Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase

Definitions

• 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.
• 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.
• amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
• ⁇ -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).
• 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- ⁇ - amylase) which may be achieved with a variant according to the present invention are * increased stability and/or ⁇ -amylolytic activity at neutral to relatively high pH values, increased ⁇ -amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for ⁇ -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.
• 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.
• 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.
• An essential component of the detergent compositions of the present invention is a specific amylase enzyme.
• Such specific amylase enzymes are particularly useful as enzymes.
• composition comprises more than
• composition comprises less than 0.005% 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 amylase enzymes, it is not economical. If the composition comprises less than 0.005% 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 amylase enzymes, it is not economical. If the composition comprises less than 0.005% 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 amylase enzymes, it is not economical. If the composition comprises less than 0.005% 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 amylase enzymes, it is not economical. If the composition comprises less than 0.005% pure enzyme by weight of total composition
• 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.
• Specific amylase enzymes for use in the detergent compositions of the present invention therefore include :
• ⁇ -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 ® ⁇ -amylase activity assay.
• Phadebas ® ⁇ -amylase activity assay is described at pages 9-1 0, WO95/26397.
• ⁇ -amylases according (a) comprising the amino sequence shown in SEQ ID No. 1 or an ⁇ -amylase being at least 80% homologous with the amino acid sequence shown in SEQ ID No.1 .
• ⁇ -amylases according (a) comprising the amino sequence shown in SEQ ID No.2 or an ⁇ -amylase being at least 80% homologous with the amino acid sequence shown in SEQ ID No.2.
• ⁇ -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 ⁇ -amylase being at least 80% homologous with the amino acid sequence shown (SEQ ID No.3) or an ⁇ -amylase being at least 80% homologous with the amino acid sequence shown (SEQ ID No.3) or an ⁇ -amylase being at least 80% homologous with the amino acid sequence shown (SEQ ID No.3) or an ⁇ -amylase being at least 80% homologous with the amino acid sequence shown (SEQ ID No.3) or an ⁇ -amylase being at least 80% homologous with the amino acid sequence shown (SEQ ID No.3) or an ⁇ -amylase being at least 80% homologous with the amino
• 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
• ⁇ -amylases according (a-d) wherein the ⁇ -amylase is obtainable from an alkalophilic Bacillus species.
• 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.
• At least one amino acid residue of said parent ⁇ -amylase has been deleted; and/or 2. at least one amino acid residue of said parent ⁇ -amylase has been replaced by a different amino acid residue; and/or
• At least one amino acid residue has been inserted relative to said parent ⁇ -amylase; said variant having an ⁇ -amylase activity and exhibiting at least one of the following properties relative to said parent ⁇ -amylase increased thermostability, increased stability towards oxidation, reduced Ca ion dependency, increased stability and/or ⁇ -amylolytic activity at neutral to relatively high pH values, increased ⁇ -amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for ⁇ -amylase variant to the pH of the medium.
• 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.
• 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%,
• Cationic surfactant preferably from about 0.002% to about 0.005% pure enzyme by weight of total composition of cellulase.
• Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-live
• cationic surfactants include the ammonium surfactants such as alkylt ⁇ methylammonium halogenides, and those surfactants having the formula •
• each R 3 is selected from the group consisting of -CH2CH2-, -CH 2 CH(CH 3 )-, -CH2CH(CH2OH)-, -CH 2 CH 2 CH2-, and mixtures thereof; each R 4 IS selected from the group consisting of C -
• 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.
• Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
• Rl R2 R 3 R 4 N + x" M wherein 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.
• 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
• cationic surfactants include di-alkyl imidazolines. 235 Other cationic surfactants also include quaternary ammonium surfactant suitable for the present invention having the formula (I):
• 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.
• 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
• R6 is C1 -C4 alkyl and z is 1 or 2.
• Preferred quat ammonium surfactants are those as defined in formula
• 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
• 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 preferably from about 0.2% to about 25 %, preferably from about 1 % to about 8% by weight of such cationic surfactants.
• the detergent compositions of the invention may also contain additional detergent components.
• additional detergent 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.
• 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.
• compositions suitable for use in a laundry When formulated as compositions suitable for use in a laundry
• 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
• Laundry compositions can also contain softening agents, as additional detergent components.
• 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.
• 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.
• 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.
• Surfactant other than cationic surfactants are preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.
• 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,
• 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.
• 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
• 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.
• nonionic surfactants of this type include Igepal ⁇ M CO-630, marketed by the GAF Corporation; and TritonTM X-45, X- 1 1 4, X- 100 and X-102, all marketed by the Rohm & Haas Company.
• alkylphenol alkoxylates e.g , alkyl phenol ethoxylates
• 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
• 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.
• condensation products 350 with from about 2 to about 1 0 moles of ethylene oxide per mole of alcohol.
• Examples of commercially available nonionic surfactants of this type include Tergitol ⁇ M 1 5-S-9 (the condensation
• Neodol ⁇ M 45-9 the condensation product of C14-C 1 5 linear alcohol with 9 moles of ethylene oxide
• NeodolTM 23-3 the condensation product of C 1 2-C 1 3 linear alcohol with 3.0 moles of ethylene oxide
• NeodolTM 45 the condensation product of C -* - j -C i 5 linear alcohol with 9 moles ethylene oxide
• TergitolTM 24-L-6 NMW the condensation product of C -
• 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
• alkylpolysaccha ⁇ des 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 polysaccha ⁇ de, e.g. a polyglycoside,
• 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
• 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
• R 2 O(C n H2 n O)t ⁇ g'VC ⁇ syl) x
• R 2 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,
• the glycosyl is preferably derived from glucose.
• 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 -
• 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.
• 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.
• 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 -
• Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula. R2 - C - N - Z
• 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
• R ⁇ is methyl
• R2 is a straight C-j 1 - 1 5 alkyl or C i 6_ ⁇ s alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
• Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
• the nonionic agent When included in such laundry detergent compositions, the nonionic compound
• 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
• 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 -
• 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
• M is H
• a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted- ammonium cation.
• a metal cation e.g., sodium, potassium, lithium, calcium, magnesium, etc.
• ammonium or substituted- ammonium cation e.g., sodium, potassium, lithium, calcium, magnesium, etc.
• Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations
• 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-
• 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.
• alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:
• R 3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
• R 4 is a C - ⁇ -CQ hydrocarbyl, preferably an alkyl, or combination
• 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.
• R 3 is C 10-C 1 6 alkyl
• R 4 is methyl, ethyl or
• 490 isopropyl.
• methyl ester sulfonates wherein R 3 is C - ⁇ o-C -1 6 alkyl.
• alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C-
• 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
• an alkali metal cation e.g. sodium, potassium, lithium
• ammonium or substituted ammonium e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl
• alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
• alkyl chains of C 1 2-C 1 6 are preferred for lower wash temperatures (e.g. below about 50°C) and C -
• 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
• alkyl glycerol sulfonates 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 -
• sulfosuccinates especially saturated and unsaturated CQ- C12 diesters
• acyl sarcosinates especially saturated and unsaturated CQ- C12 diesters
• acyl sarcosinates especially saturated and unsaturated CQ- C12 diesters
• acyl sarcosinates especially saturated and unsaturated CQ- C12 diesters
• acyl sarcosinates sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic ⁇ onsulfated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2 ⁇ )
• 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.
• compositions (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
• 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
• 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
• NH2 wherein R-j is a C5-C12, preferably CR-CIO a
• R-] alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
• Preferred amines according to the formula herein above are n-alkyl amines Suitable amines for use herein may be selected from 1-hexylam ⁇ ne, 1- octylamine, 1-decylam ⁇ ne and laurylamine Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl- oxypropylamine, lauryl amido propylamine and amido propylamine.
• Suitable tertiary amines for use herein include tertiary amines having the formula R1R2R3N wherein R1 and R2 are C---C8 alkylchams or
• 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 ⁇ s 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 ⁇ > (CH 2 — CH ()) ⁇ H
• R-j is CQ-C]2 a'M; n ⁇ s 2-4, 570 preferably n is 3; R2 and R3 is C1-C4.
• Most preferred amines of the present invention include 1-octylam ⁇ ne, 1-hexylam ⁇ ne, 1-decylam ⁇ ne, 1-dodecylam ⁇ ne r C8-10oxypropylam ⁇ ne, N coco 1-3d ⁇ am ⁇ nopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles
• the most preferred amines for use in the compositions herein are 1 - hexylamine, 1 -octylamine, 1 -decylami ⁇ e, 1 -dodecylamine.
• the laundry detergent compositions of the present invention may also contain, ampholytic, zwitterionic, and semi-polar surfactants, as well as the
• 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
• 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.
• 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.
• 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.
• 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.
• 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
• Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
• R 3 (OR 4 )xN(R5)2 wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms
• 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.
• amine oxide surfactants in particular include C -
• laundry detergent compositions of the present invention typically comprise from 0.2% to about 1 5%, preferably
• Suitable water-soluble organic salts are the homo- or co-polymeric
• 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
• 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
• 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.
• 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, ⁇ -glucanases, arabinosidases chondroitinase, laccase or mixtures thereof.
• 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,
• Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as
• 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 .
• composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
• 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" .
• proteases include ALCALASE ® , DURAZYM ® and SAVINASE ® from Novo and MAXATASE ® , MAXACAL®, PROPERASE ® and MAXAPEM® (protein engineered Maxacal) from Gist- Brocades.
• proteases also encompass modified bacterial serine
• 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 B"
• 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”
• 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 B
• Protease C 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
• 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
• 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,
• 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.
• Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo.
• a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
• 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%
• lipases are preferred enzymes that can be included in the detergent compositions of the present invention.
• Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutze ⁇ ATCC 19.154, as
• 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
• 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
• lipases such as M 1 Lipase R ar
• 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
• 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.
• complementary it is meant the addition of one or more amylase suitable for detergency purposes.
• Examples of complementary amylases ( ⁇ and/or ⁇ ) are described below.
• WO94/02597 and WO95/1 0603, Novo Nordisk A/S describe cleaning compositions which incorporate mutant
• amylases 790 amylases.
• Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
• ⁇ -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) .
• 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).
• ⁇ -amylases examples 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 : ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl ® at a temperature range
• 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-
• 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.
• 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
• 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.
• 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.
• enzyme oxidation scavengers are ethoxylated tetraethylene polyammes.
• Especially preferred detergent ingredients are combinations with technologies which also provide a type of color care benefit.
• technologies which also provide a type of color care benefit.
• metallo catalysts for color maintenance are metallo catalysts for color maintenance.
• 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
• 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.
• 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- nonylam ⁇ no-4-oxoperoxybytyr ⁇ c acid and diperoxydodecanedioic acid. Such
• 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
• 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
• 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
• the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of
• Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
• 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
• detergent compositions will contain about 0.025% to about 1 .25%, by weight, of sulfonated zinc phthalocyanme.
• 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
• aluminosilicate materials such as silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, diethylene t ⁇ amine pentamethyleneacetate, metal ion sequestrants such as ammopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene t ⁇ amme pentamethylenephosphonic acid.
• 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.
• Another suitable inorganic builder material is layered silicate, e.g.
• SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2 ⁇ 5>.
• Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian
• 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 fuma ⁇ c acid, as well as the ether carboxylates described in German Offenlegenschnft 2,446,686, and 2,446,687 and U.S. Patent
• 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
• 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
• 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
• 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-
• Aromatic poly-carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1 ,425,343.
• the preferred polycarboxylates are hydroxycarboxylates
• 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
• 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.
• EDDS ethylenediamme-N,N'-disuccinic acid
• Preferred EDDS compounds are ethylenediamme-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
• 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.
• 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.
• builder materials that can form part of the builder system for use in non-liquid compositions include inorganic materials such as alkali
• Suitable water-soluble organic salts are the homo- or co- polymeric acids or their salts, in which the polycarboxylic acid comprises at
• 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
• 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
• compositions can comprise a silicone/silica mixture in combination with fumed nonporous 1010 silica such as Aeros ⁇ l 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
• compositions may be employed, such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bacte ⁇ cides, tarnish inhibitors, coloring agents, and/or encapsulated or non-encapsulated perfumes.
• encapsulating materials are water soluble capsules
• Suitable water soluble encapsulating materials comprise dext ⁇ ns derived from ungelatmized starch acid-esters of substituted dicarboxylic acids such as described in US 3,455,838. These acid-ester
• 1025 dext ⁇ ns 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
• 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
• 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
• Preferred optical brighteners are anionic in character, examples of which are disodium 4,4'-b ⁇ s-(2-d ⁇ ethanolam ⁇ no-4-an ⁇ l ⁇ no -s- t ⁇ az ⁇ n-6- ylam ⁇ no)st ⁇ lbene-2:2' disulphonate, disodium 4, - 4'-b ⁇ s-(2-morphol ⁇ no-4- an ⁇ l ⁇ no-s-tr ⁇ az ⁇ n-6-ylam ⁇ no-st ⁇ lbene-2:2' - disulphonate, disodium 4,4' - bis-
• 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
• 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
• polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1 -2
• the selected polyesters herein contain about 46% by weight of dimethyl terephthalic acid, about 1 6% by weight of propane -1 .2 diol, about
• compositions comprising chlorine
• Fabric softening agents can also be incorporated into laundry detergent compositions in accordance with the present invention.
• 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
• Levels of smectite clay are normally in the range from 2% to 20%,
• 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
• 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
• 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
• 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
• 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.
• polyamine N-oxide polymers suitable for use contain units having the following structure formula :
• 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
• 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.
• the N-O group can be represented by the following general structures
• R3>z wherein R -
• 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.
• 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
• Preferred polyamine N-oxides are those wherein R is a
• heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidme, pipe ⁇ dme, quinolme, ac ⁇ dine 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.
• polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
• 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
• polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.
• polyamine N-oxides Another preferred class of polyamine N-oxides are the polyamine
• polyamine oxides wherein R groups can be aromatic such as phenyl.
• Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties
• suitable polymeric backbones are polyvmyls, polyalkyle ⁇ es, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
• 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.
• the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolyme ⁇ zation or by appropriate degree of N- oxidation
• the ratio of amine to amine N-oxide is from 2:3 to
• 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,
• 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.
• the average molecular weight is within the range of 500 to
• N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1 ,000,000,
• 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
• 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.
• 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 .
• 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.
• PVP polyvinylpyrrolidone
• 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
• 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).
• Polyvmyloxazohdone :
• 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
• 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
• 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.
• the cross-linked polymers entrap the dyes by swelling.
• 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.
• 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.
• 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
• the pH of the treatment solution is preferably from 7 to 1 1 .
• the abbreviated component identifications have the following meanings: LAS Sodium linear C-) 2 alkyl benzene sulphonate
• SAS C -
• AEC Alkyl ethoxycarboxylate surfactant of formula
• 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
• PA 30 Polyacrylic acid of average molecular weight of approximately 8,000.
• Terpolymer Terpolymer of average molecular weight approx.
• Citric Citric Acid Perborate Anhydrous sodium perborate monohydrate (PB-1 ) bleach, empirical formula NaB ⁇ 2-H2 ⁇ 2
• 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.
• Lipase Lipolytic enzyme sold under the tradename Lipolase, Lipolase Ultra by Novo Nordisk A/S
• DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060.
• PAAC pentaamine acetate cobalt (III) sal PAAC pentaamine acetate cobalt (III) sal.
• PVP Polyvinyl pyrrolidone polymer
• PVNO Poly(4-vinylpyridine)-N-Oxide 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.
• Brightener Bightener can be, for example, Disodium 4.4'- b ⁇ s(4-an ⁇ l ⁇ no-6-morphol ⁇ no- 1 ,3.5-tr ⁇ az ⁇ n-2-yl) amino) st ⁇ lbene-2:2'-d ⁇ sulfonate, and disodium 4,4'-b ⁇ s (2-sulphostyryl) biphenyl, but is not limited to these examples.
• Brightener can be a combination of two or more brighteners.
• Granular Suds 1 2% Sihcone/sihca, 1 8% stearyl alcohol, 70% Suppressor starch in granular form
• Granular fabric cleaning compositions in accord with the invention are prepared as follows:
• Polyethyleneimine (MW 0.25 - 1.00 - -
• the level of the enzymes comprised in such composition are expressed in pure enzyme by weight of total composition.
• Granular fabric cleaning compositions in accord with the invention 1330 were prepared as follows:
• the level of the enzymes comprised in such composition are 1335 expressed in pure enzyme by weight of total composition.
• Granular fabric cleaning compositions in accord with the invention were prepared as follows:
• Zeolite A 26.0 26.0 26.0 26.0 26.0 26.0 26.0 26.0 26.0
• the level of the enzymes comprised in such composition are expressed in pure enzyme by weight of total composition.
• Granular fabric cleaning compositions in accord with the invention which are especially useful in the laundering of coloured fabrics were prepared as follows :
• Citrate 14.0 15.0 7.0 7.0
• the level of the enzymes comprised in such composition are expressed in pure enzyme by weight of total composition.
• Granular fabric cleaning compositions in accord with the invention were prepared as follows:
• 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.
• a granular fabric cleaning composition in accord with the invention which provide "softening through the wash” capability were prepared as follows:
• Zeolite A 1 5.0 15.0 1 5.0
• the level of the enzymes comprised in such composition are expressed in pure enzyme by weight of total composition. 1380
• 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:
• the level of the enzymes comprised in such composition are expressed in pure enzyme by weight of total composition.
• Heavy duty liquid fabric cleaning compositions in accord with the invention were prepared as follows:
• the level of the enzymes comprised in such composition are 1400 expressed in pure enzyme by weight of total composition.
• Syndet bar fabric cleaning compositions in accord with the invention 1405 were prepared as follows:
• the level of the enzymes comprised in such composition are expressed in pure enzyme by weight of total composition.
• the level of the enzymes comprised in such composition are 1420 expressed in pure enzyme by weight of total composition.
• Lys lie Asp Pro Leu Leu Gin Ala Arg Gin Thr Phe Ala Tyr Gly Thr 385 390 395 400
• Lys lie Asp Pro He Leu Glu Ala Arg Gin Asn Phe Ala Tyr Gly Thr 385 390 395 400

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• 1997
  • 1997-05-13 EP EP97925550A patent/EP0912688A1/de not_active Withdrawn
  • 1997-05-13 JP JP9541070A patent/JPH11511785A/ja active Pending
  • 1997-05-13 AU AU30656/97A patent/AU3065697A/en not_active Abandoned
  • 1997-05-13 CA CA002254067A patent/CA2254067A1/en not_active Abandoned
  • 1997-05-13 BR BR9710440A patent/BR9710440A/pt unknown
  • 1997-05-13 WO PCT/US1997/008104 patent/WO1997043386A1/en not_active Application Discontinuation
  • 1997-05-14 MA MA24608A patent/MA24180A1/fr unknown

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