WO1997043386A1

WO1997043386A1 - Detergent compositions comprising improved amylases, cellulase and cationic surfactant

Info

Publication number: WO1997043386A1
Application number: PCT/US1997/008104
Authority: WO
Inventors: Chun Hua Huang; Kaori Minamikawa; Susumu Murata
Original assignee: The Procter & Gamble Company
Priority date: 1996-05-15
Filing date: 1997-05-13
Publication date: 1997-11-20
Also published as: MA24180A1; CA2254067A1; AU3065697A; BR9710440A; JPH11511785A; EP0912688A1

Abstract

Disclosed is a detergent composition comprising a specific amylase enzyme at a level from about 0.005 % to about 0.05 % pure enzyme, typically by weight of total composition, a cellulase, typically at a level from about 0.002 % to about 0.02 % pure enzyme by weight of total composition, and a cationic surfactant.

Description

DETERGENT COMPOSITIONS COMPRISING IMPROVED AMYLASES, CELLULASE AND CATIONIC SURFACTANT

TECHNICAL FIELD The present invention relates to detergent compositions comprising certain levels of specific amylase enzymes, cellulase enzyme and cationic surfactant which improve cleaning and stain removal performances in hard surface cleaning, dishwashing and laundry.

BACKGROUND OF THE INVENTION

Amylase enzymes have long been recognized in dishwashing, hard surface cleaning and laundry compositions to provide the removal of starchy food residues or starchy films from dishware, flatware, glasses and hard surfaces or to provide cleaning performance on starchy soils as well as other soils typically encountered in laundry applications.

WO/94/02597, Novo Nordisk A/S published February 03, 1 994, describes cleaning compositions which incorporate mutant amylases. See also WO/94/1 8314, Genencor, published August 1 8, 1 994 and WO/95/10603, Novo Nordisk A/S, published April 20, 1 995.

Other amylases known for use in cleaning compositions include both α- and β-amylases. α-Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91 /00353; FR 2,676,456; EP 285, 1 23; EP 525,610; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo).

Recently new amylases have been identified and are described in WO/95/26397, Novo Nordisk A/S, published October 05, 1 995, disclosing an α-amylase having a specific activity at least 25% higher than the specific activity of Termamyl^® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 1 0. Variants of these new amylases demonstrating at least one of the following properties relative to the parent enzymes : 1 ) improved thermal stability, 2) oxidation stability and 3) reduced calcium ion dependency properties Examples of other desirable improvements or modifications of properties (relative to the parent-α- amylase) which may be achieved with a variant according to the present invention are ^* increased stability and/or α-amylolytic activity at neutral to relatively high pH values, increased α-amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for α-amylase variant to the pH of the medium, have been described in the co-pending application by Novo Nordisk PCT/DK96/00056. Such newly developed amylases - hereinafter referred as "specific amylase enzymes" - are generally used in detergent compositions at levels of 0.0001 to 0.1 % pure enzyme by weight of the total composition.

Also optimized applications of such specific amylase enzymes into detergent compositions at levels of 0.0001 8% to 0.060% pure enzyme by weight of the total composition have been described in the application by Procter & Gamble PCT/US96/3276. Further, the combination of such specific amylase and cellulase has been described in the application by Procter & Gamble PCT/US96/3276 and PCT/US96/7090. However, the microfibrils that anchor the strains to the fabric need to be removed more effectively than the combination of such specific amylase and cellulase.

Based on the foregoing, there is a need for a laundry detergent composition which removes effectively the microfibrils that anchor the stains to the fabric after such specific amylase enzymes remove the starch from the fibre.

SUMMARY OF THE INVENTION The present invention relates to detergent compositions comprising

(1 ) a specific amylase enzyme at a level from about 0.005% to about 0.05% pure enzyme by weight of the total composition, (2) from about 0.002% to about 0.02% pure enzyme by weight of total composition of cellulase, and (3) a cationic surfactant. Such a detergent composition satisfies the need for a detergent composition which removes effectively the microfibrils that anchor the stains to the fabric after such specific amylase enzymes remove the starch from the fibre. These and other features, aspects and advantages of the present 75 invention will become evident to those skilled in the art from a reading of the present disclosure.

DETAILED DESCRIPTION OF THE INVENTION While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention 80 will be better understood from the following description.

All percentages are by weight of total composition unless specifically stated otherwise.

All ratios are weight ratios unless specifically stated otherwise. As used herein, "comprising" means that other steps and other 85 ingredients which do not affect the end result can be added. This term encompasses the terms "consisting of" and "consisting essentially of" .

All percentages of enzymes are pure enzyme level (as active protein level) of total composition unless specifically stated otherwise.

All cited references are incorporated herein by reference in their 90 entireties. Citation of any reference is not an admission regarding any determination as to its availability as prior art to the claimed invention. Specific Amylase Enzymes

An essential component of the detergent compositions of the present invention is a specific amylase enzyme. Such specific amylase enzymes

95 include those described in WO95/26397 and in co-pending application by

Novo Nordisk PCT/DK96/00056. If the composition comprises more than

0.05% pure enzyme by weight of total composition of such specific amylase enzymes, it is not economical. If the composition comprises less than 0.005% pure enzyme by weight of total composition of such specific

100 amylase enzymes, enough cleaning performance is not expected. These enzymes are incorporated into detergent compositions typically at a level from about 0.005% to about 0.05% pure enzyme by weight of the total composition, more preferably from 0.005% to 0.01 % pure enzyme by weight of total weight composition.

105 Specific amylase enzymes for use in the detergent compositions of the present invention therefore include :

(a) α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl^® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 1 0, measured by the Phadebas^® α-amylase activity assay. Such Phadebas^® α-amylase activity assay is described at pages 9-1 0, WO95/26397.

(b) α-amylases according (a) comprising the amino sequence shown in SEQ ID No. 1 or an α-amylase being at least 80% homologous with the amino acid sequence shown in SEQ ID No.1 . (c) α-amylases according (a) comprising the amino sequence shown in SEQ ID No.2 or an α-amylase being at least 80% homologous with the amino acid sequence shown in SEQ ID No.2.

(d) α-amylases according (a) comprising the following amino sequence in the N-terminal : His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln- Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp (SEQ ID No.3) or an α-amylase being at least 80% homologous with the amino acid sequence shown (SEQ ID

No.3) in the N-terminal.

A polypeptide is considered to be X% homologous to the parent amylase if a comparison of the respective amino acid sequences, performed via algorithms, such as the one described by Lipman and Pearson in Science

227, 1 985, p. 1435, reveals an identity of X%

(e) α-amylases according (a-d) wherein the α-amylase is obtainable from an alkalophilic Bacillus species.

(f) α-amylase according to (e) wherein the amylase is obtainable from any of the strains NCIB 1 2289, NCIB 1 251 2, NCIB 1 251 3 and DSM

935.

In the context of the present invention, the term "obtainable from" is intended not only to indicate an amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced in an host organism transformed with said DNA sequence.

(g)α-amylase showing positive immunological cross-reactivity with antibodies raised against an α-amylase having an amino acid sequence corresponding respectively to SEQ ID No.1 , ID No.2 or ID No.3. (h) Variants of the following parent α-amylases which (i) have one of the amino acid sequences shown in SEQ ID No. 1 , ID No.2 or ID No.4 respectively, or (ii)displays at least 80% homology with one or more of said amino acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an α-amylase having one of said amino acid sequences, and/or is encoded by a DNA sequence which hybridizes with the same probe as a DNA sequence encoding an α-amylase having one of said amino acid sequence; in which variants :

1 . at least one amino acid residue of said parent α-amylase has been deleted; and/or 2. at least one amino acid residue of said parent α-amylase has been replaced by a different amino acid residue; and/or

3. at least one amino acid residue has been inserted relative to said parent α -amylase; said variant having an α-amylase activity and exhibiting at least one of the following properties relative to said parent α-amylase increased thermostability, increased stability towards oxidation, reduced Ca ion dependency, increased stability and/or α-amylolytic activity at neutral to relatively high pH values, increased α-amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for α-amylase variant to the pH of the medium.

Said variants are described in the co-pending patent application PCT/DK96/00056. Cellulase enzyme

The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A- 2.095.275 and DE-OS-2.247.832. Examples of such cellulases are cellulases produced by a strain of

Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1 800.

Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 41 5 amino acids. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91 202879.2, filed November 6, 1 991 (Novo). The cellulases are used to remove the microfibrils that anchor the stains to the fabric. If the composition comprises more than 0.02% pure enzyme by weight of total composition of cellulose, it is not economical and it may cause fabric damage. If the composition comprises less than 0.002% pure enzyme by weight of total composition of cellulase, enough microfibrils removal effect is not expected. The compositions of the present invention comprises typically from about 0.002% to about 0.02%,

185 preferably from about 0.002% to about 0.005% pure enzyme by weight of total composition of cellulase. Cationic surfactant

Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-

190 chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltπmethylammonium halogenides, and those surfactants having the formula ^•

[R²(OR³)y][R⁴(OR³)_y]₂R⁵N + X- wherein R2 ,s an alkyl or alkyl benzyl group having from about 8 to about

195 1 8 carbon atoms in the alkyl chain, each R³ is selected from the group consisting of -CH2CH2-, -CH₂CH(CH₃)-, -CH2CH(CH2OH)-, -CH₂CH₂CH2-, and mixtures thereof; each R⁴ IS selected from the group consisting of C -| - C4 alkyl, C 1 -C4 hydroxyalkyl, benzyl ring structures formed by joining the two R⁴ groups, -CH2CHOH-CHOHCOR⁶CHOHCH2OH wherein R⁶ is any

200 hexose or hexose polymer having a molecular weight less than about 1 000, and hydrogen when y is not 0; R IS the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R^ IS not more than about 1 8; each y is from 0 to about 10 and the sum of the y values is from 0 to about 1 5, and X is any compatible anion.

205 Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :

Rl R2^R3^R4^{N + x"} M wherein R-| is CQ-C ^ Q alkyl, each of R2, R3 and R4 is independently C1 -C4 210 alkyl, C1 -C4 hydroxy alkyl, benzyl, and -(C2H4θ)_xH where x has a value from 2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl.

The preferred alkyl chain length for R -| is C i 2~C l 5 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm 215 kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R2, P>3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions. Examples of suitable quaternary ammonium compounds of formulae (i) for 220 use herein are : coco alkyl trimethyl ammonium chloride or bromide; coco alkyl methyl di[hydroxyethyl] ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; 225 C-1 2-1 5 a'kyl dimethyl hydroxyethyl ammonium chloride or bromide; coco alkyl dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulfate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide; 230 choline esters (compounds of formula (i) wherein R-- is

CH2-CH2-O-C-C 1 2-I 4 alkyl and R2R3R4 are methyl) .

I I 0

Other cationic surfactants include di-alkyl imidazolines. 235 Other cationic surfactants also include quaternary ammonium surfactant suitable for the present invention having the formula (I):

Formula I

240 whereby R 1 is a short chainlength alkyl (C6-C 1 0) or alkylamidoalkyl of the formula (II) :

Formula II y is 2-4, preferably 3.

245 whereby R2 is H or a C1 -C3 alkyl, whereby x is 0-4, preferably 0-2, most preferably 0, whereby R3, R4 and R5 are either the same or different and can be either a short chain alkyl (C1 -C3) or alkoxylated alkyl of the formula III, whereby X^" is a counterion, preferably a halide, e.g. chloride or

250 methylsulfate.

Formula III R6 is C1 -C4 alkyl and z is 1 or 2.

Preferred quat ammonium surfactants are those as defined in formula

255 I whereby

R-j is Cs alkyl, C -J O alkyl or mixtures thereof, x = 0, R3, R4 = CH3 and R5 = CH2CH2OH.

Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1 980 and in European

260 Patent Application EP 000,224. Cationic surfactant is used in order to enhance cleaning performance and stabilize enzyme. If the composition comprises more than 25% by weight of total composition of cationic surfactants, it is not economical. If the composition comprises less than 0.2% by weight of total composition of cationic surfactants, enough

265 cleaning performance is not expected.

The laundry detergent compositions of the present invention typically comprise from about 0.2% to about 25 %, preferably from about 1 % to about 8% by weight of such cationic surfactants. Detergent components

270 The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.

275 The compositions of the invention may for example, be formulated as hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabrics, rinse added fabric softener compositions.

When formulated as compositions suitable for use in a laundry

280 machine washing method, the compositions of the invention preferably contain both a surfactant other than cationic surfactant and a builder compound and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil

285 suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents, as additional detergent components.

The compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or 290 boost the performance of conventional detergent compositions.

The density of the granular laundry detergent compositions herein ranges from 400g to 1 200g/liter, preferably 600g to 950g/liter of composition measured at 20°C.

The "compact" form of the granular laundry detergent compositions 295 herein is best reflected by high density (e.g. 600g to 950g/liter) and, in terms of composition, by a reduced amount of inorganic filler salt. Inorganic filler salts are conventional ingredients of detergent compositions in powder form. In conventional detergent compositions, the filler salts are present in substantial amounts, typically 1 7-35% by weight of the total 300 composition.

In the compact compositions, the filler salt is present in amounts not exceeding 1 5% of the total composition, preferably not exceeding 1 0%, most preferably not exceeding 5% by weight of the composition.

The inorganic filler salts, such as meant in the present compositions 305 are selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides.

A preferred filler salt is sodium sulphate.

Liquid detergent compositions according to the present invention can also be in a "concentrated form", in such case, the liquid detergent 310 compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents.

Typically the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition. 315 Surfactant other than cationic surfactants

The detergent compositions according to the present invention can further comprise one or more surfactants other than cationic surfactants wherein the surfactants can be selected from the group consisting of nonionic surfactants, anionic surfactants, ampholytic surfactants,

320 zwitterionic surfactants and semi-polar surfactants.

The additional surfactants are typically present at a level of from 0.1 % to 60% by weight. More preferred levels of incorporation are 1 % to 35% by weight, most preferably from 1 % to 20% by weight of laundry compositions in accord with the invention.

325 The surfactants are chosen to be compatible with enzyme components present in the composition.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide

330 condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an

335 amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 1 5 moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal^M CO-630, marketed by the GAF Corporation; and Triton™ X-45, X- 1 1 4, X- 100 and X-102, all marketed by the Rohm & Haas Company. These

340 surfactants are commonly referred to as alkylphenol alkoxylates (e.g , alkyl phenol ethoxylates).

The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the

345 present invention. The alkyl chain of the aliphatic alcohol can either 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 an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 1 0 to about 1 8 carbon atoms,

350 with from about 2 to about 1 0 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products. Examples of commercially available nonionic surfactants of this type include Tergitol^M 1 5-S-9 (the condensation

355 product of C -* -_j -C i 5 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C -| 2"C i 4 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol^M 45-9 (the condensation product of C14-C 1 5 linear alcohol with 9 moles of ethylene oxide), 360 NeodolTM 23-3 (the condensation product of C 1 2-C 1 3 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45^.7 (the condensation product of C14-C 1 5 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of C 1 4-C 1 5 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, Kyro^M -=QB (the

365 condensation product of C 1 3-C 1 5 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA O3O or O5O (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-1 1 and most preferred from 8-1 0.

370 Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysacchaπdes disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1 986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 1 6 carbon atoms and a polysacchaπde, e.g. a polyglycoside,

375 hydrophilic group containing from about 1 .3 to about 10, preferably from about 1 .3 to about 3, most preferably from about 1 .3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is

380 attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside). The mtersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units. The preferred alkylpolyglycosides have the formula

385 R²O(C_nH2_nO)t<g'VCθsyl)_x wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 1 0 to about 1 8, preferably from about 1 2 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,

390 preferably 0; and x is from about 1 .3 to about 1 0, preferably from about 1 .3 to about 3, most preferably from about 1 .3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -

395 position). The additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1 500 to about 1 800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially-available Pluronic^M surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 1 1 ,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic^M compounds, marketed by BASF.

Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C8-C 1 4 alkyl phenol ethoxylates having from 3 to 1 5 ethoxy groups and Cs-Ci s alcohol ethoxylates (preferably C -| o avg.) having from 2 to 1 0 ethoxy groups, and mixtures thereof.

Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula. R2 - C - N - Z

I I I

435 O R ¹ wherein R ^ is H, or R ^ is C1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative

440 thereof. Preferably, R^ is methyl, R2 is a straight C-j 1 - 1 5 alkyl or C i 6_ι s alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.

When included in such laundry detergent compositions, the nonionic

445 surfactant systems of the present invention act to improve the greasy/oily stain removal properties of such laundry detergent compositions across a broad range of laundry conditions.

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants which are water soluble salts or acids of the formula

450 RO(A)_mSO3M wherein R is an unsubstituted C 1 0-C24 alkyl or hydroxyalkyl group having a C -^* 0"C24 alkyl component, preferably a C1 2-C20 alkyl or hydroxyalkyl, more preferably C -| 2"Cι s alkyl ^or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H

455 or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted- ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations

460 and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C12-C1 8 alkyl polyethoxylate ( 1 .0) sulfate (Ci 2" C-| sE( 1 .0)M), C 1 2-C1 8 alkyl polyethoxylate (2.25) sulfate (C 1 2-

465 C-| 8E(2.25)M), C12-C18 ^a|M polyethoxylate (3.0) sulfate (C 1 2- C -| 8^E(3.0)M), and C1 2-C1 8 alkyl polyethoxylate (4.0) sulfate (C 1 2- C-| 8E(4.0)M), wherein M is conveniently selected from sodium and potassium. Other suitable anionic surfactants to be used are alkyl ester sulfonate 470 surfactants including linear esters of C8-C20 carboxylic acids (i.e. , fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 ( 1 975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc. 475 The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:

0

I I

480 R³ - CH - C - OR⁴

SO3M wherein R³ is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R⁴ is a C -\ -CQ hydrocarbyl, preferably an alkyl, or combination

485 thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R³ is C 10-C 1 6 alkyl, and R⁴ is methyl, ethyl or

490 isopropyl. Especially preferred are the methyl ester sulfonates wherein R³ is C -ι o-C -1 6 alkyl.

Other suitable anionic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C-| o~C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl

495 having a C 10-C2O ^a"^<V' component, more preferably a C 1 2-C 1 8 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl

500 piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) . Typically, alkyl chains of C 1 2-C 1 6 are preferred for lower wash temperatures (e.g. below about 50°C) and C -| 6- 1 8 ^a'ky' chains are preferred for higher wash temperatures (e.g. above about 50° C).

505 Other suitable anionic surfactants include alkylbenzene sulfonates. Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and

510 triethanolamine salts) of soap, C8-C22 primary of secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1 ,082, 1 79, C8-C24 alkylpolyglycolethersulfates (containing up to 1 0 moles of ethylene

515 oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N- acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C -| 2"C i 8 monoesters)

520 and diesters of sulfosuccinates (especially saturated and unsaturated CQ- C12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic πonsulfated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2θ)|_<-

525 CH2COO-M + wherein R is a C8-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as 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

530 Detergents" (Vol. I and II by Schwartz, Perry and Berch) . A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1 975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference). If the composition comprises more than 40% by weight of total composition of anionic

535 surfactants, it is not economical. If the composition comprises less than 1 % by weight of total composition of anionic surfactants, enough cleaning performance is not expected. When included therein, the laundry detergent compositions of the present invention typically comprise from about 1 % to about 40%, preferably from about 3% to about 20% by weight of such

540 anionic surfactants. The detergent composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines Suitable primary amines for use herein include amines according to the

545 formula R-|NH2 wherein R-j is a C5-C12, preferably CR-CIO ^a|M chain or R4X(CH2)rv ^{x ιs} -0-,-C(0)NH- or -NH-_; R4 is a C6-C12 alkyl chain n is between 1 to 5, preferably 3. R-] alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.

550 Preferred amines according to the formula herein above are n-alkyl amines Suitable amines for use herein may be selected from 1-hexylamιne, 1- octylamine, 1-decylamιne and laurylamine Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl- oxypropylamine, lauryl amido propylamine and amido propylamine.

555 Suitable tertiary amines for use herein include tertiary amines having the formula R1R2R3N wherein R1 and R2 are C---C8 alkylchams or

R5

— (CH₂ CH θ)χH

R3 is either a CR-CI2, preferably CQ-C^Q alkyl chain, or R3 is R4X(CH2)n< whereby X is -0-, -C(0)NH- or -NH- R4 is a C4-C12, ^{n ιs} between 1 to 5, 560 preferably 2-3. R5 is H or C1-C2 alkyl and x is between 1 to 6.

R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.

Preferred tertiary amines are R1R2R3N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or ϊ> (CH₂ — CH ())χH

565 where R5 is H or CH3 and x = 1-2.

Also preferred are the amidoamines of the formula:

0 Ri — C-NH — ( CH₂ )— N— ( R₂ )

'n

wherein R-j is CQ-C]2 a'M; ^{n ιs} 2-4, 570 preferably n is 3; R2 and R3 is C1-C4.

Most preferred amines of the present invention include 1-octylamιne, 1-hexylamιne, 1-decylamιne, 1-dodecylamιne_rC8-10oxypropylamιne, N coco 1-3dιamιnopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles

575 propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-1 0 amidopropyldimethylamine and C1 0 amidopropyldimethylamine.

The most preferred amines for use in the compositions herein are 1 - hexylamine, 1 -octylamine, 1 -decylamiπe, 1 -dodecylamine. Especially

580 desirable are n-dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.

The laundry detergent compositions of the present invention may also contain, ampholytic, zwitterionic, and semi-polar surfactants, as well as the

585 nonionic and/or anionic surfactants other than those already described herein.

Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or

590 aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 1 8 carbon atoms, and at least one contains an anionic water- solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No.

595 3,929,678 to Laughlin et al., issued December 30, 1 975 at column 1 9, lines 1 8-35, for examples of ampholytic surfactants.

When included therein, the laundry detergent compositions of the present invention typically comprise from 0.2% to about 1 5%, preferably from about 1 % to about 10% by weight of such ampholytic surfactants.

600 Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No.

605 3,929,678 to Laughlin et al., issued December 30, 1 975 at column 1 9, line 38 through column 22, line 48, for examples of zwitterionic surfactants.

When included therein, the laundry detergent compositions of the present invention typically comprise from 0.2% to about 1 5%, preferably from about 1 % to about 10% by weight of such zwitterionic surfactants. 610 Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 1 0 to about 1 8 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine

615 oxides containing one alkyl moiety of from about 1 0 to about 1 8 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 1 8 carbon atoms and a moiety selected from the group consisting

620 of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

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

O

625 t-

R³(OR⁴)xN(R5)2 wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms

630 or mixtures thereof; x is from 0 to about 3; and each R^ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R-5 groups can be attached to each other, e.g. , through an oxygen or nitrogen atom, to form a ring structure.

635 These amine oxide surfactants in particular include C -| 0"C i 8 ^a"^<y' dimethyl amine oxides and C8-C 1 2 alkoxy ethyl dihydroxy ethyl amine oxides.

When included therein, the laundry detergent compositions of the present invention typically comprise from 0.2% to about 1 5%, preferably

640 from about 1 % to about 10% by weight of such semi-polar nonionic surfactants.

Optional detergent ingredients : A.Dispersant

It has been found that combinations of specific amylase enzyme

645 according to the present invention with a dispersant enhance the overall cleaning and stain removal performance. It has been found that the use of low molecular weight polymeric dispersant in the presence of an α-amylase gives a significant improvement in starch cleaning. Increasing enzyme concentration or dispersant alone do

650 not give improved starch cleaning at lower temperature. However the addition of a dispersant to the α-amylase boosts significantly the starch removal at low temperature, enhancing the removal of the hydrolysed fragments of the starch molecules.

Suitable water-soluble organic salts are the homo- or co-polymeric

655 acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.

Polymers of this type are disclosed in GB-A- 1 , 596, 756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic

660 anhydride, such copolymers having a molecular weight of from 1 ,000 to 1 00,000.

Especially, copolymer of acrylate and methylacrylate such as the 480N having a molecular weight of 4000, at a level from 0.5-20% by weight of composition can be added in the detergent compositions of the

665 present invention.

B. Other detergent enzymes

The detergent compositions of the present invention can in addition to specific amylase enzymes and cellulase further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.

670 Said enzymes include enzymes selected from, hemicellulases, peroxidases, proteases, gluco-amylases, other amylases, xylanases, lipases, esterases, cutinases, pectinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases chondroitinase, laccase or mixtures thereof.

675 A preferred combination is a cleaning composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.

Peroxidase enzymes are used in combination with oxygen sources,

680 e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as

685 chloro- and bromo-peroxidase.

Peroxidase-contaming detergent compositions are disclosed, for example, in PCT International Application WO 89/09981 3 and in European Patent application EP No. 91 202882.6, filed on November 6, 1 991 .

Said peroxidases are normally incorporated in the detergent

690 composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.

It has been found that combination of specific amylase enzyme according to the present invention with protease, enhance the overall cleaning and stain removal performance.

695 Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8- 1 2, developed and sold as ESPERASE^® by Novo Industries A/S of Denmark, hereinafter " Novo" . The

700 preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 to Novo. Other suitable proteases include ALCALASE^®, DURAZYM^® and SAVINASE^® from Novo and MAXATASE^®, MAXACAL®, PROPERASE^® and MAXAPEM® (protein engineered Maxacal) from Gist- Brocades. Proteolytic enzymes also encompass modified bacterial serine

705 proteases, such as those described in European Patent Application Serial Number 87 303761 .8, filed April 28, 1 987 (particularly pages 1 7, 24 and 98), and which is called herein "Protease B", and in European Patent Application 1 99,404, Venegas, published October 29, 1 986, which refers to a modified bacterial serine protealytic enzyme which is called "Protease

710 A" herein. Suitable is what is called herein "Protease C" , which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 1 04, serine replaced asparagine at position 1 23, and alanine replaced threonine at position 274. Protease C is described in EP 9091 5958:4, corresponding to WO

715 91 /06637, Published May 1 6, 1 991 . Genetically modified variants, particularly of Protease C, are also included herein.

A preferred protease referred to as "Protease D" is a carbonyl hydrolase variant having an ammo acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different

720 ammo acid for a plurality of ammo acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more ammo acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, + 107, +123, +27, +105, +109, +126, +128, +135, +156, +166,

725 +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, + 265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677, filed October 13,

730 1994.

Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP^® described in WO91/02792 and their variants described in WO 95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338

735 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-hke protease

740 for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516200 by Unilever.

The proteolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1%

745 pure enzyme by weight of the composition.

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeπ ATCC 19.154, as

750 disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as

755 "Amano-P". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases

760 are lipases such as M 1 Lipase^{R ar|}d Lipomax^R (Gist-Brocades) and Lipolase^R and Lipolase Ultra^R(Novo) which have found to be very effective when used in combination with the compositions of the present invention. Also suitables are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/2261 5 by Novo Nordisk and in WO 94/03578, WO 95/35381

765 and WO 96/00292 by Unilever.

Also suitable are cutinases [EC 3.1 .1 .50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant

770 Genetic System) and WO 94/14963 and WO 94/1 4964 (Unilever).

The lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.

It has been found that combination of specific amylase enzyme

775 according to the present invention with a complementary amylase, enhances the overall cleaning and stain removal performance of the detergent composition of the present invention. In particular, it has been found that the inclusion of a multiple amylase system comprising amylases with different temperature optima significantly improves the cleaning

780 performance over a broad range of temperature, especially from 40°C to 65 °C. Indeed, the specific amylases according to the present invention demonstrate improved cleaning properties at low temperature versus complementary amylases such as Termamyl. Combinations of low temperature active with high temperature active amylases is therefore

785 contemplated.

By "complementary" it is meant the addition of one or more amylase suitable for detergency purposes. Examples of complementary amylases (α and/or β) are described below. WO94/02597 and WO95/1 0603, Novo Nordisk A/S describe cleaning compositions which incorporate mutant

790 amylases. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91 /00353; FR 2,676,456; EP 285, 1 23; EP 525,61 0; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo) . Other suitable amylases are stability- 795 enhanced amylases described in W094/1 8314, and WO96/05295, Genencor and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/1 0603. Also suitable are amylases described in EP 277 21 6 (Novo Nordisk).

800 Examples of commercial α-amylases products are Purafect Ox Am^® from Genencor and Termamyl^®, Ban^® ,Fungamyl^® and Duramyl\ all available from Novo Nordisk A/S Denmark. W095/26397 describes other suitable amylases : α-amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl^® at a temperature range

805 of 25°C to 55°C and at a pH value in the range of 8 to 1 0, measured by the Phadebas^® α-amylase activity assay. Suitable are variants of the above enzymes, descπbed in W096/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in

810 W095/35382.

Preferred complementary amylases for the present invention are the amylases sold under the tradename Purafect Ox Am^R described in WO 94/1 8314, WO96/05295 sold by Genencor; Termamyl^®, Fungamyl^®, Ban^® and Duramyl^® all available from Novo Nordisk A/S and Maxamyl^® by Gist-

815 Brocades.

Said complementary amylase is generally incorporated in the detergent compositions of the present invention a level of from 0.0001 % to 2%, preferably from 0.0001 8% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.

820 Preferably a weight of pure enzyme ratio of specific amylase to the complementary amylase is comprised between 9: 1 to 1 9, more preferably between 4: 1 to 1 :4, and most preferably between 2 1 and 1 .2.

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin

825 Said enzymes are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.

It has been found that combination of specific amylase enzyme according to the present invention with a cloπne scavenger, enhance the

830 overall cleaning and stain removal performance. Suitable detergent ingredients that can be added are the enzyme oxidation scavengers which are described in the copending European patent application 9287001 8.6 filed on January 31 , 1 992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyammes.

835

C.Color care benefits

Especially preferred detergent ingredients are combinations with technologies which also provide a type of color care benefit. Examples of these technologies are metallo catalysts for color maintenance. Such

840 metallo catalysts are described in the European patent EP 0 596 184 and in the copending European Patent Application No. 94870206.3. D. Bleaching agent

It has been found that combinations of specific amylase enzyme according to the present invention with a bleach system enhance the overall

845 cleaning and stain removal performances.

Bleach systems that can be included in the detergent compositions of the present invention include bleaching agents such as anhydrous sodium perborate monohydrate, anhydrous sodium perborate tetrahydrate and percarbonate with a particle size of 400-800 microns. These bleaching

850 agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one or more bleach activators. When present oxygen bleaching compounds will typically be present at levels of from about 1 % to about 25%. In general, bleaching compounds are optional components in non-liquid formulations, e g. granular detergents

855 The bleaching agent component for use herein can be any of the bleaching agents useful for detergent compositions including oxygen bleaches as well as others known in the art.

The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.

860 One category of oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4- nonylamιno-4-oxoperoxybytyrιc acid and diperoxydodecanedioic acid. Such

865 bleaching agents are disclosed in U.S Patent 4,483,781 , U.S. Patent Application 740,446, European Patent Application 0, 1 33, 354 and U.S. Patent 4,41 2,934. Highly preferred bleaching agents also include 6- nonylamιno-6-oxoperoxycaproιc acid as described in U.S Patent 4,634,551

870 The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene-sulfonate (NOBS, described in US 4,41 2, 934), 3,5,- tnmethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 1 20, 591 ) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as

875 the active bleaching species, leading to improved bleaching effect. Also suitable activators are acylated citrate esters such as disclosed in Copending European Patent Application No. 91 870207.7.

Useful bleaching agents, including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds for use in

880 detergent compositions according to the invention are described in our co- pending applications USSN 08/1 36,626, PCT/US95/07823, W095/27772, W095/27773, W095/27774 and W095/27775.

The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of

885 generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91 202655.6 filed October 9, 1 991

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching

890 agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanmes. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanme is activated

895 and, consequently, the substrate is bleached. Preferred zinc phthalocyanme and a photoactivated bleaching process are described in U S. Patent 4,033,71 8. Typically, detergent compositions will contain about 0.025% to about 1 .25%, by weight, of sulfonated zinc phthalocyanme. E.Builder system

900 The compositions according to the present invention may further comprise a builder system. It has been found that the combination of specific amylase enzyme according to the present invention with builder component, enhance the overall cleaning and stain removal performance. Any conventional builder system is suitable for use herein including

905 aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, diethylene tπamine pentamethyleneacetate, metal ion sequestrants such as ammopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene tπamme pentamethylenephosphonic acid.

910 Though less preferred for obvious environmental reasons, phosphate builders can also be used herein.

Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.

915 Another suitable inorganic builder material is layered silicate, e.g.

SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2θ5>.

Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian

920 Patent Nos. 831 ,368, 821 ,369 and 821 ,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolhc acid, tartaric acid, tartronic acid and fumaπc acid, as well as the ether carboxylates described in German Offenlegenschnft 2,446,686, and 2,446,687 and U.S. Patent

925 No. 3,935,257 and the sulfmyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241 , lactoxysuccinates described in Netherlands

930 Application 7205873, and the oxypolycarboxylate materials such as 2-oxa- 1 , 1 ,3-propane tπcarboxylates described in British Patent No. 1 ,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccmates disclosed in British Patent No. 1 ,261 ,829, 1 , 1 ,2,2-ethane tetracarboxylates, 1 , 1 ,3,3-propane tetracarboxylates and 1 , 1 ,2,3-propane

935 tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S. Patent No 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No 1 ,082, 1 79, while polycarboxylates containing phosphone substituents are disclosed in British

940 Patent No 1 ,439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentane- cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5- tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1 ,2,3,4,5,6-

945 hexane -hexacar-boxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic poly-carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1 ,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates

950 containing up to three carboxy groups per molecule, more particularly citrates.

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

955 such as citric acid.

A suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamme-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds

960 are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.

965 Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.

Other builder materials that can form part of the builder system for use in non-liquid compositions include inorganic materials such as alkali

970 metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and ammo polycarboxylates.

Other suitable water-soluble organic salts are the homo- or co- polymeric acids or their salts, in which the polycarboxylic acid comprises at

975 least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1 ,596,756 Examples of such salts are polyacrylates of MW 2,000- 1 0,000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from

980 about 4,000 to about 80,000, especially from about 5,000 to about

20,000.

Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight. 985 F.Suds suppressor

Another optional ingredient is a suds suppressor, exemplified by sihcones, and sihca-silicone mixtures. Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic 990 silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier. Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or 995 more of the other components.

A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672 Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent publication No. 2 646 1 27 published on April 28, 1 977 An example of 1000 such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred suds controlling agents are the suds suppressor systems comprising a mixture of silicone oils and 2-alkyl-alcanols. A suitable 2-alkyl-alkanol is 2-butyl-octanol which are commercially available under the trade name Isofol 1 2 R. 1005 Such suds suppressor systems are described in Copending European

Patent application No. 928701 74.7 filed 1 0 November, 1 992

Especially preferred silicone suds controlling agents are described in Copending European Patent application N °92201 649 8 Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous 1010 silica such as Aerosιl^R.

The suds suppressors described above are normally employed at levels of from 0.001 % to 2% by weight of the composition, preferably from 0.01 % to 1 % by weight G.Others

1015 Other components used in detergent compositions may be employed, such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bacteπcides, tarnish inhibitors, coloring agents, and/or encapsulated or non-encapsulated perfumes.

Especially suitable encapsulating materials are water soluble capsules

1020 which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1 ,464,61 6.

Other suitable water soluble encapsulating materials comprise dextπns derived from ungelatmized starch acid-esters of substituted dicarboxylic acids such as described in US 3,455,838. These acid-ester

1025 dextπns are, preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating materials include N-Lok manufactured by National Starch The N-Lok encapsulating material consists of a modified maize starch and glucose The starch is modified by adding monofunctional substituted groups such as

1030 octenyl succinic acid anhydride.

Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and maleic

1035 anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvmyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably

1040 from 1 % to 6% by weight of the composition

Preferred optical brighteners are anionic in character, examples of which are disodium 4,4'-bιs-(2-dιethanolamιno-4-anιlιno -s- tπazιn-6- ylamιno)stιlbene-2:2' disulphonate, disodium 4, - 4'-bιs-(2-morpholιno-4- anιlιno-s-trιazιn-6-ylamιno-stιlbene-2:2' - disulphonate, disodium 4,4' - bis-

1045 (2,4-dιanιlιno-s-trιazιn-6-ylamιno)stιlbene-2 2' - disulphonate, monosodium 4',4" -bιs-(2,4-dιanιlιno-s-trι-azιn-6 ylamιno)stιlbene-2-sulphonate, disodium 4,4' -bιs-(2-anιlιno-4-(N-methyl-N-2-hydroxyethylamιno)-s-tπazιn-6- ylamιno)stιlbene-2,2' - disulphonate, di-sodium 4,4' -bιs-(4-phenyl-2, 1 ,3- trιazol-2-yl)-stιlbene-2,2' disulphonate, di-so-dium 4,4'bιs(2-anιlιno-4-( 1 -

1050 methyl-2-hydroxyethylamιno)-s-tπazιn-6- ylamι-no)stιlbene-2, 2 'disulphonate, sodium 2(stilbyl-4"-(naphtho- 1 ',2' :4,5)- 1 ,2,3 - triazole-2"-sulphonate and 4,4'-bis(2-sulphostyryl)biphenyl. Highly preferred brighteners are the specific brighteners of copending European Patent application No. 95201 943.8.

1055 Other useful polymeric materials are the polyethylene glycols, particularly those of molecular weight 1 000- 1 0000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric

1060 polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.

Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene

1065 glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 41 1 6885 and 471 1 730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula

1070 (CH₃(PEG)43>o.75(POH)o.25[^T-^pO>2.8(T-PEG)₀.4]T(PO-

H)θ.25'(PEG>43CH₃)o.75 where PEG is -(0C2H4>0-,P0 is (OC3H6O) and T is (PCOC6H4CO).

Also very useful are modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1 -2

1075 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol. The target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups. However, some copolymers will be

1080 less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1 -2 diol, thereof consist "secondarily" of such species.

The selected polyesters herein contain about 46% by weight of dimethyl terephthalic acid, about 1 6% by weight of propane -1 .2 diol, about

1085 1 0% by weight ethylene glycol about 1 3% by weight of dimethyl sulfobenzoic acid and about 1 5% by weight of sulfoisophthalic acid, and have a molecular weight of about 3.000. The polyesters and their method of preparation are described in detail in EPA 31 1 342.

Is is well known in the art that free chlorine in tap water rapidly

1090 deactivates the enzymes comprised in detergent compositions. Therefore, using chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0. 1 % by weight of total composition, in the formulas will provide improved through the wash stability of the specific amylase enzymes. Compositions comprising chlorine

1095 scavenger are described in the European patent application 9287001 8.6 filed January 31 , 1 992. H. Softening agents

Fabric softening agents can also be incorporated into laundry detergent compositions in accordance with the present invention. These

1 100 agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A- 1 400 898 and in USP 5,01 9,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-BO 01 1 340 and their combination with mono C1 2-C14 quaternary ammonium salts are

1 105 disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 91 9. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 31 3 1 46.

Levels of smectite clay are normally in the range from 2% to 20%,

1 1 10 more preferably from 5% to 1 5 % by weight, with the material being added as a dry mixed component to the remainder of the formulation. Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1 % to 3% by weight whilst the high molecular

1 1 15 weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1 % to 2%, normally from 0.1 5% to 1 .5% by weight. These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other

1 120 solid components of the composition. I.Dye transfer inhibition

The detergent composition of the present invention can also include compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering

1 125 operations involving colored fabrics.

J. Polymeric dye transfer inhibiting agents

The detergent compositions according to the present invention also comprise from 0.001 % to 10 %, preferably from 0.01 % to 2%, more preferably from 0.05% to 1 % by weight of polymeric dye transfer inhibiting

1 130 agents. Said polymeric dye transfer inhibiting agents are normally incorporated into detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other

1 135 articles in the wash.

Especially suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.

1 140 Addition of such polymers also enhances the performance of the enzymes according the invention, a) Polyamine N-oxide polymers

The polyamine N-oxide polymers suitable for use contain units having the following structure formula :

1 145 P

(D A,

R 1 150 wherein P is a polymerisable unit, whereto the R-N-0 group can be attached to or wherein the R-N-0 group forms part of the polymerisable unit or a combination of both. 0 0 O

I I I I I I

1 155 A is NC, CO, C, -O-,-S-, -N- ; x is O or 1 ;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups. 1 160 The N-O group can be represented by the following general structures

O O

T T

(R-l )x -N- (R₂)V = N- (R ₁ )x

1 165

(R3>z wherein R -| , R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached

1 170 or wherein the nitrogen of the N-O group forms part of these groups.

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

Suitable polyamine N-oxides wherein the N-O group forms part of the

1 175 polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.

One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the

R-group. Preferred polyamine N-oxides are those wherein R is a

1 180 heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidme, pipeπdme, quinolme, acπdine and derivatives thereof.

Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group.

1 185 Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.

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

1 190 of said R group.

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

Another preferred class of polyamine N-oxides are the polyamine

1 195 oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is attached to said R groups.

Examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.

1200 Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties Examples of suitable polymeric backbones are polyvmyls, polyalkyleπes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.

1205 The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10 1 to 1 : 1 000000. However the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymeπzation or by appropriate degree of N- oxidation Preferably, the ratio of amine to amine N-oxide is from 2:3 to

1210 1 : 1 000000. More preferably from 1 4 to 1 1 000000, most preferably from 1 :7 to 1 : 1 000000. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa < 1 0,

1215 preferably PKa < 7, more preferred PKa < 6.

The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.

Typically, the average molecular weight is within the range of 500 to

1220 1 000,000; preferably from 1 ,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1 ,000,000,

1225 preferably from 5,000-200,000.

Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N- vinylimidazole N-vmylpyrrohdone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably

1230 from 8,000 to 30,000, most preferably from 1 0,000 to 20,000 The average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W Chemical Analysis Vol 1 1 3, "Modern Methods of Polymer Characterization" .

Highly preferred N-vinylimidazole N-vmyipyrrohdone copolymers have 1235 an average molecular weight range from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 1 0,000 to 20,000.

The N-vmyhmidazole N-vmylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance 1240 of detergent compositions formulated therewith.

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

1245 The detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 1 5,000. Suitable

1250 polyvinyipyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K- 1 5 (viscosity molecular weight of 1 0,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 1 60,000), and PVP K-90 (average molecular weight of 360,000) Other suitable

1255 polyvinyipyrrolidones which are commercially available from BASF Corporation include Sokalan HP 1 65 and Sokalan HP 12, polyvinyipyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696). d) Polyvmyloxazohdone :

1260 The detergent compositions of the present invention may also utilize polyvmyloxazohdone as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably

1265 from about 5,000 to about 1 5,000. e) Polyvmylimidazole : The detergent compositions of the present invention may also utilize polyvmylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average about 2,500 to about 400,000, 1270 preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 1 5,000. f) Cross-linked polymers :

Cross-linked polymers are polymers whose backbone are

1275 interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches, cross-linked polymers have been described in the Journal of Polymer

Science, volume 22, pages 1035-1039.

In one embodiment, the cross-linked polymers are made in such a 1280 way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure. In another embodiment, the cross-linked polymers entrap the dyes by swelling.

Such cross-linked polymers are described in the European patent publication No. 71 9856. 1285 Method of washing

The cleaning compositions according to the invention can be liquid, paste, gels, bars, tablets, powder or granular forms Granular compositions can also be in "compact " form, the liquid compositions can also be in a "concentrated" form. 1290 The compositions of the invention may be formulated as hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the pretreatment or soaking of stained fabric, rinse added fabric softener compositions.

The compositions of the invention may be used in essentially any 1295 washing or cleaning methods, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate rinse aid composition may be added.

For laundering fabrics, the process herein comprises contacting fabrics with a laundering solution in the usual manner and exemplified 1300 hereunder.

The process is conveniently carried out at 5 °C to 95 ° C, especially between 10°C and 60°C. The specific amylase enzymes within the specified enzymatic concentration, have demonstrated superior starch cleaning even for wash cycles occuring at very low temperatures (between

1305 1 0°C and 25°C). The pH of the treatment solution is preferably from 7 to 1 1 .

The aspects and embodiments of the present invention set forth in this document have surprising advantages in effective removal of the microfibrils that anchor stains to the fabric after said specific amylase 1310 enzymes remove the starch from the fibre.

The following examples further describe and demonstrate the preferred embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration, and are not to be construed as limitations of the present invention since many variations

1315 thereof are possible without departing from its spirit and scope.

In the detergent compositions, the abbreviated component identifications have the following meanings: LAS Sodium linear C-) 2 alkyl benzene sulphonate

Alkyl Sulfate AS :

TAS Sodium tallow alkyl sulphate

AES : Alkyl Ethoxy Sulfate

Cχ.γAS : Sodium 0χ - Cy alkyl sulfate

SAS : C -| 2"C ι 4 secondary (2,3) alkyl sulfate in the form of the sodium salt.

APG Alkyl polyglycoside surfactant of formula C -^* 2 -

(glycosyl)_x, where x is 1 .5,

AEC : Alkyl ethoxycarboxylate surfactant of formula

C -| 2 ethoxy (2) carboxylate. ss Secondary soap surfactant of formula 2-butyl octanoic acid

25EY A C1 2-C 1 5 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide

Cχ-Z^EY A 0χ - C^*7 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide

Cχ-γEzS A 0χ - Cy sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole

Nonionic C1 3-C 1 5 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafax LF404 by BASF Gmbh

C 1 4- 1 5 predominantly linear primary alcohol condensed with an average of 7 moles of

C45E7 ethylene oxide

CFAA Cl 2"C l 8 alkyl N-methyl glucamide

TFAA C1 6-C 1 8 alkyl N-methyl glucamide.

Silicate Amorphous Sodium Silicate (Siθ2'Na2θ ratio 2.0)

NaSKS-6 Crystalline layered silicate of formula δ- Na2Si2θ5

Carbonate Anhydrous sodium carbonate Metasihcate Sodium metasilicate (SιO_?:Na,0 ratio = 2.0)

Phosphate or STPP Sodium tπpolyphosphate

MA/AA Copolymer of 4: 1 -1 :4 maleic/acrylic acid, average molecular weight about 4,000-80,000

PA 30 Polyacrylic acid of average molecular weight of approximately 8,000. Terpolymer Terpolymer of average molecular weight approx.

7,000, comprising acrylιc:maleic:ethylacrylic acid monomer units at a weight ratio of

60:20:20

480N Random copolymer of 3:7 acrylic/methacrylic acid, average molecular weight about 3,500.

Polyacrylate Polyacrylate homopolymer with an average molecular weight of 8,000 sold under the tradename PA30 by BASF GmbH

Zeolite A Hydrated Sodium Aluminosilicate of formula Na-| 2<A 1 θ2Siθ2) ι 2- 27H20 having a primary particle size in the range from 1 to 1 0 micrometers

Zeolite MAP Alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1 .33

Citrate Tri-sodium citrate dihydrate

Citric Citric Acid Perborate Anhydrous sodium perborate monohydrate (PB-1 ) bleach, empirical formula NaBθ2-H2θ2

Nonanoyloxy benzene sulfonate in the form of

NOBS the sodium salt

PB4 Anhydrous sodium perborate tetrahydrate.

Percarbonate Anhydrous sodium percarbonate bleach of empirical formula 2Na2Cθ3.3H2θ2

TAED Tetraacetyl ethylene diamine

Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall.

Pectinase Pectolytic enzyme sold under the tradename Pectinex AR by Novo Nordisk A/S.

Xylanase Xylanolytic enzyme sold under the tradenames Pulpzyme HB or SP431 by Novo Nordisk A/S or Lyxasan (Gist-Brocades) or Optipulp or Xylanase (Solvay).

Protease Protease can be for example, Proteolytic enzyme sold under the tradename Savinase, Alcalase, Durazym by Novo Nordisk A/S, Maxacal, Maxapem sold by Gist-Brocades, Biosam sold by Showa Denko and proteases described in patents WO91 /06637 and/or W095/1 0591 and/or EP 251 446, but is not limited to these examples. Specific amylase One of the specific amylase enzymes (a)-(h) enzyme which are described in the DETAILED DESCRIPTION OF THE INVENTION according to the present invention.

Complementary Amylolytic enzyme sold under the tradename amylase Purafect Ox Am^R described in WO 94/1 8314, WO96/05295 sold by Genencor; Termamyl^®, Fungamyl^®, Ban^® and Duramyl^® all available from Novo Nordisk A/S and Maxamyl^® by Gist- Brocades.

Lipase Lipolytic enzyme sold under the tradename Lipolase, Lipolase Ultra by Novo Nordisk A/S

Peroxidase Peroxidase enzyme

Cellulase Cellulosic enzyme sold under the tradename Carezyme or Celluzyme by Novo Nordisk A/S.

CMC Sodium carboxymethyl cellulose

HEDP 1 , 1 -hydroxyethane diphosphonic acid

DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060.

PAAC pentaamine acetate cobalt (III) sal.

BzP Benzoyl peroxide.

PVP Polyvinyl pyrrolidone polymer.

PVNO Poly(4-vinylpyridine)-N-Oxide. SRP (Soil Release Soil Release polymer can be, for example, Polymer) sulfonated poly-ethoxy/propoxy end capped ester oligomer and sulfobenzoyl and capped esters with oxyethyleneoxy and terephtaloyl backone, but is not limited these examples.

EDDS Ethylenediamine -N, N'- disuccinic acid, [S,S] isomer in the form of the sodium salt.

Brightener Bightener can be, for example, Disodium 4.4'- bιs(4-anιlιno-6-morpholιno- 1 ,3.5-trιazιn-2-yl) amino) stιlbene-2:2'-dιsulfonate, and disodium 4,4'-bιs (2-sulphostyryl) biphenyl, but is not limited to these examples. Brightener can be a combination of two or more brighteners.

Suds Suppressor 25% paraffin wax Mpt 50°C, 1 7% hydrophobic silica, 58% paraffin oil.

Granular Suds 1 2% Sihcone/sihca, 1 8% stearyl alcohol, 70% Suppressor starch in granular form

SCS Sodium cumene sulphonate

Sulphate Anhydrous sodium sulphate.

HMWPEO High molecular weight polyethylene oxide

PGMS Polyglycerol monostearate having a tradename of Radiasurf 248

TAE 25 Tallow alcohol ethoxylate (25)

PEG Polyethylene glycol BTA Benzotriazole

Bismuth nitrate Bismuth nitrate salt

KOH 100% Active solution of Potassium Hydroxide

SMP Sugar matrix protected zeolite - perfume carrier.

pH Measured as a 1 % solution in distilled water at 20°C.

Silicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 1 0: 1 to 1 00: 1

Example 1

1320

Granular fabric cleaning compositions in accord with the invention are prepared as follows:

1 II III IV V

LAS 18.0 9.4 21.0 21.5 21.5

AS - 11.3 - 6.55 6.55

AES - 1.00 - - -

C-12-15E3S 1.5 - - - -

Alkyl Ci 2-14 ^me thyl 0.7 0.6 0.7 1.5 2 dihydroxyethyl ammonium chloride

C45E7 0.9 - - - -

Nonionic - 1.5 1.2 3.3 3.3

Phosphate 22.5 - 40 - -

MA/AA 1.0 - - 7.10 7.10

Soil release polymer 0.2 0.4 0.3 0.3 0.3

CMC 0.75 - 0.3 - -

Polyethyleneimine (MW 0.25 - 1.00 - -

1800)

Na-SKS-6 - - - 3.3 3.3

Aluminosilicate - 24.8 8.00 8.4 8.4

Carbonate 5.0 22.4 21.7 18.9 18.9

Silicate 7.6 14.7 2.0 11.7 11.7 sulfate - 5.4 - 5.2 5.2

PVNO - - 0.5 - -

Polyacrylate - 2.3 - - -

PEG 4000 - 1.6 - 0.2 0.2

Suds suppressor - 0.60 0.25 0.4 0.4

Specific amylase enzyme (c) 0.005 0.01 0.02 0.03 0.04

Complementary _< amylase - - - - 0.004

Protease 0.006 0.01 0.014 0.03 0.03

Lipase 0.002 - 0.024 - -

Cellulase 0.005 0.005 0.007 0.008 0.009

DTPA - 0.8 - - -

PB1 - 1.0 0.5 4.0 4.0 NOBS - - - 4.0 4.0

HEDP - 0.5

DETPMP 0.6 - - -

MgS04 0.8 - - -

SMP - 1 .5 - -

Brightener 0.20 0.1 7 0.10 0.31 0.31

Perfume 0.4 0.3 0.25 0.25

Water & minors Up to 100%

The level of the enzymes comprised in such composition are expressed in pure enzyme by weight of total composition.

Example 2

Granular fabric cleaning compositions in accord with the invention 1330 were prepared as follows:

1 II III IV V V

LAS 22.0 22.0 22.0 22.0 22.0 22.0

Coco-alkyl-dimethyl 0.3 1 .0 1 .5 2.0 2.4 1 .2 hydroxyethyl ammonium chloride

Phosphate 23.0 23.0 23.0 23.0 23.0 23.0

Carbonate 23.0 23.0 23.0 23.0 23.0 23.0

Silicate 1 4.0 1 4.0 1 4.0 1 4.0 14.0 1 4.0

Zeolite A 8.2 8.2 8.2 8.2 8.2 8.2

DETPMP 0.4 0.4 0.4 0.4 0.4 0.4

Sodium sulfate 5.5 5.5 5.5 5.5 5.5 5.5

Specific amylase 0.005 0.02 0.01 0.03 0.02 0.02 enzyme (c)

Complementary - - - - - 0.00 amylase

Protease 0.01 0.02 0.01 0.005 - -

Pectinase 0.02 - - - - -

Xylanase - - 0.01 0.02 - -

Lipase 0.005 0.01 - - - -

Cellulase 0.002 0.005 . 0.01 0.02 0.01 0.01

Water & minors Up to 100%

The level of the enzymes comprised in such composition are 1335 expressed in pure enzyme by weight of total composition. Example 3

Granular fabric cleaning compositions in accord with the invention were prepared as follows:

1340

I II III IV V VI

LAS 12.0 12.0 12.0 12.0 12.0 12.0

Zeolite A 26.0 26.0 26.0 26.0 26.0 26.0

SS 4.0 4.0 4.0 4.0 4.0 4.0

SAS 5.0 5.0 5.0 5.0 5.0 5.0

Coco-alkyl-dimethyl 0.4 1.0 1.5 2.0 2.0 1.2 hydroxyethyl ammonium chloride

Citrate 5.0 5.0 5.0 5.0 5.0 5.0

Sodium Sulfate 17.0 17.0 17.0 28.0 17.0 17.0

Perborate 16.0 16.0 16.0 - 16.0 16.0

TAED 5.0 5.0 5.0 - 5.0 5.0

Protease 0.06 0.03 0.02 0.08

Lipase 0.005 0.01 -

Complementary - - - - - o.01 amylase

Specific amylase 0.01 0.015 0.01 0.02 0.005 0.005 enzyme (h) cellulase 0.004 0.005 0.01 0.02 0.004 0.002

Water & minors Up to 100%

Example 4

1345

Granular fabric cleaning compositions in accord with the invention which are especially useful in the laundering of coloured fabrics were prepared as follows :

1 II III IV

LAS 1 1 .4 10.7 - -

TAS 1.8 2.4 - -

TFAA - - 4.0 4.0

C₁₄._{1 5}AS 3.0 3.1 10.0 10.0

C14-1 5E7 4.0 4.0 - -

^C12-15E3^S - - 3.0 3.0

Coco-alkyl-dimethyl hydrc ixyethyl 1 .2 1 .2 0.9 0.8 ammonium chloride

C16-18^E1 1 1 .8 1 .8 - -

^C12-15^E5 - - 8.0 8.0

Citrate 14.0 15.0 7.0 7.0

Carbonate - - 10 10

Citric 3.0 2.5 3.0 3.0

Zeolite A 32.5 32.1 25.0 25.0

Na-SKS-6 - - 9.0 9.0

MA/AA 5.0 5.0 5.0 5.0

DETPMP 1 .0 0.2 0.8 0.8

Protease 0.02 0.02 0.01 0.01

Specific amylase enzyme (0 0.03 0.03 0.005 0.005

Cellulase 0.01 0.015 0.005 0.003

Complementary amylase - - - 0.02

Silicate 2.0 2.5 - -

Sulphate 3.5 5.2 3.0 3.0

PVP 0.3 0.5 - -

Poly <4-vinylpyridine)-N- - - 0.2 0.2 oxide/copolymer of vinyl- imidazole and vinyl-pyrrolidone

Perborate 0.5 1 .0 - -

Peroxidase 0.01 0.01 - -

Phenol sulfonate 0.1 0.2 - - Water/Minors Up to 100%

1350

Example 5

1355

I II

LAS 6.5 8.0

Coco-alkyl-dimethyl 0.5 0.7 hydroxyethyl ammonium chloride

Sulfate 1 5.0 1 8.0

Zeolite A 26.0 22.0

Sodium nitrilotriacetate 5.0 5.0

PVP 0.5 0.7

TAED 3.0 3.0

Boric acid 4.0 -

Perborate 0.5 1 .0

Phenol sulphonate 0.1 0.2

Protease 0.06 0.02

Silicate 5.0 5.0

Carbonate 1 5.0 1 5.0

Peroxidase 0.1 0.1

Pectinase 0.02 -

Cellulase 0.005 0.01

Lipase 0.01 -

Specific amylase enzyme (c) 0.01 0.01

Water/minors Up to 100%

1360 The level of the enzymes comprised in such composition are expressed in pure enzyme by weight of total composition. Example 6

1365 A compact granular fabric cleaning compositions in accord with the invention were prepared as follows:

1 II

^C14-1 5^AS 8.0 8.0

^C1 2-1 5^E3S 2.0 2.0

Coco-alkyl-dimethyl hydroxyethyl ammonium 0.6 0.8 chloride

C12-15^E5 3.0 3.0 ^C12-15^E3 3.0 3.0 TFAA 2.5 2.5

Zeolite A 17.0 17.0

NaSKS-6 12.0 12.0

Citric acid 3.0 3.0

Carbonate 7.0 7.0

MA/AA 5.0 5.0

CMC 0.4 0.4

Poly (4-vinylpyridine)-N-oxide/ 0.2 0.2 copolymer of vinylimidazole and vinylpyrrolidone

Protease 0.05 0.05

Lipase 0.005 0.005

Cellulase 0.005 0.007

Specific amylase enzyme (c) 0.01 0.02

Complementary amylase - 0.005

TAED 6.0 6.0

Percarbonate 22.0 22.0

EDDS 0.3 0.3

Granular suds suppressor 3.5 3.5 water/minors Up to 100%

The level of the enzymes comprised in such composition are 1370 expressed in pure enzyme by weight of total composition. Example 7

A granular fabric cleaning compositions in accord with the invention which provide "softening through the wash" capability were prepared as follows:

1 II III

Cl 4-1 5^AS - 10.0 10.0

LAS 7.6 - -

C_{1 6}._{1 8}AS 1 .3 - -

C14-1 5^E7 4.0 - -

C12-1 5^E3 - 5.0 5.0

Coco-alkyl-dimethyl hydroxy¬ 0.9 1.0 1 .0 ethyl ammonium chloride

Citrate 5.0 3.0 3.0

Na-SKS-6 - 1 1 .0 1 1 .0

Zeolite A 1 5.0 15.0 1 5.0

MA/AA 4.0 4.0 4.0

DETPMP 0.4 0.4 0.4

Perborate 1 5.0 - -

Percarbonate - 1 5.0 1 5.0

TAED 5.0 5.0 5.0

Smectite clay 10.0 10.0 10.0

HMWPEO - 0.1 0.1

Protease 0.02 0.01 0.01

Lipase 0.02 0.01 0.01

Specific amylase enzyme (d) 0.02 0.005 0.005

Complementary ι amylase - - 0.02

Cellulase 0.01 0.004 0.002

Silicate 3.0 5.0 5.0

Carbonate 10.0 10.0 10.0

Granular suds su ppressor 1 .0 4.0 4.0

CMC 0.2 0.1 0.1

Water/minors Up to 100%

The level of the enzymes comprised in such composition are expressed in pure enzyme by weight of total composition. 1380

Example 8

Heavy duty liquid fabric cleaning compositions suitable for use in the pretreatment of stained fabrics, and for use in a machine laundering 1385 method, in accord with the invention were prepared as follows:

I II

C12-14AS 20.0 20.0 ss 5.0 5.0

Coco-alkyl-dimethyl 2.0 1.0 hydroxyethyl ammonium chloride

Citrate 1.0 1.0

^C11-12^E3 13.0 13.0

Monethanolamine 2.5 2.5

Protease 0.005 0.03

Lipase 0.002 0.01

Specific amylase enzyme 0.05 0.005

(b)

Cellulase 0.02 0.005

Pectinase 0.02 0.02

Water/propylene glycol/ethanol (100:1:1)

1390

Example 9

Heavy duty liquid fabric cleaning compositions in accord with the invention were prepared as follows:

1395

1 II

C-J 2-14 alkenyl succinic 3.0 8.0 acid

Citric acid 1 0.0 1 5.0

Ci 2-1 5 AS acid form 8.0 8.0

C-j 2-1 5^E2§ acid form - 3.0

C1 2- 1 5^E7 - 8.0

C1 2-1 5^E3 8.0 -

DETPMP 0.2 -

Oleic acid 1 .8 -

Ethanol 4.0 4.0

Propanediol 2.0 2.0

Protease 0.02 0.02

Specific amylase enzyme(c) 0.005 0.01

Cellulase 0.003 0.005

Coco-alkyl dimethyl hydroxy 0.5 0.9 ethyl ammonium chloride

PVP 1 .0 2.0

Perborate - 1 .0

Phenol sulphonate - 0.2

Peroxidase - 0.01

NaOH Up to pH 7.5

Water / minors Up to 100%

The level of the enzymes comprised in such composition are 1400 expressed in pure enzyme by weight of total composition. Example 10

Syndet bar fabric cleaning compositions in accord with the invention 1405 were prepared as follows:

1 II

C1 2-1 6 alkyl sulfate, Na 20.0 20.0

C12-14 N-methyl glucamide 5.0 5.0

C1 1 -13 alkyl benzene 10.0 10.0 sulphonate, Na

Coco-alkyl-dimethyl hydroxyethyl 3.0 1 .5 ammonium chloride

Sodium carbonate 25.0 25.0

Sodium pyrophosphate 7.0 7.0

Sodium tripolyphosphate 7.0 7.0

Zeolite A 5.0 5.0

Carboxymethylcellulose 0.2 0.2

Polyacrylate (MW 1400) 0.2 0.2

Coconut monethanolamide 5.0 5.0

Specific amylase enzyme (c) 0.01 0.02

Cellulase 0.005 0.01 5

Protease 0.3 -

Brightener, perfume 0.2 0.2

CaSO4 1 .0 1 .0

MgSO4 1.0 1 .0

Water 4.0 4.0

Filler* : balance to 100%

*Can be selected from convenient materials such as CaCO3, talc, clay 1410 (Kaolinite, Smectite), silicates, and the like.

The level of the enzymes comprised in such composition are expressed in pure enzyme by weight of total composition. Example 11

The following high density and bleach-containing detergent formulations, according to the present invention were prepared.

I II III IV V

LAS 22.53 22.53 22.53 22.53 22.53

AS(Ci4-i5 alkyl 6.88 6.88 6.88 6.88 6.88 sulfate)

^C12-15^E9 ³-^{46 3}-^{46 3}-⁴⁶ 3-46 3.46

Coco-alkyl- 0.49 0.49 - 0.49 0.49 dimethyl hydroxyethyl ammonium chloride

Coco-methyl bis - - 0.49

(hydroxyethyl) ammonium chloride

MA/AA 10.04 10.04 10.04 10.04 10.04

NaSKS-6 3.43 3.43 3.43 3.43 3.43

Zeolite A 8.83 8.83 8.83 8.83 8.83

Silicate 11.97 11.97 11.97 11.97 11.97

Carbonate 19.59 19.59 19.59 19.59 19.59 Protease 0.03008 0.03008 0.03008 0.03008 0.03008

( = 0.94% ( = 0.94% ( = 0.94% ( = 0.94% ( = 0.94% of Biosam of Biosam of Biosam of Biosam of Biosam

3.0 3.0 3.0 3.0 3.0 supplied supplied supplied supplied supplied by Showa by Showa by Showa by Showa by Showa

Denko) Denko) Denko) Denko) Denko)

Specific amylase 0.01 0.005 0.005 0.005 0.005 enzyme (c)

Cellulase 0.005930 0.002906 0.002906 0.005930 0.005930

2 9 9 2 2

( =0.51 % ( = 0.25% ( = 0.25% ( = 0.51 % ( = 0.51 % of of of of of

Carezyme carezyme carezyme Carezyme Carezyme

5.0T 5.0T 5.0T 5.0T 5.0T supplied supplied supplied supplied supplied by Novo by Novo by Novo by Novo by Novo

Nordisk Nordisk Nordisk Nordisk Nordisk

A/S) A/S) A/S) A/S) A/S)

Brightner 0.31 0.31 0.31 0.31 0.31

PB-1 0.50 0.50 0.50 0.50

NOBS

SRP 0.74 0.74 0.74 0.74 0.74

Silica 0.31 0.31 0.31 0.31 0.31

Perfume 0.25 0.25 0.25 0.25 0.25

Silicone antifoam 0.17 0.17 0.17 0.17 0.17

PEG 0.20 0.20 0.20 0.20 0.20

Water & Minors Up to 100% The level of the enzymes comprised in such composition are 1420 expressed in pure enzyme by weight of total composition.

The embodiments disclosed and represented by the previous examples have many advantages. For example, they can provide better removal effect of the microfibrils that anchor the stains to the fabric after 1425 said specific amylase enzymes remove the starch from the fibre.

It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to one skilled in the art without departing 1430 from the scope of the present invention.

SEQUENCE LISTING

Sequence description : SEQ ID No. 1 1435 ( 1 ) GENERAL INFORMATION: (i) APPLICANT

(A) NAME: The Procter & Gamble Company

(B) STREET: One Procter & Gamble Plaza

(C) CITY: Cincinnati, Ohio 1440 (E) COUNTRY: US

(F) POSTAL CODE (ZIP): 45202

(G) TELEPHONE: (51 3) 627-7025 (H) TELEFAX: (51 3) 627-6333

(I) TELEX: 1445 (ii) TITLE OF INVENTION: DETERGENT COMPOSITIONS

COMPRISING IMPROVED AMYLASES, CELLULASE AND

CATIONIC SURFACTANT

(iii) NUMBER OF SEQUENCE: 4

(iv) COMPUTER READABLE FORM: 1450 (A) MEDIUM TYPE: Floppy disk

(B) COMPUTER: IBM PC compatible

(C) OPERATING SYSTEM: MS-DOS

(D) SOFTWARE: Windows 3. 1 (2) INFORMATION FOR SEQ ID NO: 1 :

1455 (i) SEQUENCE CHARACTERISTICS:

(A) LENGTH: 485 amino acids

(B) TYPE: amino acid

(C) STRANDEDNESS: single

(D) TOPOLOGY: linear 1460 (ii) MOLECULE TYPE: peptide

(xi) SEQUENCE DESCRIPTION : SEQ ID No. 1 His His Asn Gly Thr Asn Gly Thr Met Met Gin Tyr Phe Glu Trp Tyr 1 5 10 1 5

Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Arg Asp Asp Ala Ala 1465 20 25 30

Asn Leu Lys Ser Lys Gly He Thr Ala Val Trp He Pro Pro Ala Trp 35 40 45 Lys Gly Thr Ser Gin Asn Asp Val Gly Tyr Gly Ala Tyr Asp Leu Tyr 1470 50 55 60

Asp Leu Gly Glu Phe Asn Gin Lys Gly Thr Val Arg Thr Lys Tyr Gly 65 70 75 80

Thr Arg Asn Gin Leu Gin Ala Ala Val Thr Ser Leu Lys Asn Asn Gly 85 90 95

1475 He Gin Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Ala Asp 100 105 1 1 0

Gly Thr Glu He Val Asn Ala Val Glu Val Asn Arg Ser Asn Arg Asn

1 1 5 120 1 25

Gin Glu Thr Ser Gly Glu Tyr Ala He Glu Ala Trp Thr Lys Phe Asp 1480 1 30 135 140

Phe Pro Gly Arg Gly Asn Asn His Ser Ser Phe Lys Trp Arg Trp Tyr 145 1 50 1 55 1 60

His Phe Asp Gly Thr Asp Trp Asp Gin Ser Arg Gin Leu Gin Asn Lys 1 65 1 70 1 75

1485 He Tyr Lys Phe Arg Gly Thr Gly Lys Ala Trp Asp Trp Glu Val Asp 1 80 1 85 1 90

Thr Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Ala Asp Val Asp Met

1 95 200 205

Asp His Pro Glu Val He His Glu Leu Arg Asn Trp Gly Val Trp Tyr 1490 210 21 5 220

Thr Asn Thr Leu Asn Leu Asp Gly Phe Arg He Asp Ala Val Lys His 225 230 235 240

He Lys Tyr Ser Phe Thr Arg Asp Trp Leu Thr His Val Arg Asn Thr 245 250 255

1495 Thr Gly Lys Pro Met Phe Ala Val Ala Glu Phe Trp Lys Asn Asp Leu

260 265 270

Gly Ala He Glu Asn Tyr Leu Asn Lys Thr Ser Trp Asn His Ser Val

275 280 285

Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Ala Ser Asn Ser Gly 1500 290 295 300

Gly Tyr Tyr Asp Met Arg Asn lie Leu Asn Gly Ser Val Val Gin Lys 305 31 0 31 5 320

His Pro Thr His Ala Val Thr Phe Val Asp Asn His Asp Ser Gin Pro 325 330 335

1505 Gly Glu Ala Leu Glu Ser Phe Val Gin Gin Trp Phe Lys Pro Leu Ala

340 345 350

Tyr Ala Leu Val Leu Thr Arg Glu Gin Gly Tyr Pro Ser Val Phe Tyr 355 360 365

1510 Gly Asp Tyr Tyr Gly He Pro Thr His Gly Val Pro Ala Met Lys Ser 370 375 380

Lys lie Asp Pro Leu Leu Gin Ala Arg Gin Thr Phe Ala Tyr Gly Thr 385 390 395 400

Gin His Asp Tyr Phe Asp His His Asp He He Gly Trp Thr Arg Glu 1515 405 410 41 5

Gly Asn Ser Ser His Pro Asn Ser Gly Leu Ala Thr lie Met Ser Asp

420 425 430

Gly Pro Gly Gly Asn Lys Trp Met Tyr Val Gly Lys Asn Lys Ala Gly 435 440 445

1520 Gin Val Trp Arg Asp lie Thr Gly Asn Arg Thr Gly Thr Val Thr He 450 455 460

Asn Ala Asp Gly Trp Gly Asn Phe Ser Val Asn Gly Gly Ser Val Ser 465 470 475 480

Val Trp Val Lys Gin 1525 485

(2) INFORMATION FOR SEQ ID No. 2 1530 (i) SEQUENCE CHARACTERISTICS:

(A) LENGTH: 485 amino acids

(B) TYPE: amino acid

(C) STRANDEDNESS: single

(D) TOPOLOGY: linear 1535 (ii) MOLECULE TYPE: peptide

(xi) SEQUENCE DESCRIPTION : SEQ ID No. 2 His His Asn Gly Thr Asn Gly Thr Met Met Gin Tyr Phe Glu Trp His 1 5 10 1 5

Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Arg Asp Asp Ala Ser 1540 20 25 30

Asn Leu Arg Asn Arg Gly He Thr Ala lie Trp He Pro Pro Ala Trp

35 40 45

Lys Gly Thr Ser Gin Asn Asp Val Gly Tyr Gly Ala Tyr Asp Leu Tyr 50 55 60

1545 Asp Leu Gly Glu Phe Asn Gin Lys Gly Thr Val Arg Thr Lys Tyr Gly 65 70 75 80

Thr Arg Ser Gin Leu Glu Ser Ala He His Ala Leu Lys Asn Asn Gly

85 90 95

Val Gin Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Ala Asp 1550 100 105 1 10

Ala Thr Glu Asn Val Leu Ala Val Glu Val Asn Pro Asn Asn Arg Asn

1 1 5 1 20 1 25

Gin Glu He Ser Gly Asp Tyr Thr He Glu Ala Trp Thr Lys Phe Asp 1 30 135 140

1555 Phe Pro Gly Arg Gly Asn Thr Tyr Ser Asp Phe Lys Trp Arg Trp Tyr 145 1 50 155 160

His Phe Asp Gly Val Asp Trp Asp Gin Ser Arg Gin Phe Gin Asn Arg

1 65 1 70 1 75

He Tyr Lys Phe Arg Gly Asp Gly Lys Ala Trp Asp Trp Glu Val Asp 1560 1 80 1 85 1 90

Ser Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Ala Asp Val Asp Met

1 95 200 205

Asp His Pro Glu Val Val Asn Glu Leu Arg Arg Trp Gly Glu Trp Tyr 210 21 5 220

1565 Thr Asn Thr Leu Asn Leu Asp Gly Phe Arg lie Asp Ala Val Lys His 225 230 235 240

He Lys Tyr Ser Phe Thr Arg Asp Trp Leu Thr His Val Arg Asn Ala 245 250 255

1570 Thr Gly Lys Glu Met Phe Ala Val Ala Glu Phe Trp Lys Asn Asp Leu

260 265 270

Gly Ala Leu Glu Asn Tyr Leu Asn Lys Thr Asn Trp Asn His Ser Val

275 280 285

Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Ala Ser Asn Ser Gly 1575 290 295 300

Gly Asn Tyr Asp Met Ala Lys Leu Leu Asn Gly Thr Val Val Gin Lys 305 310 31 5 320

His Pro Met His Ala Val Thr Phe Val Asp Asn His Asp Ser Gin Pro 325 330 335

1580 Gly Glu Ser Leu Glu Ser Phe Val Gin Glu Trp Phe Lys Pro Leu Ala

340 345 350

Tyr Ala Leu He Leu Thr Arg Glu Gin Gly Tyr Pro Ser Val Phe Tyr

355 360 365

Gly Asp Tyr Tyr Gly He Pro Thr His Ser Val Pro Ala Met Lys Ala 1585 370 375 380

Lys lie Asp Pro He Leu Glu Ala Arg Gin Asn Phe Ala Tyr Gly Thr 385 390 395 400

Gin His Asp Tyr Phe Asp His His Asn He lie Gly Trp Thr Arg Glu 405 410 41 5

1590 Gly Asn Thr Thr His Pro Asn Ser Gly Leu Ala Thr lie Met Ser Asp

420 425 430

Gly Pro Gly Gly Glu Lys Trp Met Tyr Val Gly Gin Asn Lys Ala Gly

435 440 445

Gin Val Trp His Asp He Thr Gly Asn Lys Pro Gly Thr Val Thr He 1595 450 455 460

Asn Ala Asp Gly Trp Ala Asn Phe Ser Val Asn Gly Gly Ser Val Ser 465 470 475 480

He Trp Val Lys Arg 485 1600 (2) INFORMATION FOR SEQ ID No. 3

(i) SEQUENCE CHARACTERISTICS:

(A) LENGTH: 20 amino acids

(B) TYPE: amino acid

(C) STRANDEDNESS: single 1605 (D) TOPOLOGY: linear

(ii) MOLECULE TYPE: peptide

(xi) SEQUENCE DESCRIPTION : SEQ ID No. 3 His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro- Asn-Asp 1610

(2) INFORMATION FOR SEQ ID No. 4

(i) SEQUENCE CHARACTERISTICS:

(A) LENGTH: 51 5

(B) TYPE: amino acid

1615 (C) STRANDEDNESS: single

(D) TOPOLOGY: linear (ii) MOLECULE TYPE: peptide

(xi) SEQUENCE DESCRIPTION : SEQ ID No. 4

AAPFNGTMMQ YFEWYLPDDG TLWTKVANEA NNLSSLGITA LWLPPAYKGT

1620 SRSDVGYGVY DLYDLGEFNQ KGAVRTKYGT KAQYLQAIQA AHAAGMQVYA

DVVFDHKGGA DGTEWVDAVE VNPSDRNQEI SGTYQIQAWT KFDFPGRGNT

YSSFKWRWYH FDGVDWDESR KLSRIYKFRG IGKAWDWEVD TENGNYDYLM

YADLDMDHPE VVTELKSWGK WYVNTTNIDG FRLDAVKHIK FSFFPDWLSD

VRSQTGKPLF TVGEYWSYDI NKLHNYIMKT NGTMSLFDAP LHNKFYTASK

1625 SGGTFDMRTL MTNTLMKDQP TLAVTFVDNH DTEPGQALQS WVDPWFKPLA

YAFILTRQEG YPCVFYGDYY GIPQYNIPSL KSKIDPLLIA RRDYAYGTQH

DYLDHSDIIG WTREGVTEKP GSGLAALITD GPGGSKWMYV GKQHAGKVFY

DLTGNRSDTV TINSDGWGEF KVNGGSVSVW VPRKTTVSTI AWSITTRPWT

DEFVRWTEPR LVAWP

1630

Claims

What is claimed is:

1 . A detergent composition comprising

( 1 ) at least one specific amylase selected from the group consisting of:

(a) α-amylase characterised by having a specific activity at least 25% higher than the specific activity of Termamyl^® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 1 0, measured by the Phadebas^® α-amylase activity assay;

(b) α-amylase according to (a) comprising the amino sequence shown in SEQ ID No. 1 or an α-amylase being at least 80% homologous with the amino acid sequence shown in SEQ ID No.1 ;

(c) α-amylase according to (a) comprising the amino sequence shown in SEQ ID No.2 or an α-amylase being at least 80% homologous with the amino acid sequence shown in SEQ ID No.2;

(d) α-amylase according to (a) comprising the following amino sequence in the N-terminal : His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu- Trp-Tyr-Leu-Pro-Asn-Asp (SEQ ID No.3) or an α-amylase being at least 80% homologous with the amino acid sequence shown (SEQ ID No.3) in the N- terminal;

(e) α-amylase according to (a-d) wherein the α-amylase is obtainable from an alkalophilic Bacillus species;

(f) α-amylase according to (e) wherein the amylase is obtainable from any of the strains NCIB 1 2289, NCIB 1 251 2, NCIB 1 251 3 and DSM 935;

(g)α-amylase showing positive immunological cross-reactivity with antibodies raised against an α-amylase having an amino acid sequence corresponding respectively to SEQ ID No.1 , ID No.2 or ID No.3 and; (h) Variant of a parent α-amylase, which parent α-amylase (i) has one of the amino acid sequences shown in SEQ ID No.1 , ID No.2 or ID No.4 respectively, or (ii)displays at least 80% homology with one or more of said amino acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an α-amylase having one of said amino acid sequences, and/or is encoded by a DNA sequence which hybridizes with the same probe as a DNA sequence encoding an α-amylase having one of said amino acid sequence; in which variants :

(i) at least one amino acid residue of said parent α-amylase has been deleted; and/or (ii) at least one amino acid residue of said parent α-amylase has been replaced by a different amino acid residue; and/or

(iii) at least one amino acid residue has been inserted relative to said parent α-amylase; said variant having an α-amylase activity and exhibiting at least one of the following properties relative to said parent α-amylase increased thermostability, increased stability towards oxidation, reduced Ca ion dependency, increased stability and/or α-amylolytic activity at neutral to relatively high pH values, increased α-amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for α-amylase variant to the pH of the medium; (2) a cellulase; and

(3) a cationic surfactant.

2. A detergent composition according to claim 1 wherein the specific amylase of claim 1 is comprised at a level of from about 0.005% to about 0.05% pure enzyme by weight of total composition.

3. A detergent composition comprising

(1 ) from about 0.005% to about 0.05% pure enzyme by weight of total composition of at least one specific amylase selected from the group consisting of:

(a) α-amylase characterised by having a specific activity at least 25% higher than the specific activity of Termamyl^® at a temperature range of 25°C to

55°C and at a pH value in the range of 8 to 1 0, measured by the Phadebas^® α-amylase activity assay;

(d) α-amylase according to (a) comprising the following amino sequence in the N-terminal : His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-

Trp-Tyr-Leu-Pro-Asn-Asp (SEQ ID No.3) or an α-amylase being at least 80% homologous with the amino acid sequence shown (SEQ ID No.3) in the N- terminal; (e) α-amylase according to (a-d) wherein the α-amylase is obtainable from an alkalophilic Bacillus species;

(f) α-amylase according to (e) wherein the amylase is obtainable from any of the strains NCIB 1 2289, NCIB 1 251 2, NCIB 1 251 3 and DSM 935; (g)α-amylase showing positive immunological cross-reactivity with antibodies raised against an α-amylase having an amino acid sequence corresponding respectively to SEQ ID No.1 , ID No.2 or ID No.3 and;

(h) Variant of a parent α-amylase, which parent α-amylase (i) has one of the amino acid sequences shown in SEQ ID No.1 , ID No.2 or ID No.4 respectively, or (ii)displays at least 80% homology with one or more of said amino acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an α-amylase having one of said amino acid sequences, and/or is encoded by a DNA sequence which hybridizes with the same probe as a DNA sequence encoding an α-amylase having one of said amino acid sequence; in which variants : (i) at least one amino acid residue of said parent α-amylase has been deleted; and/or

(ii) at least one amino acid residue of said parent α-amylase has been replaced by a different amino acid residue; and/or

(iii) at least one amino acid residue has been inserted relative to said parent α-amylase; said variant having an α-amylase activity and exhibiting at least one of the following properties relative to said parent α-amylase increased thermostability, increased stability towards oxidation, reduced Ca ion dependency, increased stability and/or α-amylolytic activity at neutral to relatively high pH values, increased α-amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for α-amylase variant to the pH of the medium;

(2) from about 0.002% to about 0.02% pure enzyme by weight of total composition of cellulase; and

(3) a cationic surfactant.

4. A detergent composition according to claim 3 wherein the cationic surfactant is comprised at a level of from about 0.2% to about 25% by weight of total composition.

5. A detergent composition according to claim 4 wherein the cationic surfactant is selected from the group consisting of coconut dimethyl hydroxyethyl ammonium chloride and coconut methyl dihydroxyethyl ammonium chloride.

6. A detergent composition according to claim 3 further comprising from about 1 % to about 40% by weight of total composition of anionic surfactant.

7. A detergent composition according to claim 3 further comprising a complementary amylase.

8. A detergent composition according to claim 7 wherein the weight ratio of the specific amylase of claim 3 to a complementary amylase is comprised between 9: 1 to 1 :9.

9. A detergent composition according to claim 3 further comprising a protease.

10. A method of laundering fabrics comprising the step of contacting said fabrics with an aqueous solution of the composition of claim 3 at a temperature of from about 10°C to about 25°C.