WO1999057154A1 - Compositions respectant les tissus et comprenant des domaines liant la cellulose - Google Patents

Compositions respectant les tissus et comprenant des domaines liant la cellulose Download PDF

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Publication number
WO1999057154A1
WO1999057154A1 PCT/US1998/008857 US9808857W WO9957154A1 WO 1999057154 A1 WO1999057154 A1 WO 1999057154A1 US 9808857 W US9808857 W US 9808857W WO 9957154 A1 WO9957154 A1 WO 9957154A1
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WO
WIPO (PCT)
Prior art keywords
cbd
fabric care
amino acid
fabric
softening
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PCT/US1998/008857
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English (en)
Inventor
Andre Cesar Baeck
Johan Smets
Stanton Lane Boyer
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The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU72755/98A priority Critical patent/AU7275598A/en
Priority to PCT/US1998/008857 priority patent/WO1999057154A1/fr
Priority to ARP990102046A priority patent/AR015282A1/es
Priority to BR9910100-9A priority patent/BR9910100A/pt
Priority to CN 99808137 priority patent/CN1308638A/zh
Priority to CA002326372A priority patent/CA2326372A1/fr
Priority to MA25562A priority patent/MA24905A1/fr
Priority to EP99918913A priority patent/EP1073684A1/fr
Priority to AU36718/99A priority patent/AU3671899A/en
Priority to PCT/US1999/009410 priority patent/WO1999057156A1/fr
Priority to US09/674,477 priority patent/US6906024B1/en
Publication of WO1999057154A1 publication Critical patent/WO1999057154A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/24—Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402—Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2405—Glucanases
    • C12N9/2434—Glucanases acting on beta-1,4-glucosidic bonds
    • C12N9/2437—Cellulases (3.2.1.4; 3.2.1.74; 3.2.1.91; 3.2.1.150)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K19/00—Hybrid peptides, i.e. peptides covalently bound to nucleic acids, or non-covalently bound protein-protein 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • 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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y302/00—Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01—Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01004—Cellulase (3.2.1.4), i.e. endo-1,4-beta-glucanase
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms

Definitions

  • the present invention relates to fabric care compositions comprising an amino acid sequence comprising a Cellulose Binding Domain (CBD).
  • CBD Cellulose Binding Domain
  • Modern laundry detergent and/or fabric care compositions contain various detergent ingredients having one or more purposes in obtaining fabrics which are not only clean but also have retained appearance and integrity. Therefore, detergent components such as perfumes, soil release agents, fabric brightening agents, fabric softeners, chelants, bleaching agents and catalysts, dye fixatives and enzymes, have been incorporated in laundry detergent and/or fabric care compositions.
  • detergent components such as perfumes, soil release agents, fabric brightening agents, fabric softeners, chelants, bleaching agents and catalysts, dye fixatives and enzymes, have been incorporated in laundry detergent and/or fabric care compositions.
  • enzymes especially proteases, lipases, amylases and/or cellulases.
  • cellulase enzymes are used in detergent/fabric care compositions for their cleaning and fabric care benefits.
  • the activity of cellulase is one in which cellulosic fibres or substrates are hydrolised by the cellulase and is depending on the particular function of the cellulase, which can be endo- or exo- cellulase, and on the respective hemicellulases.
  • the cellulose structures are depolymerized or cleaved into smaller and thereby more soluble or dispersible fractions. This activity in particular on fabrics provides a cleaning, rejuvenating, softening and generally improved handfeel characteristics to the fabric structure.
  • cellobiohydrolases major endoglucanases and bacterial cellulases posses a bifunctional organisation in the form of a catalytical core domain and a smaller cellulose binding domain separated by a linker or flexible hinge stretch of amino acids.
  • Fabric softening compositions impart several desirable properties to treated garments including softness and static control. Fabric softness of laundered garments is typically achieved by delivering a quaternary ammonium compound to the surface of the fabric. Consumer desirability for durable press fabric garments, particularly cotton fabric garments, has also risen. Durable press garments include those garments which resist wrinkling of the fabric both during wear and during the laundering process. Durable press garments can greatly decrease the hand work associated with laundering by eliminating ironing sometimes necessary to prevent wrinkling of the garment. However, in most commercially available durable press fabrics, the fabric's ability to resist wrinkling is reduced over time as the garment is repeatedly worn and laundered.
  • coloured garments have a tendency to wear and show appearance losses. A portion of this colour loss may be attributed to abrasion in the laundering process, particularly in automatic washing machines and automatic laundry dryers. Moreover, tensile strength loss of fabric appears as an unavoidable result of mechanical / chemical action due to use / wearing or washing.
  • a fabric care composition which can provide fabric softness and provide, refurbish or restore tensile strength, anti-wrinkle, anti-bobbling and anti-shrinkage properties to fabrics, as well as provide static control, colour appearance and fabric anti-wear properties and benefits.
  • Enzymes linked to Cellulose Binding Domains are described in the art : WO 91/10732 novel derivatives of cellulase enzymes combining a core region derived from an endoglucanase producible by a strain of Bacillus spp., NICMB 40250 with a CBD derived from another cellulase enzyme or a combining a core region derived from another cellulase enzyme with a CBD derived from said endoglucanase, for improved binding properties.
  • WO94/07998 describes cellulase variants of a cellulase classified in family 45, comprising a CBD, a Catalytically Active Domain (CAD) and a region linking the CBD to the CAD, wherein one or more amino acid residues have been added, deleted or substituted and /or another CBD is added at the opposite end of the CAD.
  • WO95/16782 relates to the cloning and high level expression of novel truncated cellulase proteins or derivatives thereof in Trichodeima longibrachiatum comprising different core regions with several CBDs.
  • WO97/01629 describes cellulolytic enzyme preparation wherein the mobility of the cellulase component may be reduced by adsorption to an insoluble or soluble carrier e.g. via the existing or newly introduced CBD.
  • WO97/28243 describes a process for removal or bleaching or soiling or stains from cellulosic fabrics wherein the fabric is contacted in aqueous medium with a modified enzyme which comprises a catalytically active amino acid sequence of a non-cellulolytic enzyme selected from amylases, proteases, lipases, pectinases and oxidoreductases, linked to an amino acid sequence comprising a cellulose binding domain and a detergent composition comprising such modified enzyme and a surfactant.
  • the present invention relates to fabric care compositions comprising one or more amino acid sequence(s) comprising a cellulose binding domain, providing fabric care.
  • the present invention relates to fabric care compositions wherein the amino acid sequence comprising a cellulose binding domain, is linked to a softening protein.
  • the fabric care compositions of the present invention can further comprise a softening ingredient selected from cationic surfactants, a transferase enzyme and/or clays.
  • An essential element of the fabric care compositions of the present invention is an amino acid sequence comprising a cellulose binding domain.
  • This amino acid sequence comprising a cellulose binding domain can be a naturally occuring sequence or can be a modified sequence.
  • This modified sequence corresponds to cross-linked CBDs, i.e. amino acid sequences comprising a cellulose binding domain which are cross-linked to each other or corresponds to CBDs further linked to a softening protein, i.e. an amino acid sequence comprising a cellulose binding domain linked to a softening protein.
  • the present invention relates to a fabric care composition
  • a fabric care composition comprising one or more amino acid sequence(s) comprising a cellulose binding domain.
  • CBDs provide softening, abrasion resistance and pilling prevention, indeed, without wishing to be bound by theory, it is believed that the CBDs adsorb on the fibres of the fabric.
  • CBDs are proteins and therefore provide softening.
  • adsorbed CBDs protect the fabric's fibers and thereby prevent the fibrillation of the cellulosic fibres.
  • the present invention encompasses a fabric care composition comprising cross-linked amino acid sequences comprising a cellulose binding domain. It has been surprisingly found that such cross-linked CBDs provide softness, prevent the fibrillation of cellulosic fibers as indicated above and also restore tensile strength, prevent the apparition of wrinkles, and increase the hydrophilicity of synthetic fibers. Indeed, without wishing to be bound by theory, it is believed that each cross-linked CBD adsorbs at opposite sites of the damaged fibers and thereby restore tensile strenght.
  • the present invention relates to a fabric care composition comprising the above described CBDs which are further linked to a softening protein.
  • a cellulose binding domain to a softening protein, allows a higher concentration of the softening protein onto the fabric, i.e. a closer and/or more lasting contact, resulting in a more efficient activity.
  • modified softening proteins have an increased affinity (relative to unmodified softening protein) for binding to a cellulosic fabric or textile.
  • the above described fabric care composition may further comprise a softening ingredient selected from cationic surfactants, a transferase enzyme and/or clays.
  • CBD Cellulose Binding Domain
  • amino acid sequence comprising a CBD or Cellulose Binding Domain or CBD are intended to indicate an amino acid sequence capable of effecting binding of the cellulase to a cellulosic substrate (e.g. as described in P. Kraulis et al., Determination of the three-dimensional structure of the C terminal domain of cellobiohydrolase I from Trichoderma reesei. A study using nuclear magnetic resonance and hybrid distance geometry- dynamically simulated annealing. Biochemistry 28:7241-7257, 1989). The classification and properties of cellulose binding domains are presented in P. Tomme et al., in the symposium “Enzymatic degradation of insoluble polysaccharides” (ACS Symposium Series 618, edited by J.N. Saddler and M.H. Penner, ACS, 1995).
  • Cellulose-binding (and other carbohydrate-binding) domains are polypeptide amino acid sequences which occur as integral parts of large polypeptides or proteins consisting of two or more polypeptide amino acid sequence regions, especially in hydrolytic enzymes (hydrolases) which typically comprise a catalytic domain containing the active site for substrate hydrolysis and a carbohydrate- binding domain for binding to the carbohydrate substrate in question.
  • hydrolytic enzymes hydrolases
  • Such enzymes can comprise more than one catalytic domain and one, two or three carbohydrate-binding domains, and they may further comprise one or more polypeptide amino acid sequence regions linking the carbohydrate-binding domain(s) with the catalytic domain(s), a region of the latter type usually being denoted a "linker".
  • Cellulose-binding domains have also been found in algae, e.g. in the red alga porphyra purpurea in the form of a non-hydrolytic polysaccharide- binding protein [see P. Tomme et al., Cellulose-binding domains - Classification and Properties in Enzymatic Degradation of Insoluble Carbohydrates , John N. Saddler and Michael H. Penner (Eds.), ACS Symposium Series, No. 618 (1996)].
  • CBDs which are classified and referred to by P. Tomme et al. (op. cit.) as "cellulose-binding domains"] derive from cellulases and xylanases.
  • cellulose-binding domain is intended to be understood in the same manner as in the latter reference (P. Tomme et al., op. cit. )
  • the P. Tomme et al. reference classifies more than 120 "cellulose-binding domains" into 10 families (l-X) which may have different functions or roles in connection with the mechanism of substrate binding. However, it is to be anticipated that new family representatives and additional families will appear in the future.
  • a CBD may be located at the N or C terminus or at an internal position.
  • the part of a polypeptide or protein (e.g. hydrolytic enzyme) which constitutes a CBD per se typically consists of more than about 30 and less than about 250 amino acid residues.
  • those CBDs listed and classified in Family I in accordance with P. Tomme et al. (op. cit.) consist of 33-37 amino acid residues
  • those listed and classified in Family Ha consist of 95-108 amino acid residues
  • those listed and classified in Family VI consist of 85-92 amino acid residues
  • one CBD derived from a cellulase from Clostridium thermocellum listed and classified in Family VII consists of 240 amino acid residues.
  • the molecular weight of an amino acid sequence constituting a CBD per se will typically be in the range of from about 4kD to about 40kD, and usually below about 35kD.
  • Cellulose binding domains can be produced by recombinant techniques as described in H. Stalbrand et al., Applied and Environmental Microbiology, Mar. 1995, pp. 1090-1097; E. Brun et al., (1995) Eur. J. Biochem. 231, pp. 142-148; J.B. Coutinho et al., (1992) Molecular Microbiology 6(9), pp. 1243-1252
  • a cellulose binding domain of, e.g. a cellulase several genetic engineering approaches may be used.
  • One method uses restriction enzyme to remove a portion of the gene and then to fuse the remaining gene- vector fragment in frame to obtain a mutated gene that encodes a protein truncated for a particular gene fragment.
  • Another method involves the use of exonucleases such as Ba131 to systematically delete nucleotides either externally from the 5' and the 3' ends of the DNA or internally from a restricted gap within the gene.
  • exonucleases such as Ba131 to systematically delete nucleotides either externally from the 5' and the 3' ends of the DNA or internally from a restricted gap within the gene.
  • Appropriate substrates for evaluating the binding ability include cellulosic materials such as Avicel TM and cotton fibres.
  • Other methods include the use of a selective or specific protease capable of cleaving a CBD, e.g. a terminal CBD, from the remainder of the polypeptide chain of the protein in question.
  • nucleotide sequence encoding the substrate-binding (carbohydrate- binding) region may then be manipulated in a variety of ways to fuse it to a DNA sequence encoding the amino acid sequence of interest.
  • the DNA fragment encoding the carbohydrate-binding amino acid sequence, and the DNA encoding the amino acid sequence of interest are then ligated with or without a linker.
  • the resulting ligated DNA may then be manipulated in a variety of ways to achieve expression.
  • Preferred microbial expression hosts include certain Aspergillus species (e.g. A. niger or A. oryzae), Bacillus species, and organisms such as Escherichia coli or Saccharomyces cerevisiae.
  • CBDs for the purpose of the present invention are selected from the group consisting of : CBDs CBHII from T ⁇ choderma reesei, CBDs CenC, CenA and Cex from Cellulomonas fimi, CBD CBHI from Trichoderma reesei, CBD Cellulozome from Closthdium cellulovorans, CBD E3 from Thermonospora fusca, CBD-dimer from Clost ⁇ dium stecorahum (NCIMB11754) XynA, CBD from Bacillus agaradherens (NCIMB40482) and/or CBD family 45 from Humicola insolens.
  • CBD for the purpose of the present invention are the CBD CenC from Cellulomonas fimi, CBD Cellulozome from Clost ⁇ dium cellulovorans and/or the CBD originating from the fungal Humicola Insolens cellulase sold under the tradename "Carezyme” by Novo Nordisk A/S.
  • Carezyme is an endoglucanase from family 45, derived from Humicola insolens DSM1800, having a molecular weight of about 43kDa and exhibiting cellulolytic activity
  • the fabric care composition can comprise one or more of the above described CBDs, any of these CBDs which are cross linked and/or further linked to a softening protein and/or mixtures thereof.
  • the cross-linked CBDs of the present invention can comprise the amino acid sequence comprising from 2 to 50, preferably 2 to 10 cellulose binding domains.
  • the CBDs comprised in the fabric care compositions of the present invention may originate from different sources.
  • the CBDs, the cross-linked CBDs and/or the CBD linked to a softening protein are generally comprised in the fabric care compositions of the present invention at a level of from 0.01% to 10% and preferably from 0.1% to 6% and in a concentrated fabric care composition, from 0.2% to 30%, from 2% to 20% by weight.
  • CBD by fusing the N-terminal CBD of T. reesei CBHII to the C-terminal CBD of
  • the linker region contains three amino acid residues from the natural CBHII linker followed by 21 amino acid residues from the natural CBHI linker.
  • the double CBD was cloned an produced in Escherichia coli. It has been observed that the two domains interact during binding on cellulose, resulting in a higher binding affinity of the double CBD than either of the two single domains by themselves.
  • Double CBD Peptide All DNA manipulations were performed using standard protocols. The gene constructions were first assembled into the vector pSP73 (Promega). The coding region for the pelB signal sequence of Erwinia carotovora was fused in frame with the coding region of the first 41 N-terminal residues of CBHII derived from the plasmid pTTc9, which in turn was linked to the coding region of the last 57 residues of CBHI derived from the plasmid pTTcl). For expression in E. coli, the construction was inserted into the expression vector pKK223-3, containing the isopropyl- ⁇ -D- thiogalactopyranoside-inducible tac promoter. The nucleotide sequence of the final construct was verified by sequencing.
  • Double CBD - Culture supernatant was centrifuged (10.000 rpm, 45 min) and mixed with an equal volume of 20 mM phosphate buffer, pH 8.0, containing 1.5 M ammonium sulfate and kept at 4°C overnight. Precipitation was removed by centrifugation as above, and the supernatant was filtered through a 0.45 ⁇ m Durapore (Millipore Corp.) membrane. The clarified supernatant was then loaded onto a butyl-Sepharose 4B column (Pharmacia Biotech Inc.) previously equilibrated with 10 mM phosphate buffer, pH 8.0, containing 0.75 M ammonium sulfate.
  • the column was then washed with equilibration buffer, and the bound protein was eluted with 10 mM phosphate buffer, pH 8.0.
  • the eluted peak fractions were loaded onto a Source RPC column (Pharmacia) equilibrated with Milli-Q water:trifluoroacetic acid (1000:1).
  • Bound peptide was eluted with an increasing linear gradient of acetonitrile.trifluoroacetic acid (1000:1).
  • the purified peptide was then lyophilized.
  • the double CBD was identified by the monoclonal antibody CI-89, which is specific toward the CBHI CBD. All chromatographic steps were run on a fast protein liquid chromatography (Pharmacia) system.
  • Proteolytic Cleavage The lyophilized peptide was redissolved in 100 mM Tris buffer, pH 8.2 (2 mg/ml) and 10 units of immobilized trypsin (Sigma T-4019) added per mg of peptide. The suspension was incubated at 37°C overnight, purified by the chromatography on Source RPC media (see above), and then lyophilized. The cleavage products were characterized and identified by amino acid analysis and MALDI-MS.
  • the fabric care composition can also comprise the above described amino acid sequences further linked to a softening protein.
  • Enzyme proteins used in the present invention are those generically defined as a class of proteins having a particular structure for catalytic action. In other words, all proteins that possess a structure for catalytic action can be used, whether or not they exhibit catalytic action. However, enzyme proteins suitable for the purpose of the present invention are inactive. Inactivation can occur for example by inhibition, by the distortion of the three-dimensional structure for example by thermal or chemical means. When proteins other than enzyme proteins are used, the effects of the present invention may be obtained to some extent, but sufficient effect may not be achieved. Enzyme proteins have different biological origins: animal, plant and microbial origins.
  • Enzyme proteins of any origin are usable for the present invention.
  • Such enzyme proteins include hydrolases, lyases, oxidoreductases, ligases, transferases and isomerases, all of which are usable for the present invention.
  • hydrolases exemplified by proteases (peptidase), glucosidases such as cellulase and amylase, and esterases such as lipase.
  • the molecular weight of the enzyme protein is preferably not lower than 10,000, more preferably in the range of from 20,000 to 300,000. Being not lower than 10,000 in molecular weight, some enzyme proteins cannot penetrate the single fiber/monofilament (lamella structure) of cellulosic fibers such as a natural cellulose fiber and rayon. Also, they may not penetrate the monofilament of synthetic fibers, because the monofilament internal structure is dense. Enzyme adsorption sites of cellulosic fibers and synthetic fibers are therefore limited to the surface of the single fiber/monofilament.
  • the softening enzyme protein will be chosen from inactive enzyme comprising a CBD in nature, such as cellulase, xylanases, mannanases, arabinofuranosidases, acetylesterases and chitinases.
  • inactive enzyme comprising a CBD in nature, such as cellulase, xylanases, mannanases, arabinofuranosidases, acetylesterases and chitinases.
  • JP01280079 describes another type of softening proteins that can be used in the fabric care compositions of the present invention.
  • These softening proteins are polyamino acid resin solution that adhere to synthetic, semi synthetic or cotton fabrics and thereby provide softness.
  • These polyamino acids are preferably alpha amino acid such as glutamic acid, glycine, ornithine, mono- or co-polymer such as poly-gamma-L-glutamate.
  • C18 alkyl quaternary wheat protein derivatives sold under the tradename Coltide HQS by Croda Colloids Ltd. These wheat proteins derivatives generally included at levels of 0.04% to 0.2% by weight, are known to provide great conditioning effect, i.e. to provide great handfeeling, softeness, to prevent fibres erosion of cotton and wool fabrics and to increase the lubricity of wool fibres.
  • CBD hybrids and/or softening protein hybrids Such amino acid sequence comprising one ore more CBDs and/or being further linked to a softening proteins
  • CBD hybrids and/or softening protein hybrids can be prepared and purified by methods known in the art [see, e.g., WO 90/00609, WO 94/24158 and WO 95/16782, as well as Greenwood et al., Biotechnology and Bioengineering 44 (1994) pp. 1295 - 1305].
  • enzymes hybrid is given in WO 91/10732 wherein novel derivatives of cellulase enzymes combining a core region derived from a Bacillus NICB 40250 endoglucanase with a CBD derived from another cellulase enzyme or a combining a core region derived from another cellulase enzyme with a CBD derived from a Bacillus NICB 40250 endoglucanase, are constructed.
  • WO 95/16782 describes the combinations of different core regions with several CBD and the cloning and high level expression of these novel truncated cellulase proteins or derivatives thereof, in Trichoderma longibrachiatum.
  • the CBD hybrid and/or softening protein hybrid may, e.g., be prepared by transforming into a host cell a DNA construct comprising at least a fragment of DNA encoding the cellulose-binding domain ligated, with or without a linker, to a DNA sequence encoding the other cellulose binding domain and/or softening protein of interest, and growing the transformed host cell to express the fused gene.
  • a DNA construct comprising at least a fragment of DNA encoding the cellulose-binding domain ligated, with or without a linker, to a DNA sequence encoding the other cellulose binding domain and/or softening protein of interest, and growing the transformed host cell to express the fused gene.
  • CBD hybrid and/or softening protein hybrid obtainable in this matter - often referred to in the art as a "fusion protein" - may be described by one of the following general formulae:
  • CBD is an amino acid sequence comprising at least the cellulose-binding domain (CBD) per se.
  • MR (the middle region; a linking region) may be a bond, or a linking group comprising from 1 to about 100 amino acid residues, in particular of from 2 to 40 amino acid residues, e.g. from 2 to 15 amino acid residues.
  • MR may, in principle, alternatively be a non-amino-acid linker (See below).
  • X is an amino acid sequence comprising another cellulose binding domain and/or an amino acid sequence comprising the above-mentioned, inactive sequence of amino acid residues of a polypeptide encoded by a DNA sequence encoding the softening protein of interest.
  • the moieties A and B are independently optional. When present, a moiety A or B constitutes a terminal extension of a CBD or X moiety, and normally comprises one or more amino acid residues.
  • a CBD in a softening protein hybrid of the type in question may be positioned C-terminally, N- terminally or internally in the softening protein hybrid.
  • an X moiety in a softening protein hybrid of the type in question may be positioned N- terminally, C-terminally, or internationally in the softening protein hybrid.
  • Softening protein hybrids of interest in the context of the invention include softening protein hybrids which comprise more than one CBD, e.g. such that two or more CBDs are linked directly to each other, or are separated from one another by means of spacer or linker sequences (consisting typically of a sequence of amino acid residues of appropriate length).
  • Two CBDs in an softening protein hybrid of the type in question may, for example, also be separated from one another by means of an -MR-X- moiety as defined above.
  • One or more cellulose binding domain can be linked to the N-terminal and/or C-terminal parts of the cellulase core region. Any part of a CBD can be selected, modified, truncated etc.
  • CBD hybrid and/or softening protein hybrids of the type in question are particularly susceptible towards proteolytic cleavage of linker regions connecting the domains.
  • Proteases causing such cleavage may, for example, be subtilisins, which are known to often exhibit broad substrate specificities [see, e.g. : Gr ⁇ n et al., Biochemistry 3 . (1992), pp. 6011-6018; Teplyakov et al., Protein Engineering 5 (1992), pp. 413-420].
  • Glycosylation of linker residues in eukaryotes is one Nature's ways of preventing proteolytic degradation.
  • the length of the linker also plays a role in relation to accessibility by proteases. Which "solution” is optimal depends on the environment in which the softening protein hybrid is to function. When constructing new CBD hybrid and/or softening protein hybrid molecules, attention will be preferably paid to the linker stability.
  • the expression cassette may be included within a replication system for episomal maintenance in an appropriate cellular host or may be provided without a replication system, where it may become integrated into the host genome.
  • the DNA may be introduced into the host in accordance with known techniques such as transformation, microinjection or the like.
  • the host may be grown to express the fused gene. Normally it is desirable additionally to add a signal sequence which provides for secretion of the fused gene.
  • useful genes are: 1) Signal sequence - (pro-peptide) - carbohydrate-binding domain - linker -
  • CBD and/or softening protein sequence of interest or
  • the recombinant product may be glycosylated or non- glycosylated.
  • linker or “linking region” or “Middle region - MR” is intended to indicate a region that might adjoin the CBD and connect it to another CBD or to the amino acid sequence of a softening protein. When present, this linking can be achieved chemically or by recombinant techniques.
  • linking regions are amino acid linking regions (peptides), some examples thereof are described in N.R. Gilkes et al., Microbiol. Rev. 55, 1991 , pp. 303-315.
  • the linking region can comprise from 1 to about 100 amino acid residues, in particular of from 2 to 40 amino acid residues, e.g. from 2 to 15 amino acid residues. As stated above, it is preferred to use amino acids which are less favoured by the surrounding proteases.
  • Non amino acid/proteinic compounds referred to as “non-amino acid” can also be used for the linking of the catalytically active amino acid sequence to the 15
  • Suitable non-amino acid linking regions are the polyethylene glycol derivatives described in the Shearwater polymers, Inc. catalog of January 1996, such as the nucleophilic PEGs, the carboxyl PEGs, the electrophilically activated PEGs, the sulfhydryl-selective PEGs, the heterofunctional PEGs, the biotin PEGs, the vinyl derivatives, the PEG silanes and the PEG phospholipids.
  • suitable non-amino acid linking regions are the heterofunctional PEG, (X-PEG-Y) polymers from Shearwater such as PEG(NPC)2, PEG-(NH2)2, t- BOC-NH-PEG-Nh2, t-BOC-NH-PEG-CO2NHS, OH-PEG-NH-tBOC, FMOC-NH- PEG-CO2NHS or PEG(NPC)2 MW 3400 from Sigma, glutaric dialdehyde 50 wt% solution in water from Aldrich, disuccinimidyl suberate (DSS) form Sigma, ⁇ - maleimidobutyric acid N-hydroxysuccinimide ester (GMBS) from Sigma, 1-ethyl- 3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) from Sigma and dimethyl suberimidate hydrochloride (DMS) from Sigma.
  • PEG(NPC)2 PEG-(NH2)2, t- B
  • Non-amino acid linking regions are 1-ethyl-3-(3- dimethylaminopropyl) carbodiimide, N-ethyl-5-phenylisoaxolium-3-sulphonate, 1- cyclohexyl-3(2morpholinoethyl) carbodide metho-p-toluene sulphonate, N- ethoxycarbonyl-2-ethoxy 1 ,2, dihydroquinoline or glutaraldehyde.
  • Preferred chemical linking regions are PEG(NPC)2, (NH2)2-PEG, t-BOC-NH- PEG-NH2 polymers from Shearwater.
  • the fabric care compositions of the invention will contain at least one additional fabric care component.
  • additional fabric care component the precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.
  • the composition may comprise optional ingredients such as a dye fixing agent, a fabric softener compound and further optional ingredients.
  • the fabric care compositions of the present invention preferably further comprise a fabric care ingredient selected from cationic surfactants, a transferase enzyme and/or clays.
  • composition of the invention can be employed in stand alone product including pre-or post-wash additives. It can also be employed It can also be used in fully-formulated compositions including laundry compositions as well as rinse 16
  • the fabric care compositions of the present invention preferably further comprise a cationic surfactant. It has been surprisingly found that the fabric care compositions of the present invention further comprising a cationic surfactant, can provide improved fabric softness and provide, refurbish or restore enhanced tensile strength, anti-wrinkle, anti-bobbling and anti-shrinkage properties to fabrics, as well as provide improved static control, colour appearance and fabric anti-wear properties and benefits.
  • Typical of the cationic softening components are the quaternary ammonium compounds or amine precursors thereof as defined hereinafter.
  • Preferred quaternary ammonium fabric softening active compound have the formula
  • each R unit is independently hydrogen, C ⁇ -CQ alkyl, C ⁇ -CQ hydroxyalkyl, and mixtures thereof, preferably methyl or hydroxy alkyl; each R 1 unit is independently linear or branched C11-C22 alkyl, linear or branched C-11-C22 alkenyl, and mixtures thereof, R2 is hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and mixtures thereof; X is an anion which is compatible with fabric softener actives and adjunct ingredients; the index m is from 1 to 4, preferably 2; the index n is from 1 to 4, preferably 2.
  • An example of a preferred fabric softener active is a mixture of quaternized amines having the formula:
  • R is preferably methyl; R ⁇ is a linear or branched alkyl or alkenyl chain comprising at least 11 atoms, preferably at least 15 atoms.
  • the unit -Ri represents a fatty alkyl or alkenyl unit which is typically derived from a triglyceride source.
  • the triglyceride source is preferably derived from tallow, partially hydrogenated tallow, lard, partially hydrogenated lard, vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc. and mixtures of these oils.
  • the preferred fabric softening actives of the present invention are the Diester and/or Diamide Quaternary Ammonium (DEQA) compounds, the diesters and diamides having the formula:
  • R is preferably methyl, Q and R are as defined herein before; followed by quaternization to the final softener active.
  • Non-limiting examples of preferred amines which are used to form the DEQA fabric softening actives according to the present invention include methyl bis(2- hydroxyethyl)amine having the formula:
  • the counterion, ⁇ ( ⁇ ) above can be any softener-compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and the like, more preferably chloride or methyl sulfate.
  • the anion can also, but less preferably, carry a double charge in which case ⁇ ( ⁇ ) represents half a group.
  • Tallow and canola oil are convenient and inexpensive sources of fatty acyl units which are suitable for use in the present invention as R 1 units.
  • the following are non-limiting examples of quaternary ammonium compounds suitable for use in the compositions of the present invention.
  • the term "tallowyl” as used herein below indicates the R ⁇ unit is derived from a tallow triglyceride source and is a mixture of fatty alkyl or alkenyl units.
  • canolyl refers to a mixture of fatty alkyl or alkenyl units derived from canola oil.
  • quaternay ammoniun softening compounds are methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate; these materials are available from Witco Chemical Company under the trade names Varisoft® 222 and Varisoft® 110, respectively.
  • the fabric care compositions of the present invention preferably further comprise a transferase enzyme. It has been surprisingly found that the fabric care compositions of the present invention further comprising a transferase enzyme, can provide improved fabric softness and provide, refurbish or restore enhanced tensile strength, anti-wrinkle, anti-bobbling and anti-shrinkage properties to fabrics, as well as provide improved static control, colour appearance and fabric anti-wear properties and benefits
  • Transferase enzymes catalyse the transfer of functional compounds to a range of substrates.
  • the transferase of the invention have the potential to transfer a chemical moiety, for example a methyl group or a glycosyl group, from a small substrate to form oligomeric molecules or elongate polymeric compounds.
  • the enzyme improves the properties of garments by binding functional groups like methyl, hydroxy methyl, formyl, carboxyl, aldehyde, ketone, acyl, amino and phosphorous functional groups and/or transferring glycosyl residues to the garment surface.
  • aminoacyl transferase of the IUPAC Classification EC 2.3.2 links the amino acid(s) of the CBDs, Cross-linked CBDs, the amino acid linking regions and/or the softening proteins to the cotton fibres of the fabric and thereby provide, refurbish or restore tensile strength.
  • glycosyl transferase of the IUPAC Classification EC 2.4 transfer and link covalently the glycosyl carbohydrates that can be found on the CBDs, Cross-linked CBDs, the amino acid linking regions and/or the softening proteins to the fabric and thereby provide, refurbish or restore tensile strength.
  • aminoacyl transferases are enzymes transferring amino groups from a donor, generally an amino acid, to an acceptor. Even more preferred is the protein-glutamine ⁇ -glutamyltransferase (EC 2.3.2.13), also available under the name transglutaminase.
  • glycosyltransferases The general properties of the glycosyltransferases is to transfer a sugar from oligosaccharides to another carbohydrate as acceptor. Both hexosyltransferases and pentosyltransferases can be used in the invention.
  • glycosyltransferases examples include galactosyl transferases and fructosyltransf erases, such as 1 ,4- ⁇ -galactosyltransferase; 1 ,3- ⁇ -fructosyl- transferase; 2,3-sialyl transferase; cyclodextrin glycosyltransferase; N- acetylgluco- or -galactosaminyltransferase.
  • EC 2.4.1.24 1 ,4- ⁇ -D-glucan 1 ,4-a-D-glucan(D-glucose) 6- ⁇ -D-glucosyl transferase.
  • a particulate member of this enzyme is commercially available under the name Transglucosidase L-500.
  • mutant glycosyltransferases and/or glycosidase examples of which are described in PCT Application Publication No. WO 97/21822 to S.G. Withers Protein Eng. Net. Canada, improve the tensile strength and appearance of fabrics, e.g., reduce fabric wrinkles, enhance shape retention and reduce shrinkage
  • CCT-ase cyclomaltodextrin glucanotransferase
  • glucansucrases of which dextransucrase (EC 2.4.1.5), a glycosyltransferase, is one example.
  • Other glucansucrases that are suitable for use in the compositions described herein include, but are not limited to, various dextransucrases,retemansucrase and levansucrase.
  • Levansucrase is commercially available from Genencor.
  • transferases are preferably incorporated into the fabric care compositions in accordance with the invention at a level of from 0.0001% to 10%, more preferably from 0.0005% to 5 %, most preferred from 0.001% to 1% pure enzyme by weight of the total 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, etc.). 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 and/or chelant stability, catalytic activity and the like, of the enzyme variant is tailored to suit the particular fabric conditioning and/or 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. Colour care and fabric care benefits
  • Fabric softening agents can also be incorporated into fabric care 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.
  • the fabric care compositions of the present invention will comprise a clay. It has been surprisingly found that the fabric care compositions of the present invention further comprising a clay, can provide improved fabric softness and provide, refurbish or restore enhanced tensile strength, anti-wrinkle, anti- bobbling and anti-shrinkage properties to fabrics, as well as provide improved static control, colour appearance and fabric anti-wear properties and benefits.
  • smectite clay levels are normally in the range from 2% to 20%, more preferably from 5% to 15% by weight.
  • 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 24
  • water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
  • composition of the invention may optionally comprise a dye fixing agent.
  • Dye fixing agents or "fixatives”, are well-known, commercially available materials which are designed to improve the appearance of dyed fabrics by minimizing the loss of dye from fabrics due to washing. Not included within this definition are components which are fabric softeners or those described hereinbefore as amino-functional polymers.
  • Cationic fixatives are available under various trade names from several suppliers. Representative examples include: CROSCOLOR PMF (July 1981, Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No. 8544) from Crosfield; INDOSOL E-50 (February 27, 1984, Ref. No.
  • Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid - diamine condensates e.g.
  • a typical amount of the dye fixing agent to be employed in the composition of the invention is preferably up 90% by weight, preferably up to 50% by weight, more preferably from 0.001% to 10% by weight, most preferably from 0.5% to 5% active by weight of the composition.
  • Typical levels of incorporation of the softening compound in the fabric care composition are of from 1% to 80% by weight, preferably from 5% to 75%, more preferably from 15% to 70%, and even more preferably from 19% to 65%, by weight of the composition.
  • the fabric softener compound is preferably selected from a cationic, nonionic, amphoteric or anionic fabric softening component.
  • Typical of the cationic softening components are the quaternary ammonium compounds or amine precursors thereof as defined hereinafter.
  • the fabric care compositions of the present invention preferably further comprise a cationic surfacants.
  • Suitable amine fabric softening compounds for use herein, which may be in amine form or cationic form are selected from:
  • the preferred Component (i) is a nitrogenous compound selected from the group consisting of the reaction product mixtures or some selected components of the mixtures.
  • One preferred component (i) is a compound selected from the group consisting of substituted imidazoline compounds having the formula: wherein R? is an acyclic aliphatic C15-C21 hydrocarbon group and R ⁇ is a divalent C1-C3 alkylene group.
  • Component (i) materials are commercially available as: Mazamide® 6, sold by Mazer Chemicals, or Ceranine® HC, sold by Sandoz Colors & Chemicals; stearic hydroxyethyl imidazoline sold under the trade names of Alkazine® ST by Alkaril Chemicals, Inc., or Schercozoline® S by Scher Chemicals, Inc.; N,N"- ditallowalkoyldiethylenetriamine; 1 -tallowamidoethyl-2-tallowimidazoline (wherein in the preceding structure R ⁇ is an aliphatic C-15-C17 hydrocarbon group and R8 is a divalent ethylene group).
  • compositions (i) can also be first dispersed in a Bronsted acid dispersing aid having a pKa value of not greater than about 4; provided that the pH of the final composition is not greater than about 6.
  • a Bronsted acid dispersing aid having a pKa value of not greater than about 4; provided that the pH of the final composition is not greater than about 6.
  • Some preferred dispersing aids are hydrochloric acid, phosphoric acid, or methylsulfonic acid.
  • N,N"-ditallowalkoyldiethylenetriamine and 1-tallow(amidoethyl)-2- tallowimidazoline are reaction products of tallow fatty acids and diethylenetriamine, and are precursors of the cationic fabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate (see "Cationic Surface Active Agents as Fabric Softeners," R. R. Egan, Journal of the American Oil Chemicals' Society, January 1978, pages 118-121).
  • N,N"-ditallow aJkoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline can be obtained from Witco Chemical Company as experimental chemicals.
  • Methyl-1- tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold by Witco Chemical Company under the tradename Varisoft® 475.
  • each R2 is a C- ⁇ alkylene group, preferably an ethylene group; and G is an oxygen atom or an -NR- group; and each R, R ⁇ , R and R have the definitions given above and A" has the definitions given above for X " .
  • Compound (ii) is 1-oleylamidoethyl-2-oleylimidazolinium chloride wherein R ⁇ is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, G is a NH group, R5 is a methyl group and A" is a chloride anion.
  • R, R1 , R2, and A- are defined as above.
  • Compound (iii) is the compound having the formula:
  • R ⁇ is derived from oleic acid.
  • softening active can also encompass mixed softening active agents.
  • Preferred among the classes of softener compounds disclosed herein before are the diester or diamido quaternary ammonium fabric softening active compound (DEQA).
  • DEQA diester or diamido quaternary ammonium fabric softening active compound
  • Fully formulated fabric care compositions may contain, in addition to the hereinbefore described components, one or more of the following ingredients.
  • the liquid carrier employed in the instant compositions is preferably at least primarily water due to its low cost, relative availability, safety, and environmental compatibility.
  • the level of water in the liquid carrier is preferably at least about 50%, most preferably at least about 60%, by weight of the carrier.
  • Mixtures of water and low molecular weight, e.g., ⁇ about 200, organic solvent, e.g., lower alcohols such as ethanol, propanol, isopropanol or butanol are useful as the carrier liquid.
  • Low molecular weight alcohols include monohydric, dihydric (glycol, etc.) trihydric (glycerol, etc.), and higher polyhydric (polyols) alcohols.
  • compositions of the present invention may comprise one or more solvents which provide increased ease of formulation.
  • ease of formulation solvents are all disclosed in WO 97/03169. This is particularly the case when formulating liquid, clear fabric softening compositions.
  • the ease of formulation solvent system preferably comprises less than about 40%, preferably from about 10% to about 35%, more preferably from about 12% to about 25%, and even more preferably from about 14% to about 20%, by weight of the composition.
  • the ease of formulation solvent is selected to minimize solvent odor impact in the composition and to provide a low viscosity to the final composition.
  • isopropyl alcohol is not very effective and has a strong odor.
  • n-Propyl alcohol is more effective, but also has a distinct odor.
  • butyl alcohols also have odors but can be used for effective clarity/stability, especially when used as part of a ease of formulation solvent system to minimize their odor.
  • the alcohols are also selected for optimum low temperature stability, that is they are able to form compositions that are liquid with acceptable low viscosities and translucent, preferably clear, down to about 40°F (about 4.4°C) and are able to recover after storage down to about 20°F (about minus 6.7°C).
  • Suitable solvents can be selected based upon their octanol/water partition coefficient (P) as defined in WO
  • the ease of formulation solvents herein are selected from those having a ClogP of from about 0.15 to about 0.64, preferably from about 0.25 to about 0.62, and more preferably from about 0.40 to about 0.60, said ease of formulation solvent preferably being at least somewhat asymmetric, and preferably having a melting, or solidification, point that allows it to be liquid at, or near room temperature. Solvents that have a low molecular weight and are biodegradable are also desirable for some purposes.
  • the more assymetric solvents appear to be very desirable, whereas the highly symmetrical solvents such as 1 ,7- heptanediol, or 1 ,4-bis(hydroxymethyl) cyclohexane, which have a center of symmetry, appear to be unable to provide the essential clear compositions when used alone, even though their ClogP values fall in the preferred range.
  • the most preferred ease of formulation solvents can be identified by the appearance of the softener vesicles, as observed via cryogenic electron microscopy of the compositions that have been diluted to the concentration used in the rinse. These dilute compositions appear to have dispersions of fabric softener that exhibit a more unilamellar appearance than conventional fabric softener compositions. The closer to uni-lamellar the appearance, the better the compositions seem to perform. These compositions provide surprisingly good 30
  • Particularly preferred ease of formulation solvents include hexanediols such as 1 ,2-Hexanediol and 2-Ethyl-1,3-hexanediol and pentanediols such as 2,2,4-Trimethyl-1,3-pentanediol.
  • compositions containing both saturated and unsaturated diester quaternary ammonium compounds can be prepared that are stable without the addition of concentration aids.
  • the compositions of the present invention may require organic and/or inorganic concentration aids to go to even higher concentrations and/or to meet higher stability standards depending on the other ingredients.
  • concentration aids which typically can be viscosity modifiers may be needed, or preferred, for ensuring stability under extreme conditions when particular softener active levels are used.
  • the surfactant concentration aids are typically selected from the group consisting of (1) single long chain alkyl cationic surfactants; (2) nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures thereof. These aids are described in WO 94/20597, specifically on page 14, line 12 to page 20, line 12, which is herein incorporated by reference.
  • the total level is from 2% to 25%, preferably from 3% to 17%, more preferably from 4% to 15%, and even more preferably from 5% to 13% by weight of the composition.
  • These materials can either be added as part of the active softener raw material, (I), e.g., the mono- long chain alkyl cationic surfactant and/or the fatty acid which are reactants used to form the biodegradable fabric softener active as discussed hereinbefore, or 31
  • the total level of dispersibility aid includes any amount that may be present as part of component (I).
  • Inorganic viscosity/dispersibility control agents which can also act like or augment the effect of the surfactant concentration aids, include water-soluble, ionizable salts which can also optionally be incorporated into the compositions of the present invention.
  • ionizable salts can be used. Examples of suitable salts are the halides of the Group IA and IIA metals of the Periodic Table of the Elements, e.g., calcium chloride, magnesium chloride, sodium chloride, potassium bromide, and lithium chloride.
  • the ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity.
  • the amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desires of the formulator. Typical levels of salts used to control the composition viscosity are from about 20 to about 20,000 parts per million (ppm), preferably from about 20 to about 11 ,000 ppm, by weight of the composition.
  • Alkylene polyammonium salts can be incorporated into the composition to give viscosity control in addition to or in place of the water-soluble, ionizable salts above.
  • these agents can act as scavengers, forming ion pairs with anionic detergent carried over from the main wash, in the rinse, and on the fabrics, and may improve softness performance. These agents may stabilize the viscosity over a broader range of temperature, especially at low temperatures, compared to the inorganic electrolytes.
  • Specific examples of alkylene polyammonium salts include l-lysine monohydrochloride and 1 ,5-diammonium 2-methyl pentane dihydrochloride.
  • Stabilizers can be present in the compositions of the present invention.
  • the term "stabilizer,” as used herein, includes antioxidants and reductive agents. These agents are present at a level of from 0% to about 2%, preferably from about 0.01% to about 0.2%, more preferably from about 0.035% to about 0.1% for antioxidants, and more preferably from about 0.01% to about 0.2% for reductive agents. These assure good odor stability under long term storage conditions for the compositions and compounds stored in molten form.
  • the use of antioxidants and reductive agent stabilizers is especially critical for low scent products (low perfume).
  • antioxidants examples include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox S-1 ; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, available from Eastman Chemical Products, Inc., under the trade name Tenox-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain esters (C8-C22) of gallic acid, e.g., dodecyl gallate, available from Eastman Chemical Products, Inc.
  • Irganox® 1098 23128-74-7 N,N'-Hexamethylene bis(3,5-di-tert-butyl-4- hydroxyhydrocinnamamide
  • reductive agents examples include sodium borohydride, hypophosphorous acid, Irgafos® 168, and mixtures thereof.
  • Soil Release agents are desirably used in fabric care compositions of the instant invention. Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the fabric care compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
  • soil release agents include the METOLOSE SM100, METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (Germany), ZELCON 5126 (from Dupont) and MILEASE T (from ICI).
  • bactericides used in the compositions of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1 ,3-diol sold by Inolex Chemicals, located in Philadelphia, Pennsylvania, under the trade name Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2- methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the trade name Kathon 1 to 1 ,000 ppm by weight of the agent.
  • the present invention can contain a perfume.
  • perfumes are disclosed in U.S. Pat. 5,500,138, said patent being incorporated herein by reference.
  • perfume includes fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances.
  • natural i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants
  • artificial i.e., a mixture of different nature oils or oil constituents
  • synthetic i.e., synthetically produced
  • Such materials are often accompanied by auxiliary materials, such as fixatives, extenders, stabilizers and solvents. These auxiliaries are also included within the meaning of "perfume", as used herein.
  • perfumes are complex mixtures of a plurality of organic compounds.
  • any conventional fragrant acetal or ketal known in the art can be added to the present composition as an optional component of the conventionally formulated perfume (c).
  • Such conventional fragrant acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as acetals or ketals based on benzaldehyde, those comprising phenylethyl moieties, or more recently developed specialties such as those described in a United States Patent entitled "Acetals and Ketals of Oxo-Tetralins and Oxo-lndanes, see U.S. Pat. No. 5 ,084,440, issued January 28, 1992, assigned to Givaudan Corp.
  • perfume compositions for fully-formulated fabric softening compositions include the enol ethers of alkyl-substituted oxo-tetralins and oxo-indanes as described in U.S. Pat. 5,332,725, July 26, 1994, assigned to Givaudan; or Schiff Bases as described in U.S. Pat. 5,264,615, December 9, 1991, assigned to Givaudan.
  • the perfumes useful in the present invention compositions are substantially free of halogenated materials and nitromusks.
  • Perfume can be present at a level of from 0% to 10%, preferably from 0.1% to 5%, and more preferably from 0.2% to 3%, by weight of the finished composition.
  • Fabric care compositions of the present invention provide improved fabric perfume deposition.
  • the fabric care compositions of the present invention can further contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01% to 5%, more preferably from 0.1% to 2% by weight of the compositions.
  • a crystal growth inhibitor component preferably an organodiphosphonic acid component
  • organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.
  • the organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-1 ,1 -diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
  • a C1-C4 diphosphonic acid more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-1 ,1 -diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
  • HEDP ethane 1-hydroxy-1 ,1 -diphosphonic acid
  • compositions and processes herein can optionally employ one or more enzymes such as lipases, proteases, cellulase, amylases and peroxidases.
  • a preferred enzyme for use herein is a cellulase enzyme. Indeed, this type of enzyme will further provide a color care benefit to the treated fabric.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5. U.S.
  • 4,435,307 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212- producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® and CELLUZYME® (Novo) are especially 37
  • compositions herein will typically comprise from 0.001% to 5%, preferably 0.01 %-1% by weight of a commercial enzyme preparation.
  • activity units can also be used (e.g. CEVU or cellulase Equivalent Viscosity Units).
  • compositions of the present invention can contain cellulase enzymes at a level equivalent to an activity from 0.5 to 1000 CEVU/gram of composition.
  • Cellulase enzyme preparations used for the purpose of formulating the compositions of this invention typically have an activity comprised between 1 ,000 and 10,000 CEVU/gram in liquid or solid form.
  • the present invention can include optional components conventionally used in textile treatment compositions, for example: brighteners, colorants; surfactants; anti-shrinkage agents; fabric crisping agents; spotting agents; germicides; fungicides; anti-oxidants such as butylated hydroxy toluene, anti-corrosion agents, antifoam agents, and the like.
  • the present invention can also include other compatible ingredients, including those as disclosed in WO96/02625, WO96/21714, and WO96/21715, and dispersible poiyolefin such as Velustrol® as disclosed in co-pending application PCT/US 97/01644, and the like.
  • the present invention can also contain optional chelating agents.
  • compositions of the invention are suitable for use in any steps of the domestic treatment, that is as a pre-treatment composition, as a wash additive as a composition suitable for use in the rinse-cycle of the laundry cycle or applied on a dryer-sheet.
  • a pre-treatment composition as a wash additive as a composition suitable for use in the rinse-cycle of the laundry cycle or applied on a dryer-sheet.
  • compositions of the invention can be in a spray, foam, or aerosol form which for example can be suitable for use while ironing, or applied on the surfaces of the tumble dryer.
  • the fabric care compositions when formulated as laundry softening through- the-wash compositions according to the present invention generally comprise a surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semi-polar surfactants.
  • 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 fabric care compositions in accord with the invention.
  • the surfactant is preferably formulated to be compatible with enzyme components present in the composition.
  • the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.
  • Preferred surfactant systems to be used according to the present invention comprise as a surfactant one or more of the nonionic and/or anionic surfactants described herein.
  • Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, 39
  • the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X- 45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products.
  • nonionic surfactants of this type include TergitofTM 15-S-9 (the condensation product of C-
  • HLB in these products is from 8-11 and most preferred from 8-10.
  • the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • the preferred alkylpolyglycosides have the formula
  • R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position). The additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-position.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially-available PlurafacTM LF404 and PluronicTM surfactants, marketed by BASF.
  • nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11 ,000.
  • Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C8-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C8-C-
  • Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula.
  • R 1 is H, or R1 is C ⁇ _4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • Ri is methyl
  • R2 is a straight C-
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • the preferred alkyl ester sulfonate surfactant, especially for laundry applications comprise alkyl ester sulfonate surfactants of the structural formula:
  • R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
  • R 4 is a Ci-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 ⁇ is C ⁇ Q-C ⁇ Q alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • the methyl ester sulfonates wherein R ⁇ is C ⁇
  • 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 C12- 18 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.
  • R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12- 18 alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
  • alkyl chains of C-12-C16 are preferred for lower wash temperatures (e.g. below about 50°C) and C16-I8 a 'kyl chains are preferred for higher wash temperatures (e.g. above about 50°C).
  • anionic surfactants useful for detersive purposes can also be included in the fabric care 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.
  • 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 C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulf
  • 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.
  • alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C-
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a 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 C12-C18 alkyl polyethoxylate (1.0) sulfate (Ci2-Ci8E( 1 -0)M), C-12-C18 alkyl polyethoxylate (2.25) sulfate (Ci2-Ci ⁇ E(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (Ci2-Ci ⁇ E(3.0)M), and C12-C18 alkyl polyethoxylate (4.0) sulfate (C ⁇
  • the fabric care compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as the nonionic and/or anionic surfactants other than those already described herein.
  • Cationic detersive surfactants suitable for use in the fabric care compositions of the present invention are those having one long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula : [R 2 (OR3) y ][R 4 (OR 3 )y]2R 5 N+X- wherein 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 -CH 2 CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH 2 CH2CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, - CH2CHOH-CHOHCOR 6 CH
  • 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 (C1-C3) or alkoxylated alkyl of the formula III,
  • X " is a counterion, preferably a halide, e.g. chloride or methylsulfate.
  • Preferred quat ammonium surfactants are those as defined in formula I whereby
  • is C ⁇ , C-
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
  • is C ⁇ -C-j ⁇ alkyl
  • each of R2, R3 and R4 is independently C1-C4 alkyl
  • the preferred alkyl chain length for R-i is C12-C-15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
  • 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 dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C12-15 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-
  • the fabric care 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 fabric care 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 fabric care 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 fabric care 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.
  • the fabric care 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.
  • 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
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula 0
  • R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms
  • R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof
  • x is from 0 to about 3
  • each R ⁇ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C10-C18 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • the cleaning compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.
  • the fabric care composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines.
  • Suitable primary amines for use herein include amines according to the formula R1NH2 wherein Ri is a C6-C12, preferably C6-C10 alkyl chain or R4X(CH2)n, X is -O-,-C(O)NH- or -NH- R4 is a C ⁇ -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-1 R2R3N wherein R1 and R2 are C1-C8 alkylchains or
  • R3 is either a C ⁇ -C-12, preferably C ⁇ -C-io alkyl chain, or R3 is R4X(CH2)n. whereby X is -O-, -C(O)NH- or -NH- R4 is a C4-C-12, n is between 1 to 5, preferably 2-3.
  • R5 is H or C1-C2 alkyl and x is between 1 to 6 .
  • R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.
  • Preferred tertiary amines are R1R2R3N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or
  • R ⁇ is C5-C12 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 amidopropyl- dimethylamine, C8-10 amidopropyldimethylamine and C10 amidopropyl- dimethylamine.
  • the most preferred amines for use in the compositions herein are 1-hexylamine, 1 -octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n- dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.
  • 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 about 1% to about 25%.
  • the bleaching agent component for use herein can be any of the bleaching agents useful for fabric care compositions including oxygen bleaches as well as others known in the art.
  • the bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.
  • oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-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.
  • the hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxy- benzene-sulfonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG)or Phenolsulfonate ester of N-nonanoyl-6- aminocaproic acid (NACA-OBS, described in WO94/28106), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.
  • bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxy- benzene-sulfonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoloxybenzenes
  • acylated citrate esters such as disclosed in Copending European Patent Application No. 91870207.7 and unsymetrical acyclic imide bleach activator of the following formula as disclosed in the Procter & Gamble co-pending patent applications US serial No. 60/022,786 (filed July 30, 1996) and No. 60/028,122 (filed October 15, 1996) :
  • Ri is a C7-C13 linear or branched chain saturated or unsaturated alkyl group
  • R2 is a C
  • R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group.
  • 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 USSN 08/136,626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775.
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Metal-containing catalysts for use in bleach compositions include cobalt- containing catalysts such as Pentaamine acetate cobalt(lll) salts and manganese-containing catalysts such as those described in EPA 549 271 ; EPA 549 272; EPA 458 397; US 5,246,621; EPA 458 398; US 5,194,416 and US 5,114,611.
  • Bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in the patent application No 94870206.3.
  • 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.
  • the fabric care compositions when formulated as laundry softening through- the-wash compositions according to the present invention may further comprise a builder system.
  • a 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.
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na 2 Si 2 O 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 carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic poly-carboxylates include mellitic acid, pyromelli
  • 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.
  • 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 fabric care compositions when formulated as laundry softening through- the-wash compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • Such 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, triethylenetetra- aminehexacetates, 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 fabric care 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.
  • 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.
  • Example 1 The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.
  • 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:
  • DEQA Di-(tallow-oxy-ethyl) dimethyl ammonium chloride.
  • DEQA (2) Di-(soft-tallowyloxyethyl) hydroxyethyl methyl ammonium methylsulfate.
  • DTDMAMS Ditalllow dimethyl ammonium methylsulfate. SDASA 1:2 ratio of stearyldimethyl amine:triple-pressed stearic acid.
  • 2(A1O2SiO2)i2- 7H2O having a primary particle size in the range from 0.1 to 10 micrometers (Weight expressed on an anhydrous basis).
  • Carbonate Anhydrous sodium carbonate with a particle size between 200 and 900 micrometres.
  • TAED Tetraacetylethylenediamine.
  • DETPMP Diethyltriamine penta (methylene) phosphonate marketed by Monsanto under the Trade name Dequest 2060.
  • Protease Proteolytic enzyme sold under the tradename Savinase, Alcalase, Durazym by Novo Nordisk A/S, Maxacal, Maxapem sold by Gist-Brocades and proteases described in patents WO91/06637 and/or WO95/10591.
  • Amylase Amylolytic enzyme sold under the tradename Purafact Ox Am R described in WO 94/18314, WO96/05295 sold by Genencor; Termamyl®, Fungamyl® and Duramyl®, all available from Novo Nordisk A/S and those described in WO95/26397.
  • Lipase Lipolytic enzyme sold under the tradename Lipolase, Lipolase Ultra by Novo Nordisk A/S and Lipomax by Gist-Brocades.
  • CBD1 Double CBD comprising the N-terminal CBD of Trichoderma reesei CBHII linked to the C-terminal CBD of CBHI via a linking region of 24 amino acid ( M. Linder et al - The Journal of Biological Chemistry, Vol. 271 , No. 35, Issue of August, pp 21268-21272, 1996)
  • CBD2 CBD Cellulozome from Clost ⁇ dium cellulovorans which is sold under the tradename Cellulose Binding Domain by Sigma, linked to a C18 alkyl quaternary weat protein derivative sold under the tradename Coltide HQS by Croda Colloids Ltd.

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Abstract

Cette invention concerne des compositions respectant les tissus, lesquelles comprennent une ou plusieurs séquences d'acide aminé qui contiennent un domaine liant la cellulose de manière à prendre soin des tissus. Dans un autre mode de réalisation, cette invention concerne des compositions respectant les tissus dans lesquelles la séquence d'acide aminé comprenant un ou plusieurs domaines de liaison de la cellulose est liée à une protéine adoucissante.
PCT/US1998/008857 1998-05-01 1998-05-01 Compositions respectant les tissus et comprenant des domaines liant la cellulose WO1999057154A1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
AU72755/98A AU7275598A (en) 1998-05-01 1998-05-01 Fabric care compositions comprising cellulose binding domains
PCT/US1998/008857 WO1999057154A1 (fr) 1998-05-01 1998-05-01 Compositions respectant les tissus et comprenant des domaines liant la cellulose
ARP990102046A AR015282A1 (es) 1998-05-01 1999-04-30 Hibrido de proteina suavizante, composicion para el cuidado de telas que lo comprende y metodo para poner en contacto una tela con dicha composicion.
BR9910100-9A BR9910100A (pt) 1998-05-01 1999-04-30 Composições para proteção de tecidos compreendendo domìnios de ligação de celulose
CN 99808137 CN1308638A (zh) 1998-05-01 1999-04-30 包含纤维素结合结构域的织物护理组合物
CA002326372A CA2326372A1 (fr) 1998-05-01 1999-04-30 Compositions d'entretien des tissus comprenant des domaines de liaison de la cellulose
MA25562A MA24905A1 (fr) 1998-05-01 1999-04-30 Compositions d'entretien des tissus comprenant des domaines de fixation a la cellulose
EP99918913A EP1073684A1 (fr) 1998-05-01 1999-04-30 Compositions d'entretien des tissus comprenant des domaines de liaison de la cellulose
AU36718/99A AU3671899A (en) 1998-05-01 1999-04-30 Fabric care compositions comprising cellulose binding domains
PCT/US1999/009410 WO1999057156A1 (fr) 1998-05-01 1999-04-30 Compositions d'entretien des tissus comprenant des domaines de liaison de la cellulose
US09/674,477 US6906024B1 (en) 1998-05-01 1999-04-30 Fabric care compositions comprising cellulose binding domains

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WO2001038637A1 (fr) * 1999-11-25 2001-05-31 American Israeli Paper Mills Ltd. Produits en papier renfermant un agent de reticulation biologique
WO2001046514A1 (fr) * 1999-12-22 2001-06-28 Unilever N.V. Traitement de tissus et appareil utilise a cet effet
WO2001046357A2 (fr) * 1999-12-22 2001-06-28 Unilever N.V. Compositions detergentes comprenant des agents ameliorants
WO2001092455A1 (fr) * 2000-05-31 2001-12-06 Unilever Plc Groupes fonctionnels cibles utilises dans des catalyseurs de blanchiment
WO2002046342A2 (fr) * 2000-12-08 2002-06-13 Novaprot Gmbh Combinaison nettoyante tensioactive constituee de matieres premieres renouvelables a fort pouvoir nettoyant
WO2003031477A1 (fr) * 2001-10-03 2003-04-17 Unilever N.V. Proteines de fusion contenant un domaine de liaison aux hydrates de carbone pour la liberation d'agents therapeutiques et autres agents, et compositions les renfermant
US6579842B2 (en) 1999-12-22 2003-06-17 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Method of treating fabrics
WO2003055974A2 (fr) 2001-12-22 2003-07-10 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline obtenue a partir de bacillus sp. (dsm 14392) et agents de lavage et de nettoyage contenant cette protease alcaline
US6642196B2 (en) 1999-12-22 2003-11-04 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Method of delivering a benefit agent
DE102007032111A1 (de) 2007-07-09 2009-01-15 Henkel Ag & Co. Kgaa Neue Proteasen und Wasch- und Reinigungsmittel enthaltend diese Proteasen
DE102007036756A1 (de) 2007-08-03 2009-02-05 Henkel Ag & Co. Kgaa Neue Proteasen und Wasch- und Reinigungsmittel, enthaltend diese neuen Proteasen
EP4053256A1 (fr) * 2021-03-01 2022-09-07 Novozymes A/S Utilisation d'enzymes pour améliorer le dépôt de parfum

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DE102004034266A1 (de) * 2004-07-15 2006-02-09 Ge Bayer Silicones Gmbh & Co. Kg Schichtsilikat-enthaltende Polysiloxan-Zusammensetzungen
WO2008077395A1 (fr) * 2006-12-22 2008-07-03 Lothar Ernst Wilhelm Weber Adoucissant textile
US20170260482A1 (en) * 2016-03-08 2017-09-14 The Procter & Gamble Company Particles including enzyme
EP3401385A1 (fr) * 2017-05-08 2018-11-14 Henkel AG & Co. KGaA Composition détergente comprenant un polypeptide comprenant un domaine de liaison aux glucides
US20210009927A1 (en) * 2018-04-17 2021-01-14 Novozymes A/S Polypeptides Comprising Carbohydrate Binding Activity in Detergent Compositions And Their use in Reducing Wrinkles in Textile or Fabrics
CN109797144A (zh) * 2019-01-24 2019-05-24 中国科学院南海海洋研究所 芽孢杆菌dl-2的胞外蛋白酶在催化(±)-乙酸苏合香酯不对称水解中的应用
US20220340843A1 (en) * 2019-10-03 2022-10-27 Novozymes A/S Polypeptides comprising at least two carbohydrate binding domains

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001038637A1 (fr) * 1999-11-25 2001-05-31 American Israeli Paper Mills Ltd. Produits en papier renfermant un agent de reticulation biologique
US6586384B2 (en) 1999-12-22 2003-07-01 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Method of treating fabrics and apparatus used therein
WO2001046514A1 (fr) * 1999-12-22 2001-06-28 Unilever N.V. Traitement de tissus et appareil utilise a cet effet
WO2001046357A2 (fr) * 1999-12-22 2001-06-28 Unilever N.V. Compositions detergentes comprenant des agents ameliorants
US7041793B2 (en) 1999-12-22 2006-05-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions comprising benefit agents
US6919428B2 (en) 1999-12-22 2005-07-19 Unilever Home Products And Care Usa Division Of Conopco, Inc. Detergent compositions comprising benefit agents
WO2001046357A3 (fr) * 1999-12-22 2002-06-13 Unilever Nv Compositions detergentes comprenant des agents ameliorants
US6642196B2 (en) 1999-12-22 2003-11-04 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Method of delivering a benefit agent
US6579842B2 (en) 1999-12-22 2003-06-17 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Method of treating fabrics
US6677288B2 (en) 2000-05-31 2004-01-13 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Targeted moieties for use in bleach catalysts
WO2001092455A1 (fr) * 2000-05-31 2001-12-06 Unilever Plc Groupes fonctionnels cibles utilises dans des catalyseurs de blanchiment
WO2002046342A3 (fr) * 2000-12-08 2002-11-28 Novaprot Gmbh Combinaison nettoyante tensioactive constituee de matieres premieres renouvelables a fort pouvoir nettoyant
WO2002046342A2 (fr) * 2000-12-08 2002-06-13 Novaprot Gmbh Combinaison nettoyante tensioactive constituee de matieres premieres renouvelables a fort pouvoir nettoyant
WO2003031477A1 (fr) * 2001-10-03 2003-04-17 Unilever N.V. Proteines de fusion contenant un domaine de liaison aux hydrates de carbone pour la liberation d'agents therapeutiques et autres agents, et compositions les renfermant
WO2003055974A2 (fr) 2001-12-22 2003-07-10 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline obtenue a partir de bacillus sp. (dsm 14392) et agents de lavage et de nettoyage contenant cette protease alcaline
DE102007032111A1 (de) 2007-07-09 2009-01-15 Henkel Ag & Co. Kgaa Neue Proteasen und Wasch- und Reinigungsmittel enthaltend diese Proteasen
DE102007036756A1 (de) 2007-08-03 2009-02-05 Henkel Ag & Co. Kgaa Neue Proteasen und Wasch- und Reinigungsmittel, enthaltend diese neuen Proteasen
EP4053256A1 (fr) * 2021-03-01 2022-09-07 Novozymes A/S Utilisation d'enzymes pour améliorer le dépôt de parfum
WO2022184568A1 (fr) * 2021-03-01 2022-09-09 Novozymes A/S Utilisation d'enzymes pour améliorer le dépôt de parfum

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AU3671899A (en) 1999-11-23
AR015282A1 (es) 2001-04-18
CA2326372A1 (fr) 1999-11-11
CN1308638A (zh) 2001-08-15
MA24905A1 (fr) 2000-04-01
EP1073684A1 (fr) 2001-02-07
WO1999057156A1 (fr) 1999-11-11
BR9910100A (pt) 2000-12-26

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