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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3932—Inorganic compounds or complexes
• • 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
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
  • C11D1/66—Non-ionic compounds
  • C11D1/75—Amino oxides
• • 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
  • C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
• • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds

Definitions

• the present invention relates to detergent compositions comprising a cyclodextrin transferase enzyme and a detergent ingredient selected from a nonionic surfactant, a protease and/or a bleaching agent.
• Performance of a detergent product is judged by a number of factors, including the ability to remove soils. Therefore, detergent components such as surfactants, bleaching agents and enzymes, have been incorporated in detergents.
• detergent components such as surfactants, bleaching agents and enzymes.
• One of such specific example is the use of proteases, lipases, amylases and/or cellulases.
• amylase enzymes have long been recognised in detergent compositions to provide the removal of starchy food residues or starchy films from dishware or hard surfaces or to provide cleaning performance on starchy soils as well as other soils typically encountered in laundry and dishwashing applications.
• starchy materials such as amylose and amylopectin, constitute one of the major components of the soils /stains encountered in laundry, dishwashing or hard surfaces cleaning operations.
• the textile industry uses starchy materials in their textile finishing processes. Therefore, amylase enzymes have been since a long time incorporated into the detergent products for the removal of starch-containing stains.
• starch The changes taking place during retrogradation are of considerable importance in the industrial uses of starch. It is believed to be an important factor in the staling of bread and in the textural changes of other starch-containing foods, e.g. canned soups, peas, meat preparations, etc.
• Starch and retrograded starch are also found in the textile, paper and adhesives industries. Indeed, fabrics are sized with starch in the textile process. Depending on the sizing process, retrograded starch can be formed on the fabrics and might not be removed in the ulterior desizing processes.
• retrograded starch containing materials are found later onto the fabric, dishware and/or other hard surfaces to be cleaned.
• retrograded starch shows an increased resistance to hydrolysis by amylolytic enzymes, is only slightly soluble at ordinary temperatures and redispersed only with difficulty, especially if the retrograded starch has dried first and it further demonstrates a progressive increase in gel firmness.
• retrograded starch forms very stable structures and only melts at very high temperature such as 150°C for amylose, 60°C for amylopectin or 120°C for the complex amylose-lipid.
• the level and timing of retrogradation depends upon the starch type: it can vary from 10% to 90% of the starch content. It has been found that current detergent amylases have very little to no effect on retrograded starch.
• a substantial part of starch material remains indeed under the raw form even when processed within the food or textile industries.
• food stains such as rice, spaghettis, potatoes, corn, cereals, etc. retrieved on fabric, dishware and other hard surfaces contain a substantial amount of raw starch.
• a detergent composition comprising a cyclodextrin transferase enzyme and a detergent ingredient selected from a nonionic surfactant, a protease and/or a bleaching agent.
• cyclodextrin glucanotransferase have a transferase activity as well as an endo-, exo- hydrolytic activity on starch, that can be very useful in a cleaning applications.
• starch containing stains and soils comprise many lipids components as well.
• nonionic surfactant remove the lipids contained in the starch containing stains and soils and thereby facilitate the degradation of starch by the cyclodextrin glucanotransferase.
• the nonionic surfactant keeps the degraded starch in solution and prevents its redeposition onto the surface to be cleaned. It has been further surprisingly found that nonionic surfactant prevents the retrogradation of starch and therefore is very efficient if used with the cyclodextrin transferase in a pre-treatment step.
• starch containing stains and soils comprise many proteins components as well.
• protease enzyme hydrolyses the proteins contained in such complex stains and thereby induces the synergistic removal of such stains/soils with the cyclodextrin glucanotransferase.
• hydrolysed proteins/starch containing stains/soils have a lower molecular weight in the wash solution and this results in less redeposition of such hydrolysed stains/soils on the surface to be cleaned.
• bleaching agents oxidise the starch containing stains and soils.
• the oxidising action of the bleaching agent renders the starch more soluble and therefore easier to be synergistically removed by the cyclodextrin glucanotransferase and the bleaching agent. It results as well in less redeposition on the surface to be cleaned.
• a nonionic surfactant and/or protease provides synergistic malodour control. It is believed that the main origin for malodour derives from greasy material such as those entrapped within complex soils/stains. Without wishing to be bound by theory it is believed that the nonionic surfactant remove the lipids contained in the starch containing stains and soils. Similarly, the combination with a protease would increase the starch removal. This facilitates the degradation of starch by the cyclodextrin glucanotransferase.
• Cyclodextrin are known to encompass a hydrophobic cavity that can entrap hydrophobic molecules and thereby remove odorous material.
• the combined action of the nonionic surfactant and/or protease, and the cyclodextrin glucanotransferase results in more cyclodextrin produced and more entrapped odorous material removed and therefore in better malodour control.
• the oxidising action of the bleaching agent has a sanitisation effect in preventing the growth of micro-organism on the surface to be cleaned and thereby the formation of malodour.
• Cyclodextrin glucanotransferase enzymes find application in processes for the manufacture of cyclodextrins for various industrial applications, particularly in the food, cosmetic, chemical, agrochemical and pharmaceutical industries. Cyclodextrin glucanotransferases may also be used in a process for the manufacture of linear oligosaccharides, in particular linear oligosaccharides of 2 to 12 glucose units. Cyclodextrin glucanotransferases are also used for in situ generation of cyclodextrins, especially for methods of producing baked products, in methods for stabilizing chemical products during their manufacture, and in detergent compositions. Certain cyclodextrins are known to improve the quality of baked products.
• Cyclodextrins have an inclusion ability useful for stabilization, solubilization, etc.
• cyclodextrins can make oxidizing and photolytic substances stable, volatile substances non-volatile, poorly-soluble substances soluble, and odoriferous substances odorless, etc. and thus are useful to encapsulate perfumes, vitamins, dyes, pharmaceuticals, pesticides and fungicides.
• Cyclodextrins are also capable of binding lipophilic substances such as cholesterol, to remove them from egg yolk, butter, etc. Cyclodextrins also find utilization in products and processes relating to plastics and rubber, where they have been used for different purposes in plastic laminates, films, membranes, etc.
• cyclodextrins have been used for the manufacture of biodegradable plastics.
• EP 802 259 describes cyclodextrin transferases for the production of gamma- cyclodextrin.
• GB 169 902 discloses a polypeptide possessing cyclomaltodextrin glucanotransferase activity.
• JP07109488 describes detergent compositions comprising a cyclodextrin transferase for high detergency against starch and deodorising effect.
• JP07107971 describes a specific cyclodextrin glucanotransferase from Bacillus, with improved stability towards alkali.
• WO96/33267 and WO99/15633 are directed to specific novel cyclomaltodextrin glucanotransferase variants.
• the present invention relates to detergent compositions, including laundry, dishwashing, and/or hard surface cleaner compositions, comprising a cyclodextrin glucanotransferase and a detergent ingredient selected from a nonionic surfactant, a protease and/or a bleaching agent.
• Such compositions provide excellent removal of starch-containing stains and soils and malodour control; and when formulated as laundry compositions, excellent whiteness maintenance and dingy cleaning.
• the first essential element of the present invention is a cyclomaltodextrin glucanotransferase (E.C. 2.4.1.19), also designated cyclodextrin glucanotransferase or cyclodextrin glycosyltransferase, in the following termed CGTase, that catalyses the conversion of starch and similar substrates into cyclomaltodextrins via an intramolecular transglycosylation reaction, thereby forming cyclomaltodextrins, in the following termed cyclodextrins (or CD), of various sizes.
• CGTase cyclomaltodextrin glucanotransferase
• CD cyclodextrins
• cyclodextrins of 6, 7 and 8 glucose units which are termed a-, b- and g-cyclodextrins, respectively.
• cyclodextrins of 9, 10, and 11 glucose units which are termed d-, e-, and z-cyclodextrins, respectively.
• Cyclodextrins are thus cyclic glucose oligomers with a hydrophobic internal cavity. They are able to form inclusion complexes with many small hydrophobic molecules in aqueous solutions, resulting in changes in physical properties, e.g. increased solubility and stability and decreased chemical reactivity and volatility. Cyclodextrins find applications particularly in the food, cosmetic, chemical and pharmaceutical industries.
• CGT-ases have both starch-degrading activity and transglycosylation activity. Although some CGTases produce mainly a-cyclodextrins and some CGTases produce mainly b-cyclodextrins, CGTases usually form a mixture of a-, b- and g- cyclodextrins. Selective precipitation steps with organic solvents may be used for the isolation of separate a-, b- and g-cyclodextrins. To avoid expensive and environmentally harmful procedures, the availability of CGTases capable of producing an increased ratio of one particular type of cyclodextrin is desirable.
• CGTases from different bacterial sources including CGTases obtained from Bacillus, Brevibacterium, Clostridium, Corynebacterium, Klebsiella, Micrococcus, Thermoanaerobacter and Thermoanaerobacterium have been described in the literature.
• Kimura et al. Korean K, Kataoka S, Ishii Y, Takano T and Yamane K; J Bacteriol. 1987 169 4399-4402
• Kimura K, Kataoka S, Ishii Y, Takano T and Yamane K; J Bacteriol. 1987 169 4399-4402 describe a Bacillus sp. 1011 CGTase, Kaneko et al. [Kaneko T, Hamamoto T and Horikoshi K; J. Gen. Microbiol.
• EP 614971 describes a Brevibacterium CGTase, Haeckel & Bahl [Haeckel K, Bahl H; FEMS Microbiol. Lett. 1989 60 333-338] describe Clostridium thermosulfurogenes CGTase, Podkovyrov & Zeikus [Podkovyrov S M, Zeikus J G; J. Bacteriol. 1992 174 5400-5405] describe a Clostridium thermohydrosulfuricum CGTase, JP 7000183 describes a Corynebacte um CGTase, Binder et al.
• thermophilic Actinomycetes have been reported [Abelian V A, Afyan K B, Avakian Z G, Melkumyan A G and Af ⁇ kian E G; Biochemistry (Moscow) 1995 60 (10) 1223-1229].
• Biochemistry 1994 33 9929-9936 describe the effects on substrate binding and cyclization characteristics by replacements carried out at four residues in the active center of a Bacillus sp. Strain 1011 CGTase.
• a phenylalanine at position 183 has been replaced by leucine
• a tyrosine at position 195 has been replaced by alanine
• phenylalanine, leucine, threonine, valine, and tryptophan respectively
• a phenylalanine at position 259 has been replaced by leucine
• a phenylalanine at position 283 has been replaced by leucine.
• JP-A-7023781 describes CGTase variants derived from Bacillus sp. 1011 , in which a tyrosine residue at position 195 has been replaced by leucine, valine, phenylalanine and isoleucine, respectively.
• JP-A-5244945 describes CGTase variants derived from Bacillus stearothermophilus TC-91 , in which tyrosine residues at positions 222 and 286 (corresponding to positions 195 and 259, CGTase numbering) have been replaced by phenylalanine in order to increase the relative production of a- cyclodextrin to b-cyclodextrin.
• JP-A-5041985 describes CGTase variants derived from Bacillus sp. #1011 , in which histidine at residue 140 in region A, histidine at residue 233 in region B, and histidine at residue 327 in region C, respectively, have been replaced by arginine and asparagine residues, respectively.
• EP 630,967 describes CGTase variants in which a tyrosine residue at position 211 of a Bacillus sp. 290-3 CGTase (corresponding to position 195, CGTase numbering), at position
• CGT-ases for the purpose of the present invention are the gamma CGT-ases obtainable by screening bacteria for the secretion of a gamma CGT-ase as described in WO91/14770.
• CGT-ase for the purpose of the present invention are the enzymes described in WO96/33267.
• WO96/33267 describes variants of CGTases, which variants, when compared to the precursor enzyme, show increased product selectivity and/or reduced product inhibition. Accordingly WO96/33267 provides a CGTase variant derived from a precursor CGTase enzyme by substitution, insertion and/or deletion of one or more amino acid residue(s), which amino acid residue(s) holds a position close to the substrate.
• CGT-ases for the purpose of the present invention are the enzymes described in WO99/15633.
• WO99/15633 describes CGT-ase variants showing increased product specificity when compared to the wild-type enzyme, in which one or more of the amino acid residues corresponding to the following positions have been introduced by substitution and/or insertion (CGTase
• a CGTase variant of increased product specificity is a CGTase variant capable of producing an increased ratio of one particular type of cyclodextrin, when compared to the wild-type enzyme.
• one or more amino acid residues corresponding to the following positions have been introduced by substitution and/or insertion:
• CGTase variants showing an increased product specificity with respect to the production of ⁇ -cyclodextrin are provided, in which variants one or more of the amino acid residues corresponding to the following positions have been introduced by substitution and/or insertion
• CGTase variants showing an increased product specificity with respect to the production of ⁇ -cyclodextrin are provided, in which variants one or more of the amino acid residues corresponding to the following positions have been introduced by substitution and/or insertion
• CGTase variants showing an increased product specificity with respect to the production of ⁇ -cyclodextrin are provided, in which variants one or more of the amino acid residues corresponding to the following positions have been introduced by substitution and/or insertion (CGTase Numbering):
• the CGTase variant is derived from a strain of Thermoanaerobacter sp., one or more of the amino acid residues corresponding to the following positions may be introduced:
• the CGTase variant is derived from the strain Thermoanaerobacter sp. ATCC 53627, or a mutant or a variant thereof.
• CGTase variant is derived from a strain of Bacillus circulans one or more of the following amino acid residues may be introduced: (i) R47K/S145E/S146V/D147N; (ii) R47K/S145E/S146E/D147N; (iii) R47K/S145D/S146R; (iv) R47K/S145D/S146E; (v) R47K/S145E/S146V/D147N/D196H; (vi) R47K/S145E/S146E/D147N/D196H; (vii) R47K/S145E/S146V/D147N/D196H/D371 R; (viii) R47K/S145E/S146E/D147N/D196H/D371R; (ix) R47K/S145D/S146R/D196H; (x) R47K/S145D/S146E/D196H; (xi) R47K/
• W099/43793 describes variants of CGT-ase that has the ability to form linear oligosaccharides when acting on starch.
• Such CGT-ase variant has a modification of at least one amino acid residue in a region corresponding to residues 40-43, 78- 85, 136-139, 173-180, 189-195 or 259-268 of SEQ ID NO: 1 of W099/43793.
• Each modification may be an insertion, a deletion or a substitution, of one or more amino acid residues in the region indicated.
• the modification of the parent CGT-ase is preferably such that the resulting modified amino acid or amino acid sequence more closely resembles the corresponding amino acid or structural region in Novamyl.
• Modifications in the region 259-268 preferably include deletion of 1-3 amino acid, e.g. two.
• the region may be modified so as to correspond to Novamyl
• the CGT-ase variant may comprise further modifications in other regions, e.g. regions corresponding to amino acids 37-39, 44-45, 135, 140-145, 181-186, 269- 273, or 377-383 of Novamyl.
• Additional modifications of the amino acid sequence may be modeled on a second CGT-ase, i.e. an insertion of or substitution with an amino acid found at a given position in the second CGT-ase, or they may be made close to the substrate (less than 8 A from the substrate, e.g. less than 5 A or less than 3 A) as described in W096/33267.
• W099/43793 further describes Novamyl variants having the CGT-ase properties required within the present invention.
• Such Novamyl variant has as well the ability to form cyclodextrin when acting on starch and has a modification of at least one amino acid residue in the same regions described above for CGT-ase variants.
• the modifications are preferably in the opposite direction, i.e. such that the resulting modified amino acid or amino acid sequence more closely resembles the corresponding amino acid or structural region of a CGT-ase.
• the modification may be an insertion of or a substitution with an amino acid present at the corresponding position of a CGT-ase, or a deletion of an amino acid not present at the corresponding position of a CGT-ase.
• Preferred modifications include a deletion in the region 190-195, preferably the deletion (191-195) and/or a substitution of amino acid 188 and/or 189, preferably F188L and/or Y189Y.
• the detergent compositions of the present invention comprising a nonionic surfactant, provide synergistic removal of starch from fabrics, dishware and other hard surfaces.
• the nonionic surfactant adsorbs onto the granular surface of the starch thereby disrupting the starch structure and influencing and preventing the retrogradation process of the starch.
• Such disruption of the structure increases the CGT-ase accessibility to its substrate.
• nonionic surfactants can be used also in a pre-treatment process and therefore can reduce the retrogradation process of starch.
• the starch-containing stains / soils is more easily hydrolysed by the enzyme and a synergistic breakdown of the starch soil by the CGT-ase and the nonionic surfactant occurs.
• the nonionic surfactant for use in the present invention may also comprise an alkyl ester of a fatty acid.
• These nonionic surfactants include those having the formula: R 9 COO(R ' ' 0 ) wherein R is an alkyl group containing from 7 to 21 , preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and R ⁇ ° is a C-
• Preferred alkylpolyglycosides have the formula
• R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
• the glycosyl is preferably derived from glucose.
• Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 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 oxides containing one alkyl moiety of from about 10 to about 18 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 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
• Semi-polar nonionic detergent surfact are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl mo
• R 3 (OR4)XN(R5)2 wherein R 8 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R ⁇ 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 ⁇ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
• nonionic surfactants for the purpose of the present invention are the co-surfactant selected from the group of primary or tertiary amines.
• Suitable primary amines for use herein include amines according to the formula R-1NH2 wherein R-j is a C6-C12, preferably CQ-C- Q alkyl chain or R4X(CH2)n.
• X is -O-,- C(0)NH- or -NH- >
• R4 is a C6-C-12 alkyl chain n is between 1 to 5, preferably 3.
• 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-hexylamine, 1- octylamine, 1-decylamine 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 R-i R2R3N wherein R1 and R2 are C-j-Cs alkylchains or — ( CH 2 — CH ⁇ ) x H
• R3 is either a C6-C12, 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 is between 1 to 5, preferably 2-3.
• R5 is H or C-1-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 R1 R2R3N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1 -C3 alkyl or
• is Cg-C- ⁇ alkyl; n is 2-4, preferably n is 3; R2 and R3 is C1-C4
• Most preferred amines of the present invention include 1-octylamine, 1- hexylamine, 1-decylamine, 1-dodecylamine,C8-10oxypropylamine, N coco 1- 3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-10 amidopropyldimethylamine and C10 amidopropyldimethylamine.
• a second essential element of the detergent compositions of the present invention can be a protease enzyme.
• the starch containing stains and soils comprise many proteins components as well.
• the protease enzyme hydrolyses the proteins contains in such complex stains and thereby induces the synergistic removal of such stains/soils with the CGT-ase.
• such hydrolysed complex stains/soils have a lower molecular weight in the wash solution and therefore it results in less redeposition of such hydrolysed complex stains on the surface to be cleaned.
• proteases include ALCALASE®, DURAZYM® and SAVINASE® (protease Subtilisin 309 from Bacillius subtilis) from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades.
• Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO92/03529 A to Novo.
• a protease having decreased adsorption and increased hydrolysis is available as described in WO95/07791 to Procter & Gamble.
• a recombinant trypsin-like protease for detergents suitable herein is described in W094/25583 to Novo.
• Other suitable proteases are described in EP 516 200 by Unilever.
• Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in EP 251 446, filed April 28, 1987 (particularly the variant Y217L described on pages 17, 24 and 98), and which is called herein "Protease B”, and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protealytic enzyme which is called "Protease A” herein.
• proteases for the purpose of the present invention are the proteolytic enzymes sold under the tradename Savinase by Novo Nordisk A/S, the "Protease B” variant with the substitution Y217L described in EP 251 446, "the "protease D” variant with the substitution set N76D/S103A ⁇ /104I and the protease described in WO99/20727, WO99/20726 and WO99/20723 with the amino acid substitution set 101 G/103A/1041/159D/232V/236H/245R/248D/252K.
• Preferred bleaching agents for the detergent compositions of the present invention are the combination of percarbonate with a bleach activator selected from nonanoyloxybenzene-sulfonate (NOBS), Phenolsulfonate ester of N- nonanoyl-6-aminocaproic acid (NACA-OBS), and/or tetraacetylethylenediamine (TAED). Also preferred are the bleaching agents referred to as [Mn(Bcyclam)CI 2 ].
• Suitable bleaching agents for the purpose of the present invention include hydrogen peroxide, PB1, PB4 and percarbonate with a particle size of 400-800 microns.
• These bleaching 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 0.1 % to 30%, preferably 1% to 20% .
• 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-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
• Such bleaching agents are disclosed in U.S. Patent 4,483,781 , U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934.
• Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551.
• bleaching agents that can be used encompasses the halogen bleaching agents.
• hypohalite bleaching agents include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1-5% by weight.
• R-j is a 07-0-13 linear or branched chain saturated or unsaturated alkyl group
• R2 is a C-i-Cg linear or branched chain saturated or unsaturated alkyl group
• R3 is a C-1-C4 linear or branched chain saturated or unsaturated alkyl group.
• Those bleach activators are generally used within the detergent compositions of the present invention at a level of 0.1-10%, preferably 0.5-5% by weight of the detergent composition.
• bleaching agents including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds for use in detergent compositions according to the invention are described in our co- pending applications WO95/10592, WO97/00937, W095/27772, W095/27773, W095/27774 and W095/27775.
• transition metal bleach catalysts being complexes of a transition metal and a cross bridged macropolycyclic ligands such as described in Procter & Gamble patent applications WO98/39405, WO98/39406 and WO98/39098.
• Such transition -metal bleach catalyst can be prepared according to Procter & Gamble patent application W098/39335 or according to J.Amer.Chem.So ⁇ , (1990), 112, 8604. These bleach catalysts are generally encompassed in the detergent compositions of the present invention at a level of 0.0007-0.07%, preferably 0.005-0.05% by weight of the detergent compositions.
• Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
• One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. 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 phthalocyanine is activated and, consequently, the substrate is bleached.
• Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718.
• detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.
• bleaching species for the purpose of the present invention are a colour-safe bleach boosters that may be used in conjunction with a peroxygen source in a bleaching composition.
• the bleach booster is generally present in the detergent compositions at a level of from 0.01-10% and more preferably from 0.05-5% by weight of the composition.
• Bleach boosters to be included in the detergent compositions of the present invention comprise zwitterionic imines, anionic imine polyions having a net negative charge of from about -1 to about -3, and mixtures thereof.
• Suitable imine bleach boosters of the present invention include those of the general structure: (I)
• R " I -R4 may be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl radicals except that at least one of R1-R4 contains an anionically charged moiety.
• Preferred bleach boosters are the anionically charged moiety bonded to the imine nitrogen described in WO97/10323. Also preferred are the trkcyclic oxaziridinium compounds described in US 5,710,116 and the bleach boosters described in W098/16614. These can be prepared in accordance with the method described in WO97/10323 and/or W098/16614.
• the detergent compositions of the present invention will preferably comprise a further enzyme selected from a protease, a lipase, an ⁇ -amylase, a maltogenic alpha-amylase and/or an amyloglucosidase; and/or a bleaching agent.
• the present invention relates to a laundry and/or fabric care composition
• a laundry and/or fabric care composition comprising a CGT-ase and a detergent ingredient selected from a nonionic surfactant, a protease and/or a bleaching agent (Examples 1-17).
• the present invention relates to dishwashing or household cleaning compositions (Examples 18-23).
• compositions of the invention may for example, be formulated as hand and machine dishwashing compositions, hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pre-treatment of stained fabrics, rinse added fabric softener compositions, and compositions for use in general household hard surface cleaning operations.
• hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pre-treatment of stained fabrics, rinse added fabric softener compositions, and compositions for use in general household hard surface cleaning operations.
• the compositions of the invention preferably contain a surfactant and preferably other detergent compounds selected from organic polymeric compounds, suds enhancing agents, group II metal ions, solvents, hydrotropes and additional enzymes.
• compositions suitable for use in a laundry machine washing method preferably contain both a 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 suspension and anti-redeposition agents and corrosion inhibitors.
• Laundry compositions can also contain softening agents, as additional detergent components.
• Such compositions containing a nonionic surfactant and a CGT-ase provide starch-containing stain removal, whiteness maintenance and dingy cleaning when formulated as laundry detergent compositions.
• compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
• the detergent compositions according to the invention can be liquid, paste, gels, bars, tablets, spray, foam, powder or granular. Granular compositions can also be in "compact” form and the liquid compositions can also be in a "concentrated” form. If needed the density of the laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 500 to 950 g/litre of composition measured at 20°C.
• compositions herein are best reflected by density and, in terms of composition, by the 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 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition.
• the inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides. A preferred filler salt is sodium sulphate.
• Suitable detergent compounds for use herein are selected from the group consisting of the below described compounds.
• the surfactant is 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 30% by weight of detergent compositions in accord with the invention.
• the surfactant is preferably formulated to be compatible with enzyme components present in the composition. In liquid or gel compositions the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.
• Anionic surfactants Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C ⁇ - C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
• alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:
• R 8 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
• R4 is a C-i-C ⁇ hydrocarbyl, preferably an alkyl, or combination thereof
• 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 8 is C ⁇ Q-C ⁇ Q alkyl
• R4 is methyl, ethyl or isopropyl.
• the methyl ester sulfonates wherein R 8 is C-io-C-ig alkyl.
• alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a
• C10-C24 hydrocarbyl preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C-12-C18 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.
• an alkali metal cation e.g. sodium, potassium, lithium
• ammonium or substituted ammonium e.g.
• alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
• alkyl chains of C12-C16 are preferred for lower wash temperatures (e.g. below about 50°C) and C-
• anionic surfactants useful for detersive purposes can also be included in the 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 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.
• salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
• C8-C22 primary of secondary alkanesulfonates C8-C24 olefinsulfonates
• sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of
• alkylpolyglycolethersulfates (containing up to 10 moles of ethylene 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-
• 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 anionic surfactants.
• Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m S03M wherein R is an unsubstituted C-10-C24 alkyl or hydroxyalkyl group having a C-jrj-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C-12- C-
• Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
• Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations 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 C-12-C18 alkyl polyethoxylate (1.0) sulfate (C-i2-C-
• Cationic surfactants suitable for use in the detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
• Examples of such cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula :
• R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
• each R 3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH 2 CH(CH2 ⁇ H)-, -CH 2 CH2CH 2 -, and mixtures thereof
• each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups, - CH2CHOH-CHOHCOR6CHOHCH2OH wherein R 6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0
• R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R 5 is not more than about 18
• each y is from 0 to about 10 and the sum of the
• Quaternary ammonium surfactant suitable for the present invention has the formula (I):
• R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (II) :
• y is 2-4, preferably 3. 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 (01 -C3) or alkoxylated alkyl of the formula III,
• X" is a counterion, preferably a halide, e.g. chloride or methylsulfate.
• R6 is C-
• Preferred quat ammonium surfactants are those as defined in formula I whereby R-1 is C8, C-
• Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula: R ⁇
• R-i is CQ-C- Q alkyl
• each of R2, R3 and R4 is independently C-1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4o) x H where x has a value from 2 to 5, and X is an anion.
• R2, R3 or R4 should be benzyl.
• is C-
• Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
• Suitable quaternary ammonium compounds of formulae (i) for use herein are: coconut trimethyl ammonium chloride or bromide; coconut methyl di hydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C-12-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide; choline esters (compounds of formula (i) wherein R-j is CH2-CH2-O-C-C12-14 alkyl and R2R3R4 are methyl).
• Typical cationic fabric softening components include the water-insoluble quaternary-ammonium fabric softening actives or their corresponding amine precursor, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate.
• Preferred cationic softeners among these include the following: 1) ditallow dimethylammonium chloride (DTDMAC);
• DSOEDMAC di(stearoyloxyethyl) dimethylammonium chloride
• Biodegradable quaternary ammonium compounds have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlorides and methyl sulfates. Such quaternary ammonium compounds contain long chain alk(en)yl groups interrupted by functional groups such as carboxy groups. Said materials and fabric softening compositions containing them are disclosed in numerous publications such as EP-A-0,040,562, and EP-A-0,239,910.
• Q is selected from -O-C(O)-, -C(0)-0-, -O-0(O)-O-, -NR4-C(0)-, -C(0)- NR 4 -;
• R 2 is (CH 2 )m-Q-T4 or T5 or R 3 ;
• R 3 is C1-C4 alkyl or C-J-C4 hydroxyalkyl or H;
• R4 is H or C1-C4 alkyl or C-1-C4 hydroxyalkyl;
• T1 , T 2 , T 3 , T 4 , T 5 are independently C-
• n and m are integers from 1 to 4; and
• X- is a softener-compatible anion.
• softener-compatible anions include chloride or methyl sulfate.
• the alkyl, or alkenyl, chain T ⁇ , T 2 , T 3 , ⁇ 4, T ⁇ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.
• the chain may be straight or branched.
• Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material.
• the compounds wherein T " ! , T 2 , T 3 , T 4 , T 5 represents the mixture of long chain materials typical for tallow are particularly preferred.
• quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include:
• the detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8% by weight of such cationic surfactants.
• Ampholytic surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines 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 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.
• the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.
• Zwitterionic surfactants are also suitable for use in detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants. When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such zwitterionic surfactants.
• the detergent compositions of the present invention can comprise in addition to the CGT-ase, one or more enzymes which provide cleaning performance, fabric care and/or sanitisation benefits.
• Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, mannanases, xyloglucanases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ - glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
• the detergent compositions of the present invention will further > comprise an enzyme selected from a lipase, an ⁇ -amylase, a maltogenic alpha- amylase and/or an amyloglucosidase.
• an enzyme selected from a lipase, an ⁇ -amylase, a maltogenic alpha- amylase and/or an amyloglucosidase it has been found that the combination of the CGT-ase with an alpha-amylase, a maltogenic alpha-amylase and/or an amyloglucosidase within the detergent compositions of the present invention, provides an improved removal of raw and/or retrograded starch.
• the stains most commonly encountered in laundry, dishwashing and hard surface cleaning generally comprise a significant amount of proteins and triglyceride compounds.
• starch materials are usually associated with lipid compounds.
• the detergent compositions of the present invention provides an improved removal of such complex stains.
• the detergent compositions comprising such combination of enzymes provide enhanced removal of starch-containing stains and soils and when formulated as a laundry detergent composition, enhanced whiteness maintenance and dingy cleaning.
• the detergent compositions of the present invention will preferably comprise an ⁇ -amylase.
• Suitable ⁇ -amylases for the purpose of the present invention are described in the following : WO94/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1995.
• 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.
• amylases are stability- enhanced amylases described in W094/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, W095/26397 and W096/23873 (all by 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 of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ - amylase activity assay.
• the variants are those demonstrating improved thermal stability, more preferably those wherein at least one amino acid residue equivalent to F180, R181 , G182, T183, G184, or K185 has been deleted from the parent ⁇ -amylase.
• Particularly preferred are those variants having improved thermal stability which comprise the amino acid deletions R181 * + G182 * or T183 * + G184 * .
• Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermal stability and a higher activity level are described in W095/35382.
• Further suitable amylases are the H mutant ⁇ -amylase enzymes exhibiting improved stability described in WO98/26078 by Genencor.
• amylolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001 % to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.
• Classification EC 3.2.1.133 that hydrolyse 1 ,4- ⁇ -D-glucosidic linkages in polysaccharides so as to remove successive alpha-maltose units from the nonreducing ends of the chains.
• Suitable maltogenic alpha-amylases are described in EP 120 639, W099/43793 and W099/43794.
• Commercially available maltogenic alpha-amylase is the enzyme product sold under the tradename Novamyl by Novo Nordisk A/S.
• Such maltogenic alpha-amylase is generally comprised in the detergent compositions at a level of from 0.0002% to 10%, preferably 0.001 % to 2%, more preferably 0.001% to 1 % pure enzyme by weight of the total detergent composition.
• Amyloglucosidase Another preferred further enzyme are the amyloglucosidase classified under the IUPAC Classification as EC 3.2.1.3.
• amyloglucosidase is a glucan 1 ,4- ⁇ - glucosidase; is also referred to as "glucoamylase, ⁇ -amylase, lysosomal ⁇ - glucosidase, acid maltase or exo-1 ,4- ⁇ -glucosidase" and its systematic name is 1 ,4- ⁇ -D-glucan glucohydrolase.
• Suitable amyloglucosidase are described in WO92/00381 , WO00/04136 and W099/28448.
• amyloglucosidases are the enzyme products sold under the tradename PALKODEX by MAPS; AMG300L by Novo Nordisk A/S, Optimax 7525 (Combinations of enzymes including amyloglucosidase) and Spezyme by Genencor. Further commercial available amyloglucosidases are those from Aspergillus niger obtainable from the following companies: Ambazyme, Amano, Boehringer, Fluka, Sigma, Aldomax, Genzyme, Nagase, UOP.
• amyloglucosidases from Aspergillus species from the companies Biocatalysts or Danisco and the amyloglucosidases from Rhizopus delemar from Nagase; from Rhizopus niveus from Amano, ION, Seikagaku; from Rhizopus oryzae from Enzyme Development Co-operation.
• Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as 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 "Amano-P".
• 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.
• lipases such as M1 Lipase ⁇ an d LipomaxR (Gist-Brocades) and Lipolase ⁇ and Lipolase UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention.
• lipolytic enzymes described in EP 258 068, WO92/05249 and W095/22615 by Novo Nordisk and in WO94/03578, W095/35381 and WO96/00292 by Unilever.
• 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); WO90/09446 (Plant Genetic System) and W094/14963 and W094/14964 (Unilever).
• the lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of pure enzyme by weight of the detergent composition.
• the cellulases usable in the present invention include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and a specific activity above 50 CEVU/mg (Cellulose Viscosity Unit).
• Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
• EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and W095/26398.
• cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM
• Suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ⁇ 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243.
• suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801 , Genencor, published September 29, 1994. Especially suitable cellulases are the cellulases having color care benefits.
• cellulases examples include cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also W091/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, W096/17994 and W095/24471. Said cellulases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
• Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule. 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 chloro- and bromo-peroxidase.
• Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme. Enhancers are generally comprised at a level of from 0.1 % to 5% by weight of total composition.
• Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4- carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10- methylphenoxazine (described in W094/12621 ) and substitued syringates (C3- C5 substitued alkyl syringates) and phenols.
• Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
• Said peroxidases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of pure enzyme by weight of the detergent composition.
• the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic/et ⁇ ). Purified or non-purified forms of these enzymes may be used.
• the variants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased.
• the variant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme variant is tailored to suit the particular cleaning application.
• the isoelectric point of such enzymes may be modified by the substitution of some charged amino acids, e.g. an increase in isoelectric point may help to improve compatibility with anionic surfactants.
• the stability of the enzymes may be further enhanced by the creation of e.g. additional salt bridges and enforcing calcium binding sites to increase chelant stability. Special attention must be paid to the cellulases as most of the cellulases have separate binding domains (CBD). Properties of such enzymes can be altered by modifications in these domains.
• the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
• enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on January 31 , 1992.
• enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
• a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO93/07263 A and WO93/07260 A to Genencor International, WO89/08694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101 ,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261 ,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilised by various techniques.
• Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971 , Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
• Fabric softening agents can also be incorporated into detergent compositions in accordance with the present invention. These 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 5,019,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-B0 011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di- long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.
• Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15% 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 weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1 % to 2%, normally from 0.15% 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 solid components of the composition.
• compositions according to the present invention may further comprise a builder system.
• a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl- succinic acid and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine 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 (Na 2 Si 2 0 5 ).
• Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian 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, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
• Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241 , lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1 ,1 ,3-propane tricarboxylates described in British Patent No. 1 ,387,447.
• Polycarboxylates containing four carboxy groups include oxydisuccinates 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 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.
• Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates, 2,2,5,5- tetrahydrofuran - tetracarboxylates, 1 ,2,3,4,5,6-hexane -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.
• the preferred polycarboxylates are hydroxycarboxylates 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 such as citric acid.
• Other 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.
• Preferred builder systems for use in liquid detergent compositions of the present invention are soaps and polycarboxylates.
• builder materials that can form part of the builder system for use in granular compositions include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
• suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
• Polymers of this type are disclosed in GB-A-1 ,596,756. Examples of such salts ' are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
• Detergency builder salts are normally included in amounts of from 5% to 80% by weight of the composition preferably from 10% to 70% and most usually from 30% to 60% by weight.
• the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
• chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
• Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
• Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
• Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5-disulfobenzene.
• EDDS ethylenediamine disuccinate
• [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
• compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.
• MGDA water-soluble methyl glycine diacetic acid
• these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by weight of such compositions.
• a suds suppressor exemplified by silicones, and silica-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 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.
• the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or 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 Application DTOS 2 646 126 published April 28, 1977.
• An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer.
• Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl- alkanols are 2-butyl-octanol which are commercially available under the trade name Isofol 12 R.
• Such suds suppressor system are described in Copending European Patent application N 92870174.7 filed 10 November, 1992.
• compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as AerosilR.
• 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.
• detergent compositions may be employed, such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and/or encapsulated or non- encapsulated perfumes.
• suitable encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1 ,464,616.
• Other suitable water soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as described in US 3,455,838. These acid-ester dextrins 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 monofu notional substituted groups such as 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 anhydride- acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl 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 from 1 % to 6% by weight of the composition.
• Preferred optical brighteners are anionic in character, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino- stilbene-2:2' - disulphonate, disodium 4,4' - bis-(2,4-dianilino-s-triazin-6- ylamino)stilbene-2:2" - disulphonate, monosodium 4',4" -bis-(2,4-dianilino-s-tri- azin-6 ylamino)stilbene-2-sulphonate, disodium 4,4' -bis-(2-anilino-4-(N-methyl-N- 2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'
• polyethylene glycols particularly those of molecular weight 1000-10000, 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 glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula
• PEG is -(O ⁇ 2H4)0-,PO is (OC3H6O) and T is (pcOCe ⁇ CO).
• modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2 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.
• some copolymers will be 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 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and have a molecular weight of about 3.000.
• the polyesters and their method of preparation are described in detail in EPA 311 342.
• 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 detergent enzymes.
• Compositions comprising chlorine scavenger are described in the European patent application 92870018.6 filed January 31 , 1992.
• Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(CH2 ⁇ H2 ⁇ ) m (CH2) n CH3 wherein m is 2-3 and n is 6-12. The side- chains are ester-linked to the polyacrylate "backbone” to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.
• the detergent composition of the present invention can also contain dispersants: Suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1 ,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 1 ,000 to 100,000. 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 present invention.
• compositions of the invention may contain a lime soap peptiser compound, which has preferably a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6.
• LSDP lime soap dispersing power
• the lime soap peptiser compound is preferably present at a level from 0% to 20% by weight.
• LSDP lime soap dispersant power
• Surfactants having good lime soap peptiser capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.
• Exemplary surfactants having a LSDP of no more than 8 for use in accord with the present invention include C ⁇ Q-C ⁇ Q dimethyl amine oxide, C-
• Polymeric lime soap peptisers suitable for use herein are described in the article by M.K. Nagarajan, W.F. Masler, to be found in Cosmetics and Toiletries, volume 104, pages 71-73, (1989).
• Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6- aminohexanoyrjbenzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic bleach formulations can also be used as lime soap peptisers compounds.
• the detergent compositions 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 operations involving colored fabrics.
• 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 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 articles in the wash.
• 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. Addition of such polymers also enhances the performance of the enzymes according the invention. a) Polyamine N-oxide polymers
• polyamine N-oxide polymers suitable for use contain units having the following structure formula : P
• A is NO, CO, C, -0-,-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-0 group can be attached or wherein the nitrogen of the N-O group is part of these groups.
• the N-0 group can be represented by the following general structures:
• R1 , 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-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.
• the N-0 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-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
• polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-0 group forms part of the R-group.
• Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
• Another class of said polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-0 group is attached to the R-group.
• polyamine N-oxides are the polyamine oxides whereto the N-0 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-0 functional group is part of said R group.
• R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
• polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
• polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups.
• 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 polyvinyls, polyalkylenes, 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 :1000000.
• the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation.
• the ratio of amine to amine N-oxide is from 2:3 to 1 :1000000. More preferably from 1 :4 to 1:1000000, most preferably from 1 :7 to 1 :1000000.
• 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 ⁇ 10, 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.
• the average molecular weight is within the range of 500 to 1000,000; preferably from 1 ,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
• N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1 ,000,000, preferably from
• Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole N- vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 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 113,"Modern
• N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000; more preferably from
• N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance 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 15,000.
• PVP polyvinylpyrrolidone
• Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
• polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A- 256,696).
• the detergent compositions of the present invention may also utilize polyvinyloxazolidone 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 from about 5,000 to about 15,000.
• Polyvinylimidazole The detergent compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average 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 15,000.
• Cross-linked polymers are polymers whose backbone are 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.
• the cross-linked polymers are made in such a 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.
• Such cross-linked polymers are described in the co-pending patent application 94870213.9
• compositions of the invention may be used in essentially any washing or cleaning methods, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate rinse aid composition may be added.
• a conventional laundry method comprises treating soiled fabric with an aqueous liquid having dissolved or dispensed therein an effective amount of the laundry detergent and/or fabric care composition.
• a preferred machine dishwashing method comprises treating soiled articles with an aqueous liquid having dissolved or dispensed therein an effective amount of the machine diswashing or rinsing composition.
• a conventional effective amount of the machine dishwashing composition means from 8-60 g of product dissolved or dispersed in a wash volume from 3-10 litres.
• soiled dishes are contacted with an effective amount of the diswashing composition, typically from 0.5-20g (per 25 dishes being treated).
• Preferred manual dishwashing methods include the application of a concentrated solution to the surfaces of the dishes or the soaking in large volume of dilute solution of the detergent composition.
• a conventional hard surface method comprises treating soiled hard items with e.g. a sponge, brush, clothe, etc. with an aqueous liquid having dissolved or dispensed therein an effective amount of the hard surface cleaner and/or with such composition undiluted. It also encompasses or the soaking in a concentrated solution or in a large volume of dilute solution of the detergent composition.
• the process of the invention is conveniently carried out in the course of the cleaning process.
• the method of cleaning is preferably carried out at 5°C to 95°C, especially between 10°C and 60°C.
• the pH of the treatment solution is preferably from 7 to 12.
• the enzymes levels are expressed by pure enzyme by weight of the total composition and unless otherwise specified, the detergent ingredients are expressed by weight of the total compositions.
• the abbreviated component identifications therein have the following meanings:
• Plurafac LF404 being an alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5.
• MBAS C12-18 mid branched alkyl sulphate surfactant with an average branching of 1.5 methyl or ethyl branching groups
• MES x-Sulpho methylester of 018 fatty acid APA C ⁇ -10 amido propyl dimethyl amine.
• Na-i2(A1 ⁇ 2Si ⁇ 2)i2- 2 ?H2 ⁇ having a primary particle size in the range from 0.1 to 10 micrometers (Weight expressed on an anhydrous basis).
• Citric Anhydrous citric acid Citric Anhydrous citric acid.
• TSPP Tetrasodium pyrophosphate
• MA/AA 1 Random copolymer of 6:4 acrylate/maleate, average molecular weight about 10,000.
• Polycarboxylate Copolymer comprising mixture of carboxylated monomers such as acrylate, maleate and methyacrylate with a MW ranging between 2,000-80,000 such as
• Sokolan commercially available from BASF, being a copolymer of acrylic acid, MW4,500.
• Percarbonate Anhydrous sodium percarbonate of nominal formula a2C ⁇ 3.3H2 ⁇ 2 .
• NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
• NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate.
• LOBS Dodecanoyloxybenzene sulfonate in the form of the Na salt.
• DOBA Dodecanoylbenzoic acid DTPA Diethylene triamine pentaacetic acid. HEDP 1 ,1-hydroxyethane diphosphonic acid. DETPMP Diethyltriamine penta (methylene) phosphonate, marketed by Monsanto under the Trade name Dequest
• MnTACN Manganese 1 ,4,7-trimethyl-1 ,4,7-triazacycIononane.
• PAAC Pentaamine acetate cobalt(lll) salt PAAC Pentaamine acetate cobalt(lll) salt.
• Amylase Amylolytic enzyme sold under the tradename Termamyl ® and Duramyl® available from Novo Nordisk A S and those variants having improved thermal stability with amino acid deletions R181 * + G182 * or T183 * + G184 * as described in W095/35382.
• Lipase Lipolytic enzyme sold under the tradename Lipolase, Lipolase Ultra by Novo Nordisk A/S and Lipomax by Gist- Brocades.
• PVNO Polyvinylpyridine-N-Oxide with an average molecular weight of 50,000.
• PVPVI Copolymer of vinylimidazole and vinylpyrrolidone with an average molecular weight of 20,000.
• Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
• Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2- yl) stilbene-2:2'-disulfonate.
• Brightener 3 Disodium 4,4'bis (4,6-dianilino-1 ,3,5-triazin-2-yl)amino stilbene-2-2'-disulfonate.
• SRP 1 Anionically end capped poly esters.
• SRP2 Soil Release Polymer selected from 1 ) Non-cotton soil release polymer according to U.S. Patent 5,415,807,
• PEI Polyethyleneimine with an average molecular weight of between 600-1800 and an average ethoxylation degree of 7-20 ethyleneoxy residues per nitrogen.
• HMWPEO High molecular weight polyethylene oxide.
• PEGX Polyethylene glycol, of a molecular weight of X
• Brightener 1 or 2 or 3 0.05 0.05 0.05 - 0.05
• Brightener 1 or 2 or 3 0.2 0.2 0.3 0.1 0.2
• Enzymes (cellulase, amylase, 0.04 0.01 0.02 0.02 0.05 protease and/or lipase)
• Brightener 1 0.2 0.2 0.2 0.2 0.2
• Brightener 1 0.05 - - 0.05
• Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0
• Brightener 2 0.3 0.2 0.3 - 0.1 0.3
• Brightener 1 0.2 0.2 0.2 0.2 0.2
• Enzymes (amylase, cellulase - - - 0.05 0.04 0.05 and/or protease)
• Enzymes (amylase, cellulase, - 0.025 - 0.04 protease and/or lipase)
• laundry detergent compositions in the form of a tablet or granular formulation were prepared according to the present invention :
• Enzymes (amylase, cellulase, 0.04 0.04 0.01 0.02 0.02 0.03 protease and/or lipase)
• PVPVI/PVNO brightener, photo-bleach, speckles,...
• laundry detergent compositions were prepared according to the present invention :
• Enzymes (amylase, cellulase, - - - - 0.045 protease and/or lipase)
• PVP PVPVI/PVNO
• speckles brightener, photo-bleach,...
• liquid laundry detergent compositions were prepared according to the present invention :
• Brightener 3 0.20 0.15 0.10 0.05 - 0.05
• Example 10 The following non-aqueous liquid detergent compositions were prepared in accordance with the present invention :
• Titanium Dioxide 0.5 0.5 0.5
• a detergent base powder of composition I was prepared as follows: all the particulate material of base composition I were mixed together in a mixing drum to form a homogenous particulate mixture. During this mixing, the spray- ons were carried out.
• Tablets were then made the following way: 50g of the matrix was introduced into a mould of circular shape with a diameter of 5.5 cm, and compressed to give a tablet tensile strength (or diametrical fracture stress) of 10kPa.
• the tablets were then dipped in a bath comprising 90 parts of sebacic acid and 10 parts per weight of Nymcel-ZSB16TM by Metsa Serla at 140 °C. The time the tablet was dipped in the heated bath was adjusted to allow application of 4g of the bath mixture. The tablet was then left to cool at ambient temperature of 25°C for 24 hours. The tensile strength of the coated tablet was increased to a tensile strength of 30 kPa.
• Anionic agglomerates 1 (40% anionic, 27% zeolite and 33% 21.5 carbonate)
• Anionic agglomerates 2 (40% anionic, 28% zeolite and 32% 13.0 carbonate)
• Bleach activator agglomerates (81% TAED, 17% acrylic/maleic 5.5 copolymer (acid form) and 2% water)
• EDDS/Sulphate particle (58% of EDDS, 23% of sulphate and 19% 0.5 water)
• Photoactivated bleach (Zinc phthalocyanine sulphonate 10% active) 0.02
• Binder spray-on system (25% of Lutensit K-HD 96;75% by weight of 4.0 PEG)
• laundry detergent compositions in the form of a tablet were prepared according to the present invention :
• Brightener 1 or 2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
• Example 13 The following laundry bar detergent compositions were prepared according to the present invention (Levels are given in parts per weight, enzyme are expressed in pure enzyme) :
• Example 14 The following granular fabric detergent compositions which provide "softening through the wash” capability were prepared according to the present invention :
• Coco-alkyl-dimethyl hydroxy1.4 1.0 ethyl ammonium chloride Citrate 5.0 3.0 Na-SKS-6 - 1 1.0 Zeolite A 15.0 15.0 MA/AA 4.0 4.0 DETPMP 0.4 0.4 PB1 15.0 -
• the following rinse added fabric softener composition was prepared according to the present invention :

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• Chemical & Material Sciences (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
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• Inorganic Chemistry (AREA)
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• Enzymes And Modification Thereof (AREA)
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• 2000
  • 2000-06-30 WO PCT/US2000/018119 patent/WO2002002725A1/en not_active Application Discontinuation
  • 2000-06-30 MX MXPA03000119A patent/MXPA03000119A/es unknown
  • 2000-06-30 EP EP00946947A patent/EP1294844A1/en not_active Withdrawn
  • 2000-06-30 CA CA002412371A patent/CA2412371A1/en not_active Abandoned
  • 2000-06-30 HU HU0300967A patent/HUP0300967A2/hu unknown
  • 2000-06-30 AU AU2000260630A patent/AU2000260630A1/en not_active Abandoned
  • 2000-06-30 CZ CZ20024166A patent/CZ20024166A3/cs unknown
  • 2000-06-30 JP JP2002507969A patent/JP2004502831A/ja not_active Withdrawn
  • 2000-06-30 BR BR0017277-4A patent/BR0017277A/pt not_active IP Right Cessation
  • 2000-06-30 CN CNA008198586A patent/CN1531587A/zh active Pending

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