . Such bleaches are disclosed in US4483781, US Patent Application 740446, EP0133354 and US4412934. More 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, sodium and potassium trichloroisocyanates and dichloroisocyanates and N-chloro and N-bromo alkane sulfonamides. This substance is usually added at 0.5-10% by weight of the final product, preferably 1-5% by weight.

其中R₁是C₇-C₁₃直链或支链的饱和或不饱和烷基、R₂是C₁-C₈直链或支链的饱和或不饱和烷基和R₃是C₁-C₄直链或支链的饱和或不饱和烷基。Hydrogen peroxide releasing agents can be combined with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US4412934), 3,5-trimethylhexanoyloxy benzenesulfonate (ISONOBS, described in EP120591) or pentaacetylglucose (PAG) or N-nonanoyl-6-aminocaproic acid phenolsulfonate (NACA-OBS, described in WO94/28106) used in combination, They are perhydrolyzed to form peracids as active bleaching substances, resulting in improved bleaching. Also suitable active agents are acylated citrates, such as disclosed in unexamined European patent application 91870207.7, in unexamined patent applications US No. 60/022786 (filed on July 30, 1996) and No. 60/ Unsymmetrical acyclic imide bleach activators of the formula disclosed in 028122 (filed October 15, 1996):

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

Bleaching agents useful 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 applications USSN08/136626, PCT/US95/07823, WO95/ 27772, WO95/27773, WO95/27774 and WO95/27775.

Hydrogen peroxide can also be present by adding an enzyme system (i.e. enzyme and its substrate), which is capable of producing hydrogen peroxide at the beginning or during the washing and/or rinsing process, which was filed in EP on October 9, 1991 Disclosed in patent application 91202655.6.

Metal-containing catalysts for use in bleach compositions include cobalt-containing catalysts such as cobalt(III) pentaamine acetate salts and magnesium-containing catalysts such as the compounds described in EPA549271, EPA549272, EPA458397, US5246621, EPA458398, US5194416 and US5114611. Bleaching compositions containing peroxygen compounds, magnesium-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 deposit 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 and the soil carrier is subsequently bleached. 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. Chelating agent

The detergent compositions of the present invention may optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, as defined below. While not wishing to be bound by theory, it is believed that the effectiveness of these substances is due in part to their particular ability to remove iron and manganese ions from wash liquors by forming water-soluble chelates.

Amino carboxylates that may be used as optional chelating agents include EDTA, N-HydroxyethylEDTA, Nitrilotriacetate, EDTA , triethylenetetraminehexaacetate, diethylenetriaminepentaacetate, and ethanol diglycine, their alkali metal, ammonium, and substituted ammonium salts, and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least minimum levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylene phosphonate) such as DEQUEST . These amino phosphonates preferably do not contain alkyl or alkylene groups of more than about 6 carbon atoms.

Multifunctionally substituted arene chelating agents are also suitable for use in the compositions of the present invention. See US3812044, Connor et al., issued May 21,1974. Preferred compounds of this type in the acid form are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), particularly the [S, S] isomer described in Hartman and Perkins, November 3, 1987. Disclosed in US4704233.

The compositions of the present invention may also contain water-soluble methylglycine diacetic acid (MGDA) salts ( or acid form).

If utilized, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. Even more preferably, if used, such chelating agents comprise from about 0.1% to about 3.0% by weight of the composition. Foam suppressor

Other optional ingredients are suds suppressors, such as silicones and silica-polysiloxane mixtures. Silicones can generally be denoted as alkylated polysiloxane species, while silicas are generally used in finely divided form, eg various types of silica aerosols, xerogels and hydrophobic silicas. These materials can be incorporated as particulates where advantageously the suds suppressor is incorporated in a water soluble or water dispersible, non-surfactant detergent substantially impermeable carrier. Additionally, the suds suppressor can be dissolved or dispersed in the liquid carrier and added by spraying on 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-diol 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, commercially available under the tradename Isofol 12R.

This suds suppressor system is described in unexamined European patent application 92870174.7, filed November 10,1992.

Particularly preferred silicone suds control agents are described in unexamined European patent application 92201649.8, said compositions may contain silicone/silica mixtures in combination with fumed non-porous silicas such as Aerosil ^R .

The above-mentioned suds suppressor is usually used at a content of 0.001%-2% by weight of the composition, preferably 0.01%-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.

Preferred optical brighteners are anionic in character, an example of which is 4,4'-bis-(2-ethanolamino-4-aniline-s-triazin-6-ylamino)stilbene-2:2'disulfonic acid Disodium, 4,4'-bis-(2-morpholino-4-aniline-s-triazin-6-ylamino)stilbene-2: Disodium 2'disulfonate, 4,4'-bis -(2,4-Diphenylamine-s-triazin-6-ylamino)stilbene-2: 2' disodium disulfonate, 4',4"-bis-(2,4-diphenylamine-s-tri Azin-6-ylamino)stilbene-2: monosodium 2'disulfonate, 4,4'-bis-(2-aniline-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 : 2' disodium disulfonate, 4,4'-bis-(2-aniline-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2 : 2' disodium disulfonate, 2-(stilbene-4"-(naphtho-1',2':4,5)-1,2,3-triazole-2 "-sodium sulfonate and 4 , 4'-bis(2-sulfostyrene base) biphenyl. More preferred brighteners are specific brighteners disclosed in unexamined EP95201943.8.

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% by weight, more preferably 0.25% to 2.5% by weight. These polymers and the homo- or co-polymeric polycarboxylates mentioned above are valuable in improving whiteness retention, fabric dust deposition and wash performance on soil, protein and oxidizable soils in the presence of transition metal impurities of.

The soil release polymers 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 EP0272033, according to EP-A-0272033 especially preferred polymers have 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 aim is to have polymers capped at both ends with sulfobenzoates, and in the present invention most of the above-mentioned copolymers of the invention are "predominantly" capped with sulfobenzoates. However, some copolymers will not be fully end-capped, thus, their end groups may consist of ethylene glycol and/or propylene 1-2 glycol which "secondarily" makes up the material.

The polyester selected for the present invention contains about 46% by weight dimethyl terephthalate, about 16% by weight propylene-1,2 glycol, 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.

Enzyme stabilizers for use in the present invention depend on characteristics such as the enzyme and active ingredient used. Preferred examples of enzyme stabilizers for use in the present invention however include calcium ions, borates, sulfate-diols, propylene glycol, short chain carboxylic acids, boronic acids and mixtures thereof.

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

Alkoxylated polycarboxylates prepared from polyacrylates are useful in the present invention to provide additional oil removal performance. This material is described in WO91/08281 and PCT90/01815, page 4, 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.

The following examples serve to illustrate the compositions of the invention, but do not limit or otherwise define the scope of the invention.

In detergent compositions, enzyme levels are expressed as pure enzyme by weight of the total composition, and unless otherwise stated, detergent components are expressed by weight of the total composition.

Example

The following examples further describe and illustrate preferred embodiments within the scope of the invention. The examples are given for illustration only and do not constitute a limitation of the invention, since many variations thereof are possible without departing from its spirit and scope.

Example 1

Liquid Hard Surface Cleaning Composition

Example Components A B C D E F G Protease of the present invention 0.001 0.005 0.01 0.02 0.03 0.01 0.02EDA ^* - - - 2.90 2.90 - - citrate - - - - - 2.90 2.90C ₁₃ linear alkyl- 1.95 - 1.95 - 1.95 - benzenesulfonic acid Salt (LAS) Alkyl Sulfate (AS) 2.00 - 2.20 - 2.20 - 2.20 Alkyl Polyoxyethylene 2.00 - 2.20 - 2.20 - 2.20 Sulfate (AES) Amine Oxide 0.40 - 0.50 - 0.50 - 0.50 Solubilizer - 1.30 - 1.30 - 1.30 -Solvent ^** - 6.30 6.30 6.30 6.30 6.30 6.30Ca ⁺⁺ (CaCl ₂ ) - - 0.40 0.40 0.40 - -Water and minor components equilibrated to 100%*Tetrasodium EDTA**Diethylene glycol mono Hexyl ether 2. Dishwashing compositions

Example 2

Dishwashing Compositions

Example

A A B B C D D E E F

Protease of the present invention 0.001 0.005 0.01 0.05 0.01 0.003

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

2-Methyldodecanoic acid 4.50 4.50 -- 4.50 4.50 --

C ₁₂ alcohol ethoxylates (4) 3.00 3.00 3.00 3.00 3.00 3.00

Amine oxide 3.00 3.00 3.00 3.00 3.00 3.00

Solubilizer 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 ⁺⁺ (MgCl ₂ ) 0.20 0.20 0.20 0.20 0.20 0.20

Ca ⁺⁺ (CaCl ₂ ) 0.40 0.40 0.40 0.40 0.40 0.40

Water and minor components Balanced to 100%

*C ₁₆ -C ₁₈ alkyl N-methyl glucamide 3. Fabric washing composition

Granular Fabric Washing Compositions

The granular fabric washing compositions of the present invention contain an effective amount of one or more proteases, preferably from about 0.001% to about 10% by weight of the composition, more preferably from about 0.005% to about 5% by weight, more preferably from 0.01% to about 1% by weight active protease. (see US5679630

Example).

Example 3

Granular Fabric Detergent Compositions

Example Components A B C D Protease of the present invention 0.01 0.02 0.02 0.02 C ₁₃ Linear alkylbenzene sulfonate 22.00 22.00 22.00 22.00 Phosphate (sodium tripolyphosphate) 23.00 23.00 23.00 23.00 Sodium carbonate 23.00 23.00 23.00 23.00 Sodium silicate 14 14.00 Zeolite 8.20 8.20 8.20 8.20 DTPA ^* 0.40 - 0.40 -Ca ⁺⁺ (CaCl ₂ ) 0.40 0.40 0.40 0.40 Sodium Sulfate 5.50 5.50 5.50 5.50 Water Equilibrium to 100%*Diethylenetriaminepentaacetic acid

Example 4

Granular Fabric Detergent Compositions

Example Components A B C D Protease of the present invention 0.01 0.02 0.007 0.005 C ₁₂ alkylbenzene sulfonate 12.00 12.00 12.00 12.00 Zeolite A (1-10 μm) ^* 26.00 26.00 26.00 26.00 C ₁₂ -C ₁₄ secondary (2,3) alkyl sulfate Sodium Salt 5.00 5.00 5.00 5.00 Sodium Citrate 5.00 5.00 5.00 5.00 Optical Brightener 0.10 0.10 0.10 0.10 Sodium Sulfate 17.00 17.00 17.00 17.00 Ca ⁺⁺ (CaCl ₂ ) 0.40 0.40 100 % Balance to Filler, Water Sodium aluminosilicate hydrates of the formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O have a primary particle size (expressed on an anhydrous basis) of 0.1-10 microns

Example 5

                                        

Example Component A BDI H ₂ O 38.63 -MEA (Monoethanolamine) 0.48 9.00NaOH 4.40 1.00Pdiol 4.00 10.0 Citric Acid 2.50 2.00 Sodium Sulfate 1.75 -DTPA 0.50 1.00FWA Premix(Br 15/MEA/NI 23-9) 0.15 0.15 Na C25AE1.80S 23.50 -AE3S(H) - 4.00C11.8HLAS ^* 3.00 14.00Neodol 2.00 6.00EtOH 0.50 2.00Ca ⁺⁺ (CaCl ₂ ) 0.10 0.10 Borax Premix (Borax/MEA/Pdiol/Citrate) 2.50 -Borax- 1.00C10 Amidopropyl Dimethylamine 1.50 -TEPA105 ^** 1.20 -Dye 0.0040 0.0015 Cellulase 0.053 0.20 Amylase 0.15 0.20 Protease of the invention 0.05 0.05 Water and trace components balanced to 100% *HLAS: straight acid form Paraffinic Alkylbenzene Sulfonate (Synthetic Anionic Surfactant)** TEPA: Tetraethylenepentamine

Example 6

Soap Bar Fabric Washing Composition

Example Components A B C D Protease of the present invention 0.01 0.03 0.01 0.02 _{C 12} -C ₁₆ sodium alkyl sulfate 20.0 20.0 20.0 20.00 C ₁₂ -C ₁₄ N-methylglucamide 5.0 5.0 5.0 5.00 C ₁₁ -C ₁₃ alkyl benzene sulfonate Sodium pyrophosphate 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-.10μ) 5.0 5.0 5.0 5.00 Carboxymethyl cellulose 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 Brighteners, Fragrances 0.2 0.2 0.2 0.20 CaSO ₄ 1.0 1.0 1.0 1.00MgSO ₄ 1.0 1.0 1.0 1.00 Water 4.0 4.0 4.0 4.00 Fillers ^* Balanced to 100% from conventional materials* Optional from conventional materials Such as calcium carbonate, talc, clay, silicate, etc.

The compositions of the present invention may suitably be prepared by any method at the option of the formulator, non-limiting examples of which are in US5691297, Nassano et al, issued November 11, 1997; US5574005, Welch et al, issued November 12, 1996; US5569645 issued October 29, 1996 to Dinniwell et al; US5565422 issued October 15, 1996 to Del Greco et al; US5516448 issued May 14, 1996 to Capeci et al; issued February 6, 1996 to Capeci et al US5489392; US5486303, Capeci et al., issued Jan. 23, 1996; all patents are incorporated herein by reference.

In addition to the above examples, the cleaning compositions of the present invention may be formulated into any suitable laundry detergent composition, non-limiting examples of which are in US5679630, Baeck et al., issued October 21, 1997; issued October 15, 1996 US5565145 of Watson et al; US5478489 of Fredj et al issued December 26, 1995; US5470507 of Fredj et al issued November 28, 1995; US5466802 of Panandiker et al issued November 14, 1995; October 24, 1995 US5460752 issued by Fredj et al on October 17, 1995; US5458810 issued by Fredj et al on October 17, 1995; US5458809 issued on October 17, 1995 by Fredj et al; are listed as references in this paper.

It should be understood that the examples and embodiments described herein are for illustration only, and various modifications or changes therefrom will be suggested by those skilled in the art without departing from the scope and spirit of the invention.

Claims (10)

1. A detergent composition containing a protease, wherein the protease is screened by a method comprising the steps of: a. Measure the primary cleavage rate; b. Measuring the secondary cleavage rate; c. Calculate the ratio of the protease primary cleavage rate to the secondary cleavage rate; d. Select a protease with a primary cleavage rate above 1000 μg/min/μg and a ratio of primary cleavage rate to secondary cleavage rate below 150:1. 2. The detergent composition of claim 1, wherein the protease has a primary cleavage rate greater than 1200 [mu]g/min/[mu]g, and the ratio of the primary cleavage rate to the secondary cleavage rate is from about 50:1 to about 130:1. 3. A detergent composition according to claim 1, wherein the protease is derived from Bacillus subtilis. 4. A detergent composition comprising: a. from about 0.01% to about 60% by weight of a detersive surfactant; b. about 5% to about 80% by weight detergent builder; and c. From about 0.0001% to about 5% by weight of a protease screened by a method comprising the steps of: a. Measure the primary cleavage rate; b. Measuring the secondary cleavage rate; c. Calculate the ratio of the protease primary cleavage rate to the secondary cleavage rate; d. Select a protease with a primary cleavage rate above 1000 μg/min/μg and a ratio of primary cleavage rate to secondary cleavage rate below 150:1. 5. The detergent composition of claim 4, wherein the surfactant is selected from the group consisting of anionic, cationic, amphoteric, nonionic surfactants and mixtures thereof, and the detergent builder is selected from the group consisting of phosphate, pyrosulfate, orthophosphate , tripolyphosphates, higher phosphates, alkali metal carbonates and bicarbonates, alkali silicates, aluminosilicates, polycarboxylates, layered silicates, citrates and mixtures thereof. 6. A detergent composition according to claim 4 further comprising a bleaching agent. 7. A detergent composition according to claim 6, wherein the bleaching agent is selected from the group consisting of peroxygen, perborates, percarbonates, superphosphates and mixtures thereof. 8. The detergent composition of claim 4 further comprising other enzymes selected from the group consisting of cellulases, amylases, lipases, phospholipases, other proteases, peroxidases and mixtures thereof. 9. A method for screening proteases, comprising: a. Measure the primary cleavage rate; b. Measuring the secondary cleavage rate; c. Calculate the ratio of the protease primary cleavage rate to the secondary cleavage rate; d. Select a protease with a primary cleavage rate higher than 1000 μg/min/μg and a ratio of primary cleavage rate to secondary cleavage rate lower than 150:1. 10. The method for screening proteases of claim 9, comprising selecting proteases with a primary cleavage rate greater than 1200 μg/min/μg and a ratio of primary cleavage rate to secondary cleavage rate of about 50:1 to about 130:1.