JP2003509537A - Detergent composition containing protease - Google Patents

Abstract

  (57) [Summary] A detergent composition comprising a protease selected by a process comprising measuring a primary cleavage rate to measure a secondary cleavage rate. The ratio of the primary to secondary cleavage rate of the protease is calculated. Proteases having a primary cleavage rate higher than 1000 μg / min / μg and a ratio of primary to secondary cleavage rates lower than 150: 1 are selected.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION

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

[0002]

BACKGROUND OF THE INVENTION

Various types of enzymes have been used throughout laundry detergents to help remove some stains from fabrics. Each class of enzyme (amylase, protease, lipase, cellulase, etc.) usually catalyzes a different chemical reaction. For example, protease enzymes are known for their ability to hydrolyze other proteins (decompose compounds into two or more simpler compounds). Many foods and other organic substances contain proteins that stain fabric materials such as clothing. Protease enzymes help remove these stains by degrading proteins. Natural or engineered protease enzymes have been added to laundry detergent compositions for this reason.

Proteins usually consist of 20 types of amino acids, which form long polypeptide chains. In the polypeptide chain, each amino acid forms a peptide bond with another amino acid. Proteases hydrolyze peptide bonds as substrates. However, each protease has a different substrate specificity. For example, some proteases screen the insulin β chain and hydrolyze the peptide bond between valine (Val) and cysteine (Cys) in the insulin β chain.
Other proteases are insulin β chain proline (Pro) and lysine (Lys)
Hydrolyzes the peptide bond with. Therefore, when applying proteases to detergent compositions, we need to select the most suitable protease from many types of proteases, since protease substrate specificity is one of the most important factors. .

Detergent compositions containing proteases effective in removing soils, especially protein-based soils, and detergent compositions containing proteases screened by a process have been found herein.

[0005]

[Summary of Invention]

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

In particular, in one aspect of the invention there is provided a detergent composition comprising a protease,
The protease measures the primary cleavage rate, measures the secondary cleavage rate and calculates the ratio of the primary cleavage rate to the secondary cleavage rate of the protease, the primary cleavage rate higher than 1000 μg / min / μg and 150: 1. Selected by the process of selecting proteases with a lower ratio of primary to secondary cleavage rates. Preferably, the protease has a primary cleavage rate of greater than 1200 μg / min / μg with a ratio of primary cleavage rate to secondary cleavage rate of about 50: 1 to about 130: 1. Furthermore, the protease is preferably derived from Bacillus subtilis.

In another aspect of the invention, a) from about 0.01 to about 60% by weight of a cleaning surfactant,
b) from about 5 to about 80% by weight of detergent builder, and c) from about 0.0001 to about 0.0001 to about 0.0001 to about 1.0 μg / min / μg of primary cleavage rate and less than 150: 1 ratio of primary to secondary cleavage rate. A detergent composition comprising about 5% by weight is provided. In another aspect of the invention, a. Measure the primary cleavage rate; b. Measuring the rate of secondary cleavage; c. Calculate the ratio of primary cleavage rate to secondary cleavage rate; d. 1000
A method for screening is provided by the process comprising selecting a protease having a primary cleavage rate higher than μg / min / μg and a ratio of primary cleavage rate to secondary cleavage rate lower than 150: 1.

[0008]

[Specific Disclosure of the Invention]

While the specification concludes with claims that particularly point out and distinctly claim 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 ratios are weight ratios unless otherwise stated.

Definitions As used herein, "comprising" means that other steps and ingredients that do not affect the final result may be added. This term encompasses the terms “consisting of” and “consisting essentially of”. All references cited are incorporated herein in their entirety by reference. Citation of any reference is not an admission regarding any determination as to its availability as prior art to the claimed invention. As used herein, the term "detergent composition" or "detergent" is meant to refer to any agent commonly used to remove soil, such as synthetic or soap type household or laundry detergents. .

Protease Enzyme Selection Proteases are selected by the process of measuring the rate of primary cleavage, measuring the rate of secondary cleavage, and calculating the ratio of primary to secondary cleavage rate of the protease. The protease has a primary cleavage rate higher than 1000 μg / min / μg and a 150:
It is selected from those having a ratio of primary cleavage rate to secondary cleavage rate lower than 1. The proteases in the detergent compositions of the present invention can be obtained from natural or combined sources. If the protease is obtained from a natural source, the protease is preferably Ba
It is derived from cillus subtilis.

Cleavage Rate In assessing the characteristics of proteases for the detergent compositions of the present invention, two major characteristics of the proteases are important, one being the kinetics of hydrolysis (corresponding to the primary cleavage rate). Yes, the others are broad cleavage specificities (corresponding to secondary cleavage rates). The detergent of the present invention exhibits better cleaning performance than conventional detergents. Furthermore, we must correlate these characteristics with the rate of cleavage.

Cleavage rate measures how fast a protease hydrolyzes an insulin β chain polypeptide. The insulin β chain polypeptide consists of 30 amino acids. First, the protease is No. 15 Leucine (Leu) and No. 15 1
The peptide bond with 6-tyrosine (Tyr) is hydrolyzed to make a bi-short polypeptide. The primary cleavage rate of the present invention describes how fast a protease can hydrolyze an insulin β chain polypeptide into two short polypeptides. If the primary cleavage rate of the protease is high, the protease will hydrolyze and
Make two shorter polypeptides faster. Thus, the primary cleavage rate of the present invention represents the kinetics of protease hydrolysis. Thus, the higher the primary cleavage rate of a protease, the faster it can hydrolyze protein soils.

As noted above, insulin β chain polypeptides are hydrolyzed by proteases into two short polypeptides. These two polypeptides are Leu-Tyr
This is because it does not contain a peptide bond and one operable bond has been decomposed as described above. To hydrolyze a short polypeptide, the protease must hydrolyze peptide bonds other than Leu-Tyr. One technique for quantifying the ability of a protease to cleave another bond is defined as cleavage specificity. Cleavage specificity is the ability of a protease to cleave peptide bonds flanking different amino acids. For example, if the protease cleaves a Leu-Tyr peptide bond, the cleavage specificity is Lue. Some proteases may cleave some bonds adjacent to different amino acids in different proteins.
Proteases can hydrolyze peptides faster if they have a broad cleavage specificity.

Secondary cleavage rate describes how fast a protease hydrolyzes a short polypeptide after the above primary cleavage. If the rate of secondary cleavage is high, the protease can hydrolyze shorter polypeptides faster, which means that the protease has a broader cleavage specificity.

Without wishing to be bound by theory, it is believed that the rate of primary cleavage and the ratio of primary to secondary cleavage rates are important for hydrolyzing protein soils.
The ratio of first-order cleavage rate to second-order cleavage rate represents a balance between hydrolysis kinetics and broad cleavage specificity. If this ratio is higher than 150: 1, the protease exhibits a relatively broad cleavage specificity, leaving some protein soil residue on the fabric. Therefore, the cleaning effect is reduced.

Protease Screening Process In another aspect of the present invention there is provided a detergent composition comprising a protease, the protease comprising: a) a primary cleavage rate, a secondary cleavage rate, and a protease. Calculate the ratio of first-order cleavage rate to second-order cleavage rate; b) 1000 μg / mi
Having a primary cleavage rate higher than n / μg, preferably higher than 1200 μg / min / μg, and a ratio of primary cleavage rate to secondary cleavage rate lower than 150: 1, preferably from about 50: 1 to about 130: 1. Selected by a process consisting of selecting proteases. A certain protease is selected by the method. These proteases are WO
9920769, WO9920770, WO9920771. To measure the primary and secondary cleavage rates, we use the insulin β chain fragmentation pattern test. The insulin β chain fragmentation pattern assay is performed as follows:

Insulin β chain fragmentation pattern test The main cleavage site is defined as the site that is cleaved early in the hydrolysis of the insulin β chain (before it is hydrolyzed up to 50% of the insulin β chain).
The following method is used to identify the main cleavage site and investigate the primary cleavage rate. 1 mg
/ ml of oxidized insulin beta chain is prepared in 0.1 M Tris-HCl buffer pH 7.0 and incubated at 35 ° C for 10 minutes. Then 10 μL of the enzyme solution is mixed with the insulin solution at a final enzyme concentration of 0.1-0.2 ppm. After hydrolysis for 3 minutes, the reaction is stopped by adding an equal volume of 0.1 M HCl. The reaction mixture is then analyzed by HPLC to measure fragmented peptides. The fragmented peptide was identified by measuring MW by LC / MS. The peak was calculated quantitatively from the peak area. The primary cleavage rate is calculated from the disappearance rate of insulin β chain in 3 minutes.

The following method is used to determine the secondary cleavage rate. 1 mg / ml oxidized insulin β chain is prepared in 0.1 M Tris-HCl buffer pH 7.0 and incubated at 35 ° C. for 10 minutes. Then, 10 μL of the enzyme solution and 0.1 μl of insulin solution
Mix at a final enzyme concentration of ~ 0.2 ppm. After 2 hours of hydrolysis, an equal volume of 0.
The reaction is stopped by adding 1M HCl. The reaction mixture is then analyzed by HPLC to measure fragmented peptides. The peak is quantitatively calculated from the peak area. The secondary cleavage rate is calculated from the disappearance rate of the peptide generated by the primary hydrolysis, that is, the disappearance rate of peptide 1-15 and peptide 16-30 in 2 hours.

Detergent Compositions The detergent compositions of the present invention contain from about 0.0001 to about 5% by weight protease. With respect to the primary cleavage rate (hydrolysis kinetics) and secondary cleavage rate (broad cleavage specificity) of the protease, the present invention provides a detergent composition comprising from about 0.0001 to about 5% by weight of protease, Proteases have a primary cleavage rate higher than 1000 μg / min / μg, with a ratio of primary to secondary cleavage rates lower 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 hydrolyze protein soil faster. Moreover,
Proteases can rapidly hydrolyze both protein stains and protein stain residues because the ratio of primary to secondary cleavage rates is less than 150: 1. Detergent compositions comprising proteases selected by the above process show good cleaning performance. The detergent composition of the present invention is about 0.0001 to about 5% by weight, preferably about 0.002.
Contains about 1% protease.

The detergent composition of the detersive surfactant present invention will contain a surfactant, the surfactant of the nonionic and / or anionic and / or cationic and / or amphoteric and / or zwitterionic and And / or may be selected from the group consisting of semi-polar surfactants. Surfactants are typically present at levels of about 0.01 to about 60% by weight. A more preferred loading level is from about 1 to about 35% by weight of the detergent composition according to the present invention, and most preferably from about 1 to about 30% by weight. The surfactant is preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated to promote or at least not degrade the stability of any enzyme in these compositions. Preferred surfactants used in accordance with the present invention comprise as surfactants one or more of the nonionic and / or anionic surfactants described herein.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the present invention, with polyethylene oxide condensates being preferred. These compounds include the condensation products of alkylene oxides with alkylphenols 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 from about 2 to about 25 per mole of alkylphenol.
It is present in an amount corresponding to 1 mole, more preferably from about 3 to about 15 moles of ethylene oxide. Commercially available nonionic surfactants of this type include Igepal ^™ CO-630 sold by GAF Corporation and T sold by Rohm & Haas Company.
riton ^™ X-45, X-114, X-100 and X-102. These surfactants are commonly referred to as alkylphenol alkoxylates (eg alkylphenol ethoxylates).

Condensation products of primary and secondary fatty alcohols with about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the present invention. The alkyl chains of the aliphatic alcohols are straight or branched, primary or secondary and usually have from about 8 to about 22 carbon atoms. Condensation products of alcohols having an alkyl group of about 8 to about 20 carbon atoms, more preferably about 10 to about 18 carbon atoms, and about 2 to about 10 moles of ethylene oxide per mole of alcohol are preferred. About 2 to about 7 moles of ethylene oxide per mole of alcohol, most preferably 2 to 5 moles of ethylene oxide are present in the above condensation product. Examples of commercially available nonionic surfactants of this type include Tergito, both sold by Union Carbide Corporation.
l ^TM 15-S-9 (condensation product of C ₁₁ -C ₁₅ straight chain alcohol and 9 mol of ethylene oxide), Tergitol ^TM 24-L-6 NMW (C ₁₂ -C ₁₄ primary alcohol and 6 mol of ethylene oxide, narrow Condensation product of molecular weight distribution); Neodol ^™ 45-9 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol and 9 mol of ethylene oxide), Neodol ^™ 23-3 (C ₁₂ -C ₁₃ ) sold by Shell Chemical Company. Condensation product of linear alcohol and 3.0 mol of ethylene oxide), Neodol ^™ 45-7 (condensation product of C ₁₄ -C ₁₅ linear alcohol and 7 mol of ethylene oxide), Neodol ^™ 45-5 (C ₁₄ -C ₁ Condensation product of ₅ linear alcohols and 5 mol of ethylene oxide); The Procter & Ga
Kyro ^™ EOB (condensation product of C ₁₃ -C ₁₅ alcohol and 9 moles of ethylene oxide) sold by mble Company; Genapol LA O3 sold by Hoechst
O or O50 (condensation product of C ₁₂ -C ₁₄ alcohol and 3 or 5 mol of ethylene oxide). The preferred range of HLB in these products is 8-11, most preferably 8-10.

Hydrophobic groups having about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about. 1.3 ~
A polysaccharide having about 2.7 sugar units, eg with hydrophilic groups of polyglycosides, 19
The alkyl polysaccharides disclosed in Llenado, US Pat. No. 4,565,647, issued Jan. 21, 1986, are also useful nonionic surfactants of the present invention. Reducing sugars having 5 or 6 carbon atoms may also be used, eg glucose, galactose and galactosyl moieties may be used in place of glucosyl moieties (optionally).
Hydrophobic groups are attached at positions 2, 3, 4, etc. to give glucose or galactose rather than glucoside or galactoside). For example, there may be an intersugar linkage between one position of the additional sugar unit and the 2, 3, 4 and / or 6 position of the preceding sugar unit.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _{x where} R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and their Is selected from the group consisting of a mixture of :, wherein the alkyl group has from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2
Or 3, preferably 2; t is 0 to about 10, preferably 0; x is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to About 2.
7 Glycosyl is preferably derived from glucose. To produce these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a glucose source to produce glucoside (
Bond at position 1). Additional glycosyl units may also be attached between their 1-position and the preceding glycosyl units at the 2, 3, 4 and / or 6-positions, preferably predominantly the 2-position.

[0025]   Hydrophobicity formed by condensation of propylene oxide and propylene glycol
Condensation products of the base and ethylene oxide can also be added non-ionic cleaning surfactants of the present invention.
Suitable for use as a sex agent. The hydrophobic portion of these compounds is preferably about 150.
It has a molecular weight of 0 to about 1800 and is water insoluble. Polio to this hydrophobic part
The addition of the xyethylene moiety tends to increase the overall water solubility of the molecule, resulting in product hydration.
Keeps the polyoxyethylene content at about 50% of the total weight of the condensation product.
Which corresponds to condensation with up to about 40 moles of ethylene oxide. this
Examples of this type of compound include certain commercially available Plurafac sold by BASF. ^TM LF404 and Pluronic^TMThere is a surfactant.

As nonionic surfactants according to the invention, the products obtained from the reaction of propylene oxide with ethylenediamine and the condensation products of ethylene oxide are also suitable for use. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide and usually has a molecular weight of about 2500 to about 3000. The hydrophobic portion is condensed with ethylene oxide to the extent that the condensation product contains from about 40 to about 80 weight percent polyoxyethylene and has a molecular weight of from about 5000 to about 11,000. Examples of this type of nonionic surfactant are certain commercially available Tetronic ^™ compounds sold by BASF.

Nonionic surfactants of the present invention include polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. It is preferable for use. C ₈ -C ₁₄ alkylphenol ethoxylates having 3 to 15 ethoxy groups, C ₈ -C ₁₈ alcohol ethoxylates having 2 to 10 ethoxy groups (
Preferably the average C _10), and mixtures thereof are most preferred.

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

[Chemical 1] Or the formula ^{R 1} is H, or ^{R 1} is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, ^{R 2} is C _5-31 hydrocarbyl, Z is A polyhydroxyhydrocarbyl having a linear hydrocarbyl chain and at least 3 hydroxyls directly attached to the chain, or an alkoxylated derivative thereof. Preferably, R ¹ is methyl, R ² is a linear C _11-15 alkyl or C _16-18 alkyl or alkenyl chain such as coconut alkyl, or mixtures thereof, Z is glucose in a reductive amination reaction,
It is derived from reducing sugars such as fructose, maltose and lactose.

Suitable anionic surfactants used are those described in "The Journal of the American O
il Chemists Society ", 52 (1975 ), C 8 -C 20 carboxylic acids which are sulfonated with gaseous SO ₃ according Pp.323-329 (i.e., fatty acids), including straight-chain esters of, linear alkylbenzene sulfonates, alkyl Ester sulfonates, branched alkyl sulfonates, mid-branched alkyl sulfonate surfactants Suitable starting materials include natural fatty substances such as those derived from tallow, palm oil, etc.

Particularly preferred alkyl ester sulfonate surfactants for laundry include alkyl ester sulfonate surfactants of the following structural formula:

[Chemical 2] Where R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is an alkyl ester sulfonate. It is a cation that forms a water-soluble salt with. Suitable salt forming cations include metals such as sodium, potassium and lithium, 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. Methyl ester sulfonates in which R ³ is C ₁₀ -C ₁₆ alkyl are particularly preferred.

[0031]   Other suitable anionic surfactants include the formula ROSO_ThreeWith a water-soluble salt or acid of M
There are certain alkyl sulphate surfactants, where R is preferably C₁₀-C ₂₄ Hydrocarbyl, preferably C₁₀-C₂₀Alkyl having an alkyl moiety
Or hydroxyalkyl, more preferably C₁₂-C₁₈Alkyl or hydr
Roxyalkyl, M is H or a cation, such as an alkali metal cation (
Eg sodium, potassium, lithium), ammonium or substituted ammonium
(Eg, methyl-, dimethyl- and trimethyl-ammonium cations,
And like the tetramethylammonium and dimethylpiperidinium cations
Quaternary ammonium cations, and ethylamine, diethylamine, triethyl
Quaternary ammonium cations derived from alkylamines such as ruamine,
And their mixtures). Typically C₁₂-C₁₆Low alkyl chains
At a high cleaning temperature (eg, about 50 ° C or lower), C₁₆-C₁₈Alkyl chain is high
It is preferable that the washing temperature be high (for example, about 50 ° C. or higher).

Other anionic surfactants useful for cleaning purposes may also be included in the detergent compositions of the present invention. These 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, for example, sulfonated polycarboxylic acids, C ₈ -C ₂₄ , prepared by sulfonation of thermal decomposition products of alkaline earth metal citrates as described in British Patent Specification No. 1,082,179. Alkyl polyglycol ether sulphate (containing within 10 mol of ethylene oxide), alkyl glycerol sulphonate, fatty acyl glycerol sulphonate, fatty oleyl glycerol sulphate, alkylphenol ethylene oxide ether sulphate, paraffin sulpho Chromatography, alkyl phosphates, isethionates such as the acyl isethionates, N- acyl taurates, alkyl succinate cinnamate and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) And sulfates of alkyl polysaccharides such as diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₂ diesters), acyl sarcosinates, sulfates of alkyl polyglucosides (nonionic non-sulfate compounds are described below. ), A branched primary alkyl sulphate, and the formula RO (CH ₂ CH ₂ O) _k —CH ₂ COO ⁻ M ⁺ (R is C ₈ —
A C ₂₂ alkyl, k is an integer from 1 to 10, M is alkyl polyethoxy carboxylates such as a soluble salt-forming cation). Also suitable are resin acids and hydrogenated resin acids, such as rosins, hydrogenated rosins, resin acids and hydrogenated resin acids present in or derived from tall oil.

Another example is “Surface Active Agents and Detergents” (Vol. I and II, Schwar
tz, Perry and Berch). A variety of such surfactants are available in 19
It is also generally disclosed at column 23, line 58 to column 29, line 23 of US Patent 3,929,678, issued December 30, 1975, to Laughlin et al. (Incorporated herein by reference). ).

When included herein, the detergent composition of the present invention typically comprises from about 1 to about 40% by weight.
, Preferably about 3 to about 20% of such anionic surfactants.

Highly preferred anionic surfactants are alkylalkoxylated sulphate surfactants which are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, where R is an unsubstituted C _10- A hydroxyalkyl group having a C ₂₄ alkyl or C ₁₀ -C ₂₄ alkyl moiety, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A being an ethoxy or propoxy unit And m is greater than zero, typically about 0.5 to about 6, more preferably about 0.5 to about 3, and M is H or a cation, such as a metal cation (eg, sodium, potassium, lithium). , Calcium, magnesium, etc.), ammonium or substituted ammonium cations .
Alkyl ethoxylated sulphates and alkyl propoxylated sulphates are considered here. Specific examples of substituted ammonium cations are derived from methyl, dimethyl, trimethyl-ammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and alkylamines such as ethylamine, diethylamine, triethylamine. Things, their mixtures, and so on. Exemplary surfactants are C _12-
C ₁₈ alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C ₁₈ E
_{(1.0) M), C 12} -C 18 alkyl polyethoxylate (2.25) sulfate _{(C 12 -C 18 E (2.25} ) M), C 12 -C 18 alkyl polyethoxylate (3. 0) sulfate _{(C 12 -C 18 E (3.0} ) M) , and _C 12 _{-C 18} alkyl polyethoxylate (4.0) sulfate _{(C 12} -
C ₁₈ E (4.0) M), where M is conveniently selected from sodium and potassium.

The detergent composition of the present invention comprises a cationic, amphoteric, dipolar and semipolar surfactant,
And may also contain nonionic and / or anionic surfactants other than those already mentioned herein.

Suitable cationic detersive surfactants for use in the detergent compositions of the present invention are those that have one long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants, such as alkyl trimethyl ammonium halogenides, and surfactants having the formula: [R ² (OR ³ ) _y ] [R ⁴ ( oR ³⁾ _{y] 2} R ⁵ N ⁺ X ^- the formula ^{R 2} is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain; each ^{R 3} is _-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 C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl ring structure formed by linking two R ⁴ groups, -C
H ₂ CHOH-CHOHCOR ⁶ CHOHCH ₂ OH (R ⁶ is a hexose or hexose polymer having a molecular weight of about 1000 or less), and hydrogen when y is not 0; R ⁵ is selected from R ⁴ and R ⁴ ; Are similar or alkyl chains in which the total number of carbon atoms of R ² + R ⁵ is about 18 or less; each y is 0 to
About 10 and the sum of y values is 0 to about 15; X is any compatible anion.

[0038]   Quaternary ammonium surfactants suitable for the present invention have the formula (I):

[Chemical 3] Formula I wherein R ₁ is short chain alkyl (C ₆ -C ₁₀ ) or alkylamidoalkyl of formula (II):

[Chemical 4] Formula II (y is 2-4, preferably 3); wherein R ₂ is H or C ₁ -C ₃ alkyl; wherein x is 0-4, preferably 0-2, most preferably Is 0; wherein R ₃ , R ₄ and R ₅ are the same or different and are short chain alkyl (C ₁ -C ₃ ) or an alkoxylated alkyl of formula III below; X ⁻ is a counterion, preferably a halide such as chloride or methylsulfate;

[Chemical 5] Formula III (R ⁶ is C ₁ -C ₄ and z is 1 or 2)

Preferred quaternary ammonium surfactants have the formula where R ₁ is C ₈ , C ₁₀ or mixtures thereof, x = 0, R ₃ , R ₄ ═CH ₃ and R ₅ ═CH ₂ CH ₂ OH. As defined in I.

Highly preferred cationic surfactants are water soluble quaternary ammonium compounds useful in the present composition having the formula: R ₁ R ₂ R ₃ R ₄ N ⁺ X ⁻ (i) Wherein R ₁ is C ₈ -C ₁₆ alkyl and each of R ₂ , R ₃ and R ₄ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl and-
A _{(C 2 H 40) x H} (x has a value of 2 to 5), X is an anion.
No more than 1 of R ₂ , R ₃ or R ₄ must be benzyl. The preferred alkyl chain length for R ₁ is C ₁₂ -C ₁₅ , especially where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or synthetically derived by olefin build-up or oxoalcohol synthesis. To be done. Preferred groups for R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl groups and the anion X is selected from halide, methosulfate, acetic acid and phosphate ions.

Examples of quaternary ammonium compounds of formula (i) suitable for use herein are: coconut trimethylammonium chloride or bromide coconut methyldihydroxyethylammonium chloride or bromidodecyltriethylammonium chloride decyldimethylhydroxyethylammonium chloride or Bromide C _12-15 dimethylhydroxyethylammonium chloride or bromide Coconut dimethylhydroxyethylammonium chloride or bromide Myristyl trimethylammonium methylsulfate lauryl dimethylbenzylammonium chloride or bromidolauryl dimethyl (ethenoxy) ₄ ammonium chloride or bromide choline ester (R ₁ is CH ₂ -CH ₂ -OC (= O) -C _{12-1 4} alkyl and R ₂ , R ₃ and R ₄ are methyl compounds of formula (i) Dialkyl imidazolines (compounds of formula (i))

Other cationic surfactants useful herein are Cambre, US Pat. No. 4,228,044 and European Patent Application EP000,2, issued October 14, 1980.
24 is also described.

Typical cationic fabric softening ingredients include water insoluble quaternary ammonium fabric softening activators or their corresponding amine precursors, with dilong chain alkyl ammonium chloride or methyl sulfate being the most commonly used. There is. Among these preferred cationic softeners are: 1) ditallowdimethylammonium chloride (DTDMAC) 2) dihydrogenated tallowdimethylammonium chloride 3) dihydrogenated tallowdimethylammonium methylsulfate 4) distearyldimethylammonium Chloride 5) Dioleyldimethylammonium chloride 6) Dipalmitylhydroxyethylmethylammonium chloride 7) Stearylbenzyldimethylammonium chloride 8) Tallowtrimethylammonium chloride 9) Hydrogenated tallowtrimethylammonium chloride 10) C _12-14 alkylhydroxyethyldimethylammonium chloride chloride 11) C _12-18 alkyl dihydroxyethyl methyl ammonium chloride 12) di (stearoyl oxy ethyl) Jimechirua Moniumukurorido (DSOEDMAC) 13) di (tallow oxyethyl) dimethyl ammonium chloride 14) ditallow imidazolinium methylsulfate 15) 1- (2-tallow-ylamide ethyl) -2-tallow-yl imidazolinium methylsulfate

Biodegradable quaternary ammonium compounds have been provided as an alternative to the traditionally used di-long chain alkyl ammonium chlorides and methyl sulphates. Such a quaternary ammonium compound has a long-chain alkyl (alkenyl) group with a functional group such as a carboxy group interposed. The above substances and the fabric softening composition containing them are EP-A-0,040,562 and EP-A-0,
It is disclosed in numerous documents such as 239,910.

The quaternary ammonium compound and its amine precursor are represented by the following formula (I) or (II
)have:

[Chemical 6] In the above formula, Q is -OC (O)-, -C (O) -O-, -OC (O) -O-,-
^{NR 4 -C (O) -,} - C (O) -NR 4 - is selected from; ^{R 1} is a ^{_{(CH 2) n -Q-T}} 2 or ^{T 3; R 2} is _{(CH 2) m} -Q-T ⁴ or T ⁵ or R ³ ; R ³ is C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl or H; R ⁴ is H, C ₁ -C ₄ alkyl or C is ₁ -C ₄ ^{hydroxyalkyl; T 1, T 2, T} 3, T 4, T 5 is a _C 11 _{-C 22} alkyl or alkenyl independently; n and m are an integer of from 1 to 4; And X ⁻ are softener compatible anions. Non-limiting examples of softener compatible anions include chloride or methylsulfate.

The alkyl or alkenyl chain T ¹ , T ² , T ³ , T ⁴ , T ⁵ is at least 11
Must have at least 16 carbon atoms, preferably at least 16 carbon atoms.
The chain may be linear or branched. Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials. Particularly preferred are compounds in which T ¹ , T ² , T ³ , T ⁴ , T ⁵ represent a mixture of long chain substances typical of tallow.

Specific examples of quaternary ammonium compounds suitable for use in the present aqueous fabric softening composition include: 1) N, N-di (tallowyloxyethyl) -N, N-dimethylammonium chloride 2) N, N-di (tallowyloxyethyl) -N-methyl, N- (2-hydroxyethyl) ammonium methylsulfate 3) N, N-di (2-tallowyloxy-2-oxoethyl) -N, N-dimethylammonium Chloride 4) N, N-di (2-tallowyloxyethylcarbonyloxyethyl) -N
, N-dimethylammonium chloride 5) N- (2-tallowyloxy-2-ethyl) -N- (2-tallowyloxy-2-oxoethyl) -N, N-dimethylammonium chloride 6) N, N, N -Tri (tallowyloxyethyl) -N-methylammonium chloride 7) N- (2-tallowyloxy-2-oxoethyl) -N- (tallowyl-
N, N-dimethylammonium chloride) 8) 1,2-ditaroyloxy-3-trimethylammoniopropane chloride and mixtures of the above substances.

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

Amphoteric surfactants are also suitable for use in the detergent composition 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, where the aliphatic groups may be straight chain or It may be a branched chain. One of the aliphatic substituents is at least about 8 carbon atoms,
It typically has from about 8 to about 18 carbon atoms and at least one has an anionic water-soluble group such as a carboxy, sulfonic acid, sulfate group. For examples of amphoteric surfactants, see Laughlin et al., US Pat. No. 3,9, issued Dec. 30, 1975.
29, 678, column 19, lines 18-35. When included herein, the detergent compositions of the present invention typically contain from 0.2 to about 15% by weight, preferably from about 1 to about 10% of such amphoteric surfactants.

Dipolar surfactants are also suitable for use in the detergent composition. These surfactants are
It can be broadly described as a derivative of a secondary or tertiary amine, a derivative of a heterocyclic secondary or tertiary amine, or a derivative of a quaternary ammonium, quaternary phosphonium or tertiary sulfonium compound. For examples of zwitterionic surfactants, see 19
See Laughlin et al., US Pat. No. 3,929,678, December 19, 1975, column 19, line 38 to column 22, line 48. When included herein, the detergent compositions of the present invention typically contain from 0.2 to about 15% by weight, preferably from about 1 to about 10% of such a dipolar surfactant.

Semi-polar nonionic surfactants contain two moieties selected from the group consisting of one alkyl moiety having from about 10 to about 18 carbon atoms, an alkyl group having from about 1 to about 3 carbon atoms and a hydroxyalkyl group. Having water-soluble amine oxide; about 10 to about 1 carbon atom
A water-soluble phosphine oxide having one alkyl moiety of eight, two moieties selected from the group consisting of an alkyl group of about 1 to about 3 carbon atoms and a hydroxyalkyl group; one alkyl of about 10 to about 18 carbon atoms A special category of nonionic surfactants, including water soluble sulfoxides having moieties, moieties selected from the group consisting of alkyl and hydroxyalkyl moieties of about 1 to about 3 carbon atoms.

Semipolar nonionic detergent surfactants include amine oxide surfactants having the formula:

[Chemical 7] Wherein R ³ is an alkyl, hydroxyalkyl, alkylphenyl group having from about 8 to about 22 carbon atoms or a mixture thereof; R ⁴ is an alkylene having from about 2 to about 3 carbon atoms, a hydroxyalkylene group or A mixture thereof;
x is 0 to about 3; each R ⁵ is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms, or a polyethylene oxide group having about 1 to about 3 ethylene oxide groups. The R ⁵ groups may be linked to each other, for example via an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants include, in particular, C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxides.

When included herein, the cleaning composition of the present invention typically comprises from 0.2 to
It contains from about 15% by weight, preferably from about 0.1 to about 10% of such semipolar nonionic surfactants.

[0054]   The detergent composition of the present invention comprises a co-surfactant selected from the group of primary or tertiary amines.
Cosurfactants may also be included.   Suitable primary amines for use herein have the formula R₁NH_TwoThere are amines by
R₁Is C₆-C₁₂, Preferably C₆-C₁₀Alkyl chain, or R_FourX (CH _Two )_nAnd X is -O-, -C (O) NH- or -NH-, R_FourIs C ₆ -C₁₂It is an alkyl chain and n is 1 to 5, preferably 3. R₁Alkyl
The chain may be linear or branched and may have an ethylene number of 12 or less, preferably less than 5.
The oxidant portion may be interposed.   The preferred amine according to the above formula is an n-alkylamine. Suitable for use here
The amines include 1-hexylamine, 1-octylamine, 1-decylamine and
And laurylamine. Other preferred primary amines include C₈-C₁₀ Oxypropylamine, octyloxypropylamine, 2-ethylhexylo
Xypropylamine, laurylamidopropylamine and amidopropylami
There is

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 ₁ -C ₈ alkyl chains or

[Chemical 8] And R ₃ is a C ₆ -C ₁₂ , preferably C ₆ -C ₁₀ alkyl chain, or R ₃ is R ₄ X (CH ₂ ) _n (X is —O—, —C (O) NH -Or-NH-
R ₄ is C ₄ -C ₁₂ and n is 1-5, preferably 2-3. R ₅ is H or C ₁ -C ₂ alkyl and x is 1-6. R ₃ and R ₄ may be straight or branched and the R ₃ alkyl chain may be mediated by up to 12 and preferably less than 5 ethylene oxide moieties.

Preferred tertiary amines are those wherein R ₁ is a C ₆ -C ₁₂ alkyl chain and R ₂ and R ₃ are C ₁ -C ₃ alkyl or

[Chemical 9] (Wherein R ₅ is H or CH ₃ and x = 1 to 2), and R ₁ R ₂ R ₃ N. Also preferred are amidoamines of the formula:

[Chemical 10] In the above formula, R ₁ is C ₆ -C ₁₂ alkyl, n is 2-4, preferably n is 3, and R ₂ and R ₃ are C ₁ -C ₄ .

Most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C _8-10 oxypropylamine, N-
Coco-1,3-diaminopropane, coconut alkyldimethylamine, lauryldimethylamine, laurylbis (hydroxyethyl) amine, cocobis (hydroxyethyl) amine, 2 mole propoxylated laurylamine, 2 mole propoxylated octylamine, laurylamide There are propyldimethylamine, C _8-10 amidopropyldimethylamine and C ₁₀ amidopropyldimethylamine. The most preferred amines for use in the composition are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable is
n-dodecyldimethylamine, bishydroxyethyl coconut alkylamine,
7-ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine.

Additional Ingredients Builder The composition according to the invention may further comprise a builder. Aluminosilicate materials, silicates, polycarboxylates, alkyl or alkenyl succinic acids, and fatty acids, materials such as ethylenediaminetetraacetic acid, diethylenetriaminepentamethyleneacetic acid, sequestering agents such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriamine. Any conventional builder is suitable for use herein, including pentamethylene phosphonic acid. Phosphate builders may also be used here.

Suitable builders include inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials, more specifically hydrated synthetic zeolites such as hydrated zeolites A, X, B,
There is HS or MAP. Another suitable inorganic builder material is a laminated silicate, such as SKS-6 (
Hoechst). SKS-6 is a crystal laminated silicate made of sodium silicate (Na ₂ Si ₂ O ₅ ).

Suitable polycarboxylates having one carboxy group include lactic acid, glycolic acid and their ether derivatives, as disclosed in Belgian patents 831,368, 821,369 and 821,370. Polycarboxylates with two carboxy groups include succinic acid, malonic acid, (ethylenedioxy)
Water-soluble salts of diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and the ethers described in German Patent Publication 2,446,686, 2,446,687 and US Pat. No. 3,935,257. There are carboxylates and the sulfinyl carboxylates described in Belgian Patent 840,623. Polycarboxylates having three carboxy groups include, among others, water-soluble citrates, aconitrates and citraconates, and British Patent 1,379,241.
Carboxymethyl oxysuccinate described in US application 720587
Succinate derivatives such as lactoxysuccinate described in 3, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylate described in British Patent 1,387,447. is there.

Polycarboxylates having four carboxy groups are described in British Patent 1,261
, 829, oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,
There is 1,2,3-propane tetracarboxylate. Polycarboxylates having sulfo substituents include sulfosuccinate derivatives disclosed in British Patents 1,398,421, 1,398,422 and US Patent 3,936,448, and British Patent 1,082,179. There are sulfonated pyrolytic citrates described and polycarboxylates with phosphon substituents are described in British Patent 1,439,000.
It is disclosed in.

Cycloaliphatic and heterocyclic polycarboxylates include cyclopentane-cis,
Cis, cis-tetracarboxylate, cyclopentadienide pentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,
2,5,5-tetrahydrofuran-tetracarboxylate, 1,2,3,4
There are 5,6-hexane-hexacarboxylate and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include meritic acid, pyromellitic acid, and the phthalic acid derivatives disclosed in British Patent 1,425,343. Preferred polycarboxylates among the above are hydroxycarboxylates having up to 3 carboxy groups per molecule, more particularly citrates.

Preferred builders for use in the composition include a mixture of a water insoluble aluminosilicate builder such as Zeolite A or layered silicate (SKS-6) and a water soluble carboxylate chelating agent such as citric acid. There is. Other preferred builders are mixtures of water insoluble aluminosilicate builders such as Zeolite A and water soluble carboxylate chelating agents such as citric acid. Preferred builders for use in the liquid detergent compositions of the present invention are soaps and polycarboxylates.

Other builder substances that may form part of the builder for use in the granular composition include alkali metal carbonates, for example inorganic substances such as citrates, bicarbonates, silicates, and organic phosphonates, aminopolyalkylenephosphonates and There are organic materials such as aminopolycarboxylates. Other suitable water-soluble organic salts are homo- or copolymeric acids or their salts, in which case the polycarboxylic acids have at least two carboxyl groups separated from each other by not more than 2 carbon atoms. This type of polymer is GB-A-1,596
, 756. Examples of such salts are polyacrylates of MW 2000 to 5000 and copolymers thereof with maleic anhydride, such copolymers having a molecular weight of 20,000 to 70,000, in particular about 40,000. ing.

The cleaning builder salt comprises from 5 to about 80% by weight of the composition, preferably from about 10 to about 70%.
, Most commonly in amounts of about 30 to about 60% by weight.

Detergent Enzyme Detergent compositions may further include one or more enzymes that exert cleaning performance, fabric care and / or sanitizing benefits.

The above enzymes include cellulase, hemicellulase, peroxidase, glucoamylase, amylase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase,
There is an enzyme selected from phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase or mixtures thereof. Conventional proteases other than the protease of the present invention may also be used. A preferred combination is a detergent composition having a cocktail of conventional enzymes such as amylase, lipase, cutinase and / or cellulase together with one or more plant cell wall degrading enzymes.

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they have an optimum pH of 5-12 and 50 CEVU (Cellulose Viscosity U).
nit) or higher activity. Suitable cellulases are described in Barbesgoard et al., US Pat.
35, 307, J61078384 and WO 96/02653, where Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
The fungal cellulases produced by E. coli. EP 739982 describes a cellulase isolated from a novel Bacillus species. Suitable cellulases are GB-A-2,075,028, GB-A-2,095,275, DE-OS.
-2,247,832 and WO 95/26398.

Examples of such cellulases are strains of Humicola insolens (Humicola grisea var
.thermoidea), especially a cellulase produced by Humicola strain DSM1800. Other suitable cellulases were derived from Humicola insolens, DSM 1800, which has a molecular weight of about 50 kDa, an isoelectric point of 5.5, and contains 415 amino acids; A 43 kD endoglucanase, the preferred endoglucanase component is PCT patent application W
It has the amino acid sequence disclosed in O91 / 17243. September 2, 1994
Trichoderma described in WO 94/21801 by Genencor, published 9th
EGIII cellulase from longibrachiatum is also a suitable cellulase. Particularly suitable cellulases are those having a color-care effect. An example of such a cellulase is described in European Patent Application No. 9120287 filed Nov. 6, 1991.
Cellulase described in No. 9.2 specification. Carezyme and Celluz
yme (Novo Nordisk A / S) is especially useful. WO91 / 17244 and WO
See also 91/21801. Other cellulases suitable for fabric care and / or cleaning properties are WO96 / 34092, WO96 / 17994 and WO95 /
24471. The above cellulases are usually incorporated into detergent compositions at levels of 0.0001 to 2% pure enzyme by weight of the detergent composition.

Peroxidase enzymes are oxygen sources such as percarbonates, perborates,
Used in combination with persulfates, hydrogen peroxide, etc., and phenolic substrates as bleach enhancing molecules. They are used for "solution bleaching", ie to prevent dyes or pigments that fall off the substrate during the washing operation from migrating to other substrates in the wash liquor. Peroxidase enzymes are known in the art and include, for example, haloperoxidases such as horseradish peroxidase, ligninase, chloro and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Applications WO 89/099813, WO 89/09.
813, and European patent application EP 9120 filed Nov. 6, 1991.
EP96870013 filed 2882.6 and February 20, 1996
． 8 is disclosed. The laccase enzyme is also suitable.

Enhancers are typically included at levels of 0.1-5% by weight of the total composition. Preferred enhancers are the substituted phenothiazines and phenoxazines 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (WO94 / 12621), and substituted syringates (
C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or perborate is the preferred hydrogen peroxide source. The peroxidase is usually incorporated into detergent compositions at a pure enzyme level of 0.0001-2% by weight of the detergent composition.

Another enzyme that may be included in the detergent composition of the present invention is lipase. Suitable lipase enzymes for detergents include Pseudomona disclosed in British Patent 1,372,034.
Some are produced by microorganisms of the genus Pseudomonas, such as S. stutzeri ATCC 19.154. Suitable lipases include those produced by the microorganism Pseudomonas fluorescent IAM1057 which show a positive immune cross-reactivity with the antibodies of the lipase. This lipase is known as Lipase P "Amano" in Amano, Nagoya, Japan.
It is commercially available from Pharmaceutical Co. Ltd. and is hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, or Chromobacter viscosum, such as Chromobacter viscosum var.lipolyticum NRRLB 36 from Toyo Brewery Co., Ltd., Takata, Japan.
73-derived lipase; USBiochemical Corp. of USA and Disoyynth of The Netherlands
Chromobacter viscosum lipase from Co .; lipase from Pseudomonas gladioli. Particularly suitable lipases are M1 Lipase ^R and Lipomax ^R (Gist-Brocades
) And lipases such as Lipolase ^R and Lipolase Ultra ^R (Novo),
These have been found to be very effective when used in combination with the compositions of the present invention. No
vo Nordisk EP258068, WO92 / 05249 and WO95 / 226
15, Unilever's WO94 / 03578, WO95 / 35381 and WO96
The lipolytic enzymes described in / 00292 are also suitable.

Also suitable is a special type of lipase, namely cutinase [EC 3.1.1.50], which can be regarded as a lipase which does not require surface activity. Addition of cutinase to detergent compositions is described, for example, in W
OA-88 / 09367 (Genencor), WO90 / 09446 (Plant Geneti
c), WO94 / 14963 and WO94 / 14964 (Unilever). The lipase and / or cutinase is 0.0001 to 2% by weight of the detergent composition.
Is normally incorporated into detergent compositions at pure enzyme levels of.

Amylase (α and / or β) may be included for the removal of carbohydrate-based soils. WO94 / of Novo Nordisk A / S released on February 3, 1994
02597 describes a detergent composition incorporating a mutant amylase.
WO 95/10603 of Novo Nordisk A / S published April 20, 1995.
See also Other amylases known for detergent compositions include both α- and β-amylases. α-Amylase is known in the art and is described in US Pat.
, 257, EP252,666, WO91 / 00353, FR2,676,45
6, EP 285,123, EP 525,610, EP 368,341 and British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are disclosed in WO94 / 18314, published Aug. 18, 1994,
Genencor's stability-enhancing amylase described in WO 96/05295, published February 22, 1996, and WO 95/1060, published in April 1995.
3 is an amylase variant of Novo Nordisk A / S with additional modifications to its immediate parent, disclosed in 3. EP277216, WO95 / 26397 and WO96 / 2387
Amylases described in 3 (all Novo Nordisk) are also suitable.

An example of a commercial α-amylase product is Purafect Ox Am ^{R from} Genencor, all Novo N
ordisk A / S Termamyl ^R , Ban ^R , Fungamyl ^R and D commercially available from Denmark
It is uramyl ^R. WO95 / 26397, the other suitable amylases: as measured by Phadebas ^R alpha-amylase activity assay, temperature and 8 of 25 to 55 ° C.
It describes an α-amylase characterized by having a specific activity of at least 25% higher than that of Termamyl ^R at pH values in the 10 range. WO96 / 23
Variants of the above enzymes described in 873 (Novo Nordisk) are suitable. Other amylolytic enzymes having improved properties in terms of activity level and combination of thermostability and high activity level are described in WO 95/35382.

The starch degrading enzyme is from 0.0001 to 2% by weight of the composition, preferably 0.001.
Pure enzyme levels of 018-0.06%, more preferably 0.00024-0.048% are incorporated into the detergent compositions of the present invention.

The enzyme may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. The origin may further be mesophilic or extreme (eg, psychrophilic, eutrophic, thermophilic, pressure-sensitive, alkalophilic, acidophilic, halophilic). Purified or unpurified forms of these enzymes may also be used. It is now customary to modify the wild-type enzyme by protein / genetic engineering techniques to maximize performance efficacy with the detergent compositions of the present invention. For example, variants are designed to increase the compatibility of the enzyme with the conventional ingredients of such compositions. Alternatively, the variants may be designed such that the optimum pH, bleach or chelant stability, catalytic activity, etc. of the enzyme variant are adjusted to suit a particular cleaning application.

Particular attention should be paid to amino acids that are susceptible to oxidation in terms of bleach stability and surface charge in terms of detergent compatibility. The isoelectric point of such enzymes may be modified by substituting some charged amino acids, for example increasing the isoelectric point helps improve compatibility with anionic surfactants. Enzyme stability can be further enhanced, for example, by forming additional salt bridges and reinforcing calcium binding sites to increase cherant stability. Special attention must be paid to cellulases as most cellulases have separate binding domains (CBD). The properties of such enzymes are altered by modification of these domains.

The above enzymes are usually incorporated into detergent compositions at a pure enzyme level of 0.0001 to 2% by weight of the detergent composition. Enzymes are separate single components (globules containing one enzyme,
Granules, stabilizing liquids, etc.) or as a mixture of two or more enzymes (eg cogranulates).

Another suitable detergent ingredient that may be added is the enzyme oxidation scavenger, which is 19
Co-pending European Patent Application No. 928700188.6 filed January 31, 1992
No. specification. An example of such an enzymatic oxidation scavenger is ethoxylated tetraethylene polyamine.

A range of enzyme materials and their means of incorporation into synthetic detergent compositions are also described by Genenc.
or International, WO9307263A and WO9307260A, Novo, WO8908694A, and McCarty et al., US 5,55, Jan. 5, 1971.
3, 139. Enzymes are available from Place et al., US, July 18, 1978.
4,101,457 and Hughes US Pat. No. 4,507,2 dated 26 March 1985.
19 further discloses. Enzymatic substances useful in liquid detergent formulations and their incorporation in such formulations is described in Hora et al., US 4,26, April 14, 1981.
No. 1,868. Enzymes useful in detergents can be stabilized by various techniques. Enzyme stabilization technology is described in US Pat. No. 3,600,31 of Gedge et al., August 17, 1971.
9, Venegas EP 199,405 and EP 200, October 29, 1986.
, 586. Enzyme stabilization systems are also described, for example, in US 3,519.
, 570. A useful Bacillus sp. AC13 that provides proteases, xylanase and cellulase is described in Novo WO9401532A.

Color Care and Fabric Care Benefits Technologies that exert some type of color care benefits may also be included. An example of these technologies are metal catalysts for color preservation. Such metal catalysts are described in co-pending European patent application No. 92870181.2. Dye fixatives, polyolefin dispersants for anti-wrinkle and water absorption improvements, perfumes, amino-functional polymers for color care treatments and perfume lasting are another example of color care / fabric care technology, November 1996. It is described in co-pending patent application No. 96870140.9 filed on 7th date.

Fabric softeners may also be incorporated into the detergent composition according to the present invention. These agents may be inorganic or organic in type. Inorganic softeners are exemplified by the smectite clays disclosed in GB-A-1,400,898 and USP 5,019,292. Organic fabric softeners include GB-A1,514,276 and EP-B0,011.
, 340, a water-insoluble tertiary amine, EP-B-0,026,52.
7 and EP-B-0,026,528 mono _C 12 _-C disclosed in ₁₄ combination with quaternary ammonium salts and their di-long chain such as disclosed in, and EP-B-0,242,919 There is an amide. Other useful organic components of the fabric softening system include E
There are high molecular weight polyethylene oxide materials such as those disclosed in PA-0,299,575 and 0,313,146.

The level of smectite clay is usually 2 to 20% by weight, more preferably 5 to 15%.
%, The material is added to the rest of the formulation as a dry mix ingredient. Organic fabric softeners such as water insoluble tertiary amines or di-long chain amide materials have a .0.
5 to 5% by weight, usually 1 to 3% by weight, and the high molecular weight polyethylene oxide substance and water-soluble cationic substance are 0.1 to 2% by weight, usually 0.15 to 1%.
． Added at the 5% level. These substances are usually added to the spray-dried part of the composition, but in some cases they are added as dry mix particles or sprayed as a molten liquid onto other solid components of the composition. Is convenient.

Bleach An additional optional detergent ingredient that may be included in the detergent compositions of the present invention is a bleach. Preferred peroxygen bleaching agents are peroxygen bleaching compounds capable of generating hydrogen peroxide in aqueous solution. These compounds are well known in the art and include hydrogen peroxide, alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds such as alkali metal perborates, percarbonates, percarbonates. For example, phosphate. A preferred peroxygen bleaching agent is a peroxygen bleach selected from the group consisting of perborate, percarbonate, peroxyhydrate, peroxide, persulfate and mixtures thereof. Particularly preferred examples are sodium perborate, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide, which are commercially available in the form of mono- and tetrahydrates. Particularly preferred is sodium perborate tetrahydrate, especially sodium perborate monohydrate. Sodium perborate monohydrate is particularly preferred because it is very stable during storage but dissolves very quickly in the bleaching liquor.

These bleach components can include one or more oxygen bleaches and one or more bleach activators, depending on the bleach selected. When present, oxygen bleaching compounds are typically present at levels of about 1 to about 25%. The bleach component used herein can be any bleaching agent useful in detergent compositions including oxygen bleaching and others known in the art. Bleaching agents suitable for the present invention include activated or non-activated bleaching agents.

One category of oxygen bleaches that can be used is polycarboxylic acid bleaches and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4
-Oxoperoxybutyric acid and diperoxide decanedioic acid. Such bleaching agents are disclosed in US Pat. No. 4,483,781, US Patent Application 740,446, European Patent Application 0,133,354 and US Pat. No. 4,412,934.
Highly preferred bleaches also include 6-nonylamino-6-oxoperoxycaproic acid as described in US Pat. No. 4,634,551.

Another category of bleaches that can be used is halogen bleaches. Examples of hypohalous acid bleaches are, for example, trichloroisocyanuric acid, sodium and potassium dichloroisocyanurate, N-chloro and N-bromoalkanesulfonamide. Such materials are usually added at 0.5 to 10% by weight of the final product, preferably 1 to 5%.

Hydrogen peroxide releasing agents are tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (TAED), which is perhydrolyzed to form peracids as active bleaching species, resulting in an improved bleaching effect. NOBS, US
4,412,934), 3,5-trimethylhexanoloxybenzene sulfonate (ISONOBS, described in EP 120,591), pentaacetyl glucose (PAG) or phenol sulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA- OBS, described in WO 94/28106) and may be used in combination with a bleach activator. Co-pending European Patent Application No. 9187
An acylated citrate ester as disclosed in 0207.7, and
Procter & Gamble co-pending patent application USSN 60 / 022,786 (19
Filed on July 30, 1996) and No. 60 / 028,122 (10 October 1996)
Asymmetric acyclic imidobleach activators of the formula:

[Chemical 11] R in the above formula₁Is C₇-C_ThirteenA straight or branched chain saturated or unsaturated alkyl group
R_TwoIs C₁-C₈A straight chain or branched chain saturated or unsaturated alkyl group, R _Three Is C₁-C_FourIt is a straight chain or branched chain saturated or unsaturated alkyl group.

Useful bleaching agents, including bleach activators and peroxygen bleaching compounds, and peroxyacids, for detergent compositions according to the invention are described in our co-pending application USSN 08 / 136,626. , PCT / US95 / 0
7823, WO95 / 27772, WO95 / 27773, WO95 / 2777
4 and WO 95/27775.

Hydrogen peroxide may also be present at the beginning or during the washing and / or rinsing process by adding an enzyme system capable of generating hydrogen peroxide (ie the enzyme and its substrate). Such an enzyme system is disclosed in EP patent application 91202655.6, filed October 9, 1991.

Metal-containing catalysts for use in the bleach composition include cobalt-containing catalysts, such as pentaamine cobalt (III) acetate salts, and manganese-containing catalysts, such as EPA 54971.
EPA549272, EPA458397, US5,246,621, EPA4
58398, US 5,194,416 and US 5,114,611. A bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in patent application 94870206.3.

Bleaching agents other than oxygen bleaching agents are known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest is a light activated bleaching agent such as sulfonated zinc and / or aluminum phthalocyanines. These materials can adhere to the substrate during the cleaning process. Light exposure in the presence of oxygen, such as hanging clothes to dry in the sun, activates the sulfonated zinc phthalocyanine, resulting in bleaching of the substrate. Preferred zinc phthalocyanines and photoactivated bleaching processes are described in US Pat. No. 4,033,718. Typically, the detergent composition contains from about 0.025 to about 1.25% by weight of sulfonated zinc phthalocyanine.

Chelating Agents The detergent compositions may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctional substituted aromatic chelating agents and mixtures thereof, all as described below. Without being bound by theory, it is believed that the effects of these materials are due in part to their exceptional ability to remove iron and manganese ions from the wash liquor by forming soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid,
There are ethylenediaminetetrapropionic acid, triethylenetetraaminehexaacetic acid, diethylenetriaminepentaacetic acid and ethanoldiglycine, their alkali metal, ammonium and substituted ammonium salts, and mixtures thereof. Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are acceptable in the detergent composition, including DEQU
There is ethylenediaminetetrakis (methylenephosphonate) such as EST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups of more than about 7 carbon atoms. Polyfunctional substituted aromatic chelating agents are also useful in the present composition. May 1974 2
See US Pat. No. 3,812,044 issued by Connor et al. A preferred compound of this type is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene when in the acid form.

A preferred biodegradable chelator for use herein is Hartma, Nov. 3, 1987.
n and Perkins ethylenediamine disuccinic acid (“EDDS”) as described in US Pat. No. 4,704,233, especially the [S, S] isomer. The composition may also contain a water soluble methylglycine diacetate (MGDA) salt (or acid form) as a chelator or cobuilder useful with insoluble builders such as zeolites, layered silicates and the like.

If utilized, these chelating agents are typically about 0.1 to about 15% by weight of the detergent composition. More preferably, the chelating agent, if utilized, is about 0.1 to about 3.0% by weight of such composition.

Foam Inhibitor Another optional ingredient is a foam suppressant exemplified by silicones and silica-silicone mixtures. Silicones are typically represented by alkylated polysiloxane materials, and silica is commonly used in finely divided form, exemplified by silica aerogels, xerogels and various types of hydrophobic silica. These materials may be formulated as particles, with the foam control agent advantageously being releasably formulated in a water-soluble or water-dispersible, substantially non-surfactant detergent impermeable carrier. is there. Alternatively, the suds suppressor may be dissolved or dispersed in a liquid carrier and applied by spraying on one or more other components.

A preferred silicone suds suppressor is US Pat. No. 3,933,67 to Bartollota et al.
2 is disclosed. Another particularly useful suds suppressor is a self-emulsifying silicone suds suppressor and is disclosed in German Patent Application DTOS 2,6, published Apr. 28, 1977.
46,126. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. A particularly preferred suds suppressor is a suds suppressor comprising a mixture of silicone oil and a 2-alkyl-alkanol. A suitable 2-alkyl-alkanol is 2-butyloctanol sold under the tradename Isofol 12R. Such suds suppressor systems are described in co-pending European patent application N928870174, filed Nov. 10, 1992. A particularly preferred silicone suds suppressor is co-pending European patent application N ° 92201.
649.8. The compositions may comprise silicone / silica mixture in combination with a molten nonporous silica such as Aerosil ^R.

The suds suppressors described above are present at 0.001 to 2% by weight of the composition, preferably 0.0.
It is usually used at a level of 1 to 1% by weight.

Other soil suspension agents, soil release agents, optical brighteners, abrasives, bactericides, anti-fading agents, colorants and / or other ingredients used in detergent compositions such as encapsulated and unencapsulated perfumes. Ingredients may also be used.

A particularly suitable encapsulating material is a water-soluble capsule consisting of a matrix of polysaccharides and polyhydroxy compounds as described in GB 1,464,616. Other suitable water-soluble encapsulants are as described in US 3,455,838,
It comprises dextrin derived from an ungelatinized starch ester of a substituted dicarboxylic acid. These acid ester dextrins are preferably prepared from starches such as waxy maize, waxy sorghum, sago, tapioca and potato. A suitable example of the encapsulating material is N-Lok from National Starch. The N-Lok encapsulant consists of modified maize starch and glucose. The starch is modified by adding a monofunctional substituent such as octenyl succinic anhydride.

Preferred optical brighteners are anionic in nature, examples of which are 4,4′-bis (2
-Diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonic acid disodium salt, 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino ) Stilbene-2,2'-
Disodium disulfonate, 4,4'-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonic acid disodium, 4
', 4 "-Bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2-sulfonic acid monosodium, 4,4'-bis [2-anilino-4- (
N-methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino] stilbene-2,2'-disulfonic acid disodium salt, 4,4'-bis (4
-Phenyl-2,1,3-triazol-2-yl) stilbene-2,2'-disulfonic acid disodium, 4,4'-bis [2-anilino-4- (1-methyl-
2-Hydroxyethylamino) -s-triazin-6-ylamino] stilbene-2,2'-disulfonic acid disodium, 2-stilbir-4 "-(naphtho-1
', 2', 4,5) -1,2,3-Triazole-2 "-sodium sulfonate and 4,4'-bis (2-sulfostyryl) biphenyl. Highly preferred brighteners are It is a special brightener of pending European patent application 95201943.8.

Other useful polymeric materials are polyethylene glycols, especially molecular weights of 1000-1.
0000, more specifically 2000 to 8000, and most preferably about 4000. These are used at a level of 0.20-5% by weight, more preferably 0.25-2.5%. These polymers, and the homo- or copolymer polycarboxylate salts already described, maintain whiteness, fabric ash adhesion.
deposition) and in the presence of transition metal impurities to improve cleaning performance on soil, proteins and oxidative soils.

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 configurations. Examples of such polymers are generally assigned US Pat.
72,033. Particularly preferred polymers according to EP-A-0,272,033 has the following _{formula: (CH 3 (PEG) 43} ) 0.75 (POH) 0.25 [(T-PO) _2.8 (T -PEG) _0.4 ] T (POH) _0.25 ((PEG) ₄₃ CH ₃ ) _{0.75 In the} above formula, PEG is-(OC ₂ H ₄ ) O-, PO is (OC ₃ H ₆ O), And T is (pcOC ₆ H ₄ CO).

Modified polyesters are also very useful as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol, the end groups being predominantly sulfobenzoates and secondary ethylene glycol and / or Alternatively, it consists of a monoester of propanediol. The purpose is to obtain a polymer that is capped at both ends with sulfobenzoate groups, and in this context most of the above copolymers are endcapped with sulfobenzoate groups. However, some copolymers are not fully capped, so their end groups may consist of monoesters of ethylene glycol and / or propane-1,2-diol,
"Secondarily" consists of such species. The polyester selected here is about 46% by weight dimethyl terephthalic acid, about 1%.
6% by weight of propane-1,2-diol, about 10% by weight of ethylene glycol,
It contains about 13% by weight dimethyl sulfobenzoic acid and about 15% by weight sulfoisophthalic acid and has a molecular weight of about 3000. Polyesters and their methods of manufacture are described in detail in EPA 311 and 342.

Enzyme stabilizers useful herein depend on characteristics such as the enzyme used and the active ingredient. However, preferred examples of enzyme stabilizers useful herein are calcium ions, borates, borate diols, propylene glycols, short chain carboxylic acids, boronic acids and mixtures thereof. It is well known in the art that free chlorine in tap water rapidly inactivates the enzymes contained in detergent compositions. Therefore, when a chlorine scavenger such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine is used in the formulation at a level of 0.1% or more by weight of the total composition, an improved through-the-wash of detergent enzyme ( throuth the wash) Provides stability. Compositions comprising chlorine scavengers are described in European Patent Application 928700188.6, filed January 31, 1992.

Alkoxylated polycarboxylates, such as those made from polyacrylates, are useful herein for exerting additional fat removal performance. Such materials are described in WO 91/08281 and PCT90, incorporated herein by reference.
/ 01815, page 4 et seq. Chemically, these substances are 7-8
It comprises a polyacrylate with one ethoxy side chain per acrylate unit. Side chain of the formula _- consists _{(CH 2 CH 2 O) m} (CH 2) n CH 3, wherein m is 2 to 3, n is 6-12. The side chains are esterified to the polyacrylate "backbone" forming a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylate is about 0.05 to about 10% by weight of the composition.

The following examples are meant to illustrate the compositions of the invention and are not necessarily meant to limit or limit the scope of the invention. In detergent compositions, enzyme levels are expressed as pure enzyme by weight of total composition, unless otherwise noted detergent ingredients are expressed by weight of total composition.

Examples The following examples further describe and exemplify the preferred embodiments within the scope of the present invention. The examples are given for illustrative purposes only and should not be construed as limitations of the invention, many variations of which are possible without departing from the spirit and scope thereof.

Example 1 Liquid Hard Surface Cleaning Composition Example No. Ingredients A B C D E F G invention Protease 0.001 0.005 0.01 0.02 0.03 0.01 0.02 EDA * - - - 2.90 2.90 - - citrate - - - - - 2.90 2.90 C 13 linear alkyl benzene sulfonate (LAS) - 1.95 - 1.95 - 1.95-Alkylsulfate (AS) 2.00-2.20-2.20-2.20 Alkyl polyoxyethylene sulphate (AES) 2.00-2.20-2.20-2.20 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 CaCl ₂ ) ‐ ‐ 0.40 0.40 0.40 ‐ ‐ Water and others up to 100% ^* Na ₄ ethylenediamine diacetic acid ^** Diethylene glycol monohexyl ether

2. Dishwashing composition example 2 Dishwashing composition example No. Component ABCD 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-methylundecanoic acid 4.50 4.50-4.50 4.50-C ₁₂ Alcohol ethoxylate (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 Hydrotrope 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 MgCl ₂ ) 0.20 0.20 0.20 0.20 0.20 0.20 Ca ⁺⁺ (CaCl ₂ As)) 0.40 0.40 0.40 0.40 0.40 0.40 Water and other balance up to 100% ^* C ₁₆ -C ₁₈ alkyl N-methylglucamide

3. Fabric Cleaning Composition Granular Fabric Cleaning Composition The granular fabric cleaning composition of the present invention comprises an effective amount of one or more protease enzymes, preferably from about 0.001 to about 10% by weight of the composition, more preferably about 0. 0
It contains from 05 to about 5%, more preferably from 0.01 to about 1% active protease enzyme (see US Pat. No. 5,679,630 Examples). Example 3 Granular Fabric Cleaning Composition Example No. Ingredients A B C D present invention Protease 0.01 0.02 0.02 0.02 C ₁₃ linear alkyl benzene sulfonate 22.00 22.00 22.00 (as sodium tripolyphosphate) 22.00 phosphates 23.00 23.00 23.00 23.00 Sodium 23.00 23.00 23.00 23.00 Sodium silicate carbonate 14.00 14.00 14.00 14.00 Zeolite 8.20 8.20 ^{8.20 8.20 DTPA * 0.40 - 0.40 -} ( as _{^{CaCl 2) Ca ++) 0.40 0.40}} 0.40 0.40 sodium sulfate 5.50 5.50 5.50 5.50 water balance to 100% ^* diethylenetriaminepentaacetic acid

Example 4 Granular Fabric Cleaning Composition Example No. Ingredients A B C D present invention Protease 0.01 0.02 0.007 0.005 C ₁₂ alkyl benzene sulphonate 12.00 12.00 12.00 12.00 Zeolite ^{A (1~10μm) * 26.00 26.00 26.00} 26.00 C 12 -C 14 secondary (2,3) alkyl sulfate Na salt 5.00 5.00 5.00 (as CaCl ₂₎ 5.00 sodium citrate 5.00 5.00 5.00 5.00 fluorescent whitening agent 0.10 0.10 0.10 0.10 sodium 17.00 17.00 17.00 17.00 Ca ⁺⁺ sulfate) 0.40 0.40 0.40 0.40 filler, water, until other 100% balance ^* 0.1 The formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ having a main particle size in the range of -10 μm.
27H ₂ O hydrated sodium aluminosilicate (weight displayed on an anhydrous basis)

Example 5 Liquid Fabric Cleaning Composition Example No. Ingredients _{A B DI H 2 O 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 sulfate 1. 75-DTPA 0.50 1.00 FWA Premix (Br15 / MEA / NI 23-9) 0.15 0.15 NaC25AE1.80S 23.50-AE3S (H) -4.00 C11.8HLAS ^* 3.00 14 1.00 Neodol 2.00 6.00 EtOH 0.50 2.00 Ca ⁺⁺ (as CaCl ₂ )) 0.10 0.10 Borax Premix (borax / MEA / Pdiol / citric acid) 2.50-ho acid - 1.00 C10 amidopropyl dimethylamine 1.50 - TEPA105 ^** 1.20 - pigment 0.0040 0.0015 cellulase 0.053 0.20 amylase 0.15 0.20 present invention protease 0.0 0.05 water and to other 100% balance ^* HLAS: acid form of linear alkyl benzene sulphonate (synthetic anionic ^surfactant) ** TEPA: tetraethylene pentamine

Example 6 Solid Fabric Cleaning Composition Example No. Ingredients A B C D present invention Protease 0.01 0.03 0.01 0.02 C ₁₂ -C ₁₆ alkyl sulfates _{Na 20.0 20.0 20.0 20.00 C 12 -C} 14 N- methyl glucamide 5.0 5.0 5.0 5.00 C ₁₁ -C ₁₃ alkylbenzene sulfonate 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 to 10 μ) 5.0 5.0 5.0 5.00 Carboxymethyl cellulose 0.2 0.2 0.2 0.20 Polyacrylate (MW1400) 0.2 0.2 0.2 0.20 Coconut monoethanolamide 5.0 5.0 5.0 5.00 Whitening agent, fragrance 0.2 0.2 0.2 0.20 CaSO ₄ 1.0 1.0 1.0 1.00 MgSO ₄ 1.0 1.0 1.0 1.00 Water 4.0 4.0 4.0 4.00 Filler ^* Up to 100% ^{* From} convenient substances such as CaCO ₃ , talc, clay, silicate, etc. You can choose

The compositions of the present invention may be suitably manufactured by any process selected by the practitioner, non-limiting examples of which are US Pat.
5,691,297, US 5 of Welch et al., Issued November 12, 1996.
, 574, 005, US of Dinniwell et al., Issued October 29, 1996.
5, 569, 645, Del Greco et al., U, issued October 15, 1996.
S5,565,422, US5 of Capeci et al., Issued May 14, 1996.
, 516, 448, US Pat. No. 5,48, Capeci et al., Issued February 6, 1996.
9,392, US Pat. No. 5,486, Capeci et al., Issued Jan. 23, 1996.
303, all of which are incorporated herein by reference.

In addition to the above examples, the cleaning compositions of the present invention can be formulated into any suitable laundry detergent composition, non-limiting examples of which are US 5 of Baeck et al., Issued Oct. 21, 1997. , 679, 630, issued October 15, 1996, Watson et al., US 5,565,145, issued December 26, 1995.
Fredj et al., US 5,478,489, issued on 28 November 1995.
dj et al., US 5,470,507, Panand published November 14, 1995.
iker et al. US Pat. No. 5,466,802, Fred, issued October 24, 1995.
US Pat. No. 5,460,752, Fredj et al., US 5,458,810, issued October 17, 1995, Fredj et al., US 5,458,809, 1994, issued October 17, 1995. Huber's US issued on the 22nd of March
5,288,431, all of which are incorporated herein by reference.

It will be appreciated that the examples and embodiments described herein are for illustration purposes only, and that various modifications or changes will be suggested to those skilled in the art with reference thereto without departing from the scope of the invention. To be understood.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, SD, SL, SZ, UG, ZW), E A (AM, AZ, BY, KG, KZ, MD, RU, TJ , TM), AE, AL, AM, AT, AU, AZ, BA , BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, G B, GD, GE, GH, GM, HR, HU, ID, IL , IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, M G, MK, MN, MW, MX, NO, NZ, PL, PT , RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, V N, YU, ZA, ZW (72) Inventor Golam, Falk, Hahn             3-1-5 Naka, Koyo-cho, Higashinada-ku, Kobe City, Hyogo Prefecture             Number 1-1703 (72) Inventor Ryohei Otani             7-19 Uedanaka-cho, Nishinomiya-shi, Hyogo F-term (reference) 4H003 AB01 AB19 AB31 AC01 AC14                       AD01 AE01 DA01 DA02 DA05                       DA17 EA08 EA09 EA10 EA11                       EA15 EA16 EA28 EB08 EB16                       EC01 EC02 EC03 ED01 ED29                       EE01 EE05

Claims (10)

[Claims] 1. A. Measure the primary cleavage rate; b. Measuring the rate of secondary cleavage; c. Calculate the ratio of primary cleavage rate to secondary cleavage rate; d. A detergent composition comprising a protease selected by a process comprising the step of selecting a protease having 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. 2. The protease has a primary cleavage rate of 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. Detergent composition. 3. The detergent composition according to claim 1, wherein the protease is derived from Bacillus subtilis. 4. A. About 0.01 to about 60% by weight of a detergent surfactant, b. From about 5 to about 80% by weight detergent builder, and c. a. Measure the primary cleavage rate; b. Measuring the rate of secondary cleavage; c. Calculate the ratio of primary cleavage rate to secondary cleavage rate; d. About 0.0001 to about 5 proteases selected by a process comprising the step of selecting a protease having 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.
A detergent composition comprising by weight. 5. The surfactant is selected from the group consisting of anionic, cationic, amphoteric, nonionic surfactants and mixtures thereof, the detergent builder being phosphate, pyrophosphate, orthophosphate, tripolyphosphate, A detergent composition according to claim 4 selected from the group consisting of higher phosphates, alkali metal carbonates and bicarbonates, alkali silicates, aluminosilicates, polycarboxylates, layered silicates, citrates and mixtures thereof. 6.   The detergent composition of claim 4, further comprising bleach. 7. The detergent composition according to claim 6, wherein the bleach is selected from the group consisting of peroxygen, perborate, percarbonate, perphosphate and mixtures thereof. 8. The detergent composition according to claim 4, further comprising an additional enzyme selected from the group consisting of cellulase, amylase, lipase, phospholipase, other proteases, peroxidase and mixtures thereof. 9. a. Measure the primary cleavage rate; b. Measuring the rate of secondary cleavage; c. Calculate the ratio of primary cleavage rate to secondary cleavage rate; d. A method for selecting proteases, which comprises selecting a protease having 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. A protease having a primary cleavage rate higher than 1200 μg / min / μg is selected,
10. The method of selecting a protease according to claim 9, wherein the ratio of the primary cleavage rate to the secondary cleavage rate is about 50: 1 to about 130: 1.