MXPA97003715A - Detergent compositions containing lipase and protein - Google Patents

Detergent compositions containing lipase and protein

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Publication number
MXPA97003715A
MXPA97003715A MXPA/A/1997/003715A MX9703715A MXPA97003715A MX PA97003715 A MXPA97003715 A MX PA97003715A MX 9703715 A MX9703715 A MX 9703715A MX PA97003715 A MXPA97003715 A MX PA97003715A
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MX
Mexico
Prior art keywords
enzyme
whiteness
lipase
protease
fabrics
Prior art date
Application number
MXPA/A/1997/003715A
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Spanish (es)
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MX9703715A (en
Inventor
Margaret Wolff Ann
Baeck Andre
Kasturi Chandrika
Original Assignee
The Procter & Gamble Company
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Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority claimed from PCT/US1995/014984 external-priority patent/WO1996016154A1/en
Publication of MXPA97003715A publication Critical patent/MXPA97003715A/en
Publication of MX9703715A publication Critical patent/MX9703715A/en

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Abstract

The present invention relates to a laundry detergent composition, characterized in that it comprises: a) a lipase enzyme variant D96L of the native lipase derived from Humicola Lanuginosa, b) a protease B enzyme, and c) a surfactant, and wherein said composition comprises levels of enzyme lipase and enzyme protease sufficient to increase the whiteness performance of said composition

Description

DETERGENT COMPOSITIONS CONTAINING LIPflSfl AND PROTEflSfl FIELD OF THE INVENTION The invention relates to laundry detergent compositions containing political enzyme, proteolytic enzyme, and tensile agent, and to the use of various compositions in laundry cleaning processes, to provide whiteness preservation and / or dirt cleaning.
BACKGROUND OF THE INVENTION ce knows of the inclusion of lipase in detergent compositions to improve the performance of cleaning, v.gr. ,, the improvement of the elimination of dirt containing t-rigli cept and stains of the fabrics. Figures are the U.S. Patent. No., 769/173, Cornelissen et al., Issued August 29, 1989; Patent of U. U. No. 5,069,809, Lagerwaard et al., Issued December 3, 1991; Application PCT UO94 / 03578 and HftPPI (Household to Personal Products Tndustry) No. 28/1991. In U.S. Patent No. 4,769,173 a certain class of lipases are described which consist of 1 fungic acids of Hurnicola lanugmosa jun or with strong bleaching agents in detergent compositions. An example of a fungic lipase in this patent is the lipase ex Hurnicola lanuginosa, available from Amano ba or the Arn o-OE brand. In U.S. Pat. No. 5,069,809 describes the combination of strong bleaching agents with a lipase enzyme produced by cloning the gene encoding the lipase produced by Húmicola lanuginosa and expressing the gene in Aspergillus ory¿ae as a host for use in detergent compositions. UO 94/03578 discloses an enzymatic detergent composition containing 10 to 20,000 UL (Political Li Units) per gram of detergent composition of a lipase showing substantial lipolytic activity during the main cycle of a washing process. This lipase is selected in particular on the basis of its inactivation behavior with diisopropyl fluorophosphate (I) FP). Likewise, the inclusion of proteases in detergent compositions for improved cleaning performance is known. For example, protease enzymes are described in US Patent U. fl. No. 5,185,250 and P US lens U. fl. No. 5,204,015. In addition, protease-containing bleaching compositions having increased dirt removal properties are also known, which have been described in UO 94/10284, published May 11, 1194 by The Procter Gamble Company. Commercially available protease enzymes include Al alaR, Esperase ", DurazymR, avinase", riaxatase *, MaxacalR and HaxapernR 15 (flaxacal genetic engineering protein); Pur fectR and subtilisin BPN and RPN '"Of the lipase enzymes, only the lipases derived from Hurnicola lanugmosa and produced on Aspergillus oryzae as a host have so far found wide application as an additive for fabric washing products. It is available under the brand name Lipolase "from Novo Nordisk, Gormsen and rialrnos describe in HAPPI the Lipolase co or the first detergent lipase with a relevant commercial performance in cost based on the use of recombinant DNA technology on an industrial scale. elimination of lipoiase spots, Novo Nordisk has done a number of vanantes.UO 92/05249 describes the D96L variant of the native lug of Humicola lanugmosa that improves the efficiency of butter stain removal by a factor 4.4 over the 11 pass type wild-type (enzymes compared in an amount ranging from 0.075 to 2.5 g of protein per liter.) Example 20 herein describes the storage stability of certain of these types of liquids in liquid detergent compositions in the presence of the Alcalase® protease. The research description No. 35944 published on March 10, 1994 by Novo Nordisiv, describes that vanishing lipase (D96!) Can be added in an amount corresponding to O.OOl-lOOmg of vanishing lipase per liter of wash liquor, the compositions herein are said to optionally comprise "one or more other enzymes, such as amylase, cutmase, protease, cellulose, peroxidase and idase. " Finally, detergent compositions comprising combinations of lipolase and certain proteases are known commercially, for example in U.S. Tide "and in Europe flpelR (both brands sold by The Procter Gamble Cornpany). However, the benefits of conserving whiteness and cleaning dirt on fabrics using combinations of iipase and protease, preferably low levels of the D96L lipase variant in detergent compositions, have not been previously recognized. It has been found that the lipase enzymes can be combined with protease enzymes in surfactant compositions to obtain surprisingly effective dirt cleaning and / or preservation benefits of whiteness. Therefore, an object of the present invention is to provide improved laundry cleaning compositions using lipase enzymes, protease enzymes and surfactants. Another object in the present is to provide a means for removing greasy dirt from fabrics using laundry compositions containing iipase, protease and surfactant. A further object is to provide a means for maintaining whiteness of fabrics using laundry compositions containing lipase, protease and surfactant. These and other objects are ensured herein as can be seen from the following disclosures.
BRIEF DESCRIPTION OF THE INVENTION The present invention relates to laundry detergent compositions comprising: a) a lipase enzyme other than lopilaea; b) a protease enzyme different from Alcalase®; and c) a tension agent; and wherein said compositions comprise levels of enzyme lipase and enzyme protease sufficient to increase the whiteness performance of said compositions. Solid laundry detergent compositions (preferably granules) are preferred, comprising a) a D96L variant of native lipase lipase enzyme derived from Humic! a lanuginosa; b) a protease enzyme, and c) a surfactant agent; and wherein further said compositions comprise levels of said enzyme lipase and enzyme protease sufficient to increase the bleaching performance of said compositions. Laundry detergent compositions comprising: a) a lipase enzyme (preferably lipolase and / or a D96L variant of lipase enzyme of the native lipase derived from Hurnicola lanuginosa) are also preferred; b) a protease enzyme that is derived from a carbonyl hydrolase precursor by replacing the amino acid residue at the position in said carboyl hydrolase with a +76 amino acid residue (preferably in combination with one or more amino acid residue positions) with a different amino acid equivalent to those selected from the group consisting of +99, * 101, + 103, +104, +107, +123, * -27, +105, +109, +126, +128, -135, +156, + 166, "-195, 197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274) according to the number of Bacillus subtyle yloliguefaciens; and c) a surfactant agent; and wherein in addition said compositions comprise levels of enzyme lipase and enzyme protease sufficient to enhance the performance of said compositions. The D96L variant of the preferred lipolytic enzyme of native Humicola lanuginosa lipase is preferably incorporated in detergent compositions at a level of 50 olic units (UL) at 8500 UL per liter of wash solution. Finally. the present invention relates to? ne < For fabric laundry to preserve whiteness and provide for dirt cleaning, said methods comprise contacting fabrics that require whiteness and dirt cleaning with an aqueous solution of a composition comprising enzyme lipase and protease enzyme. sufficient levels to increase the whiteness performance of said composition. All percentages, ratios and proportions in the present are by weight, unless otherwise specified. All of the documents cited are in part relevant, and incorporated herein by reference. L, if limited to theory, it is believed that dirt stains are the result of combinations of greasy stains and particle stains. The fatty spots include lipids, proteins and pigments that are deposited over time on the fabrics by contact with human or animal skin. Most lipids are secreted from the sebaceous gland or sebum. Proteins and pigments from skin fragments are released by the breakdown of epithelial cells. The particulate stains mainly comprise dirt carried by the air and dust from the ground / floor. It is believed that sebum is the main dirt preeente in the laundry, and its elimination is important since the non-eliminated fat acts as a matrix to retain particulate dirt. It is further believed that the compounds present in the sebum can be oxidized to contribute to the yellowing of the fabrics. Particulate soils include the topsoil and products formed during the incomplete combustion of petroleum products. "Dirt cleaning", as used herein, refers to the ability of a detergent composition to eliminate such fouling, during one or more washes, resulting in a possible improvement in the appearance of the fabric. The whiteness preservation is the tracking of the whiteness of washed and used fabrics during a number of washing cycles. A detergent with good performance has a good whiteness preservation profile, that is, it ensures that the whiteness of the washed fabrics is preserved at a high level during the complete cycle of use and washing duration. "Whiteness performance", as used herein, refers to the relative ability of laundry detergent compositions comprising lipid enzymes and protease (as compared to the same compositions comprising only enzyme protease or enzyme lipase, ba or any comparative test conditions that are used) to produce cleaning results of dirt and / or preservation of whiteness.
Enzymes Lipase Lae Lipase enzymes that can be considered for inclusion in the detergent compositions of the present invention include those produced by microorganisms of the Pseudomonas group, such as Pseudornonas stutzeri ATCC 19,154, as described in British Patent No. 1,372,034. Lipids include those that show a positive inverse immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescens IflM 1057. This lipase is available from Amano Pharrnaceutical Co. Ltd., Nagoya, Japan, under the brand name Lipase P " Amano ", hereinafter referred to as" Amano-P ". Lipases include tl Lipase * and L omaxR (G? St ~ Brocades) and I ipolase * (Novo). Lipase are normally incorporated in the detergent composition at levels of 0.0001% to 2% by weight of active enzyme of the detergent composition.
A preferred component of the detergent composition according to the invention is the D96L variant of the lipolytic enzyme of the native iipase derived from Hu icola lan? Gmosa. Preferably, strain DSM 4106 of Hurnicola lanugmosa is used. This enzyme is preferably incorporated into the composition according to the invention at a level of about 50 UL to about 8500 UL per liter of wash solution. Preferably, variant D96L is present at a level of approximately 100 UL to approximately 7500 UL per liter of wash solution, and most preferably at a level of approximately 150 UL to approximately 5000 UL per liter of wash solution. By vanant D96L of lipolytic enzyme is meant the lipase variant ßsegún described in the patent application UO 92/05249 viz. wherein the residue of aspartic acid (D) of lipase native to ex Hunicola lanuginosa in position 96 is changed to Leucma (L). According to this nomenclature, said substitution of aspartic acid by leucine in position 96 is shown as D96L. To determine the activity of enzyme D96L, the normal Lu test was used (Analytical method, internal number Novo Nor-disk 95/6-GB 1991.02.07). A substrate for D96L was prepared by sizing glycerin tributyrate (Merck) using gum arabic as an emulsifier. Lipase activity was determined at pH 7 using est method. of pH. A unit of lipase activity (UL / rng) is defined as the amount needed to release a fatty acid monomorph per minute. The D96L variant of the native Lipase of Hurnicola lanuginosa has the additional advantage of giving a significant benefit in conservation of whiteness when compared to wild-type lipase.
Protease Enzymes Protease enzymes are present at sufficient levels to provide 0.005 to 0.1 flnson units Lü (AU) of activity per gram of composition. The proteolytic enzyme may be of animal, plant or microbial origin (preferably). The proteolytic enzyme of sepna of bacterial origin is preferred. Purified or unpurified forms of the enzyme can be used. The enzymes proteo! produced technologies by chemically or genetically modified mutants are included in the definition, such as the vanants of enzymes of similar structure. The proteolytic enzyme of bacterial senna obtained from Bacillus, Bacillus subtilis and / or Bacillus is particularly preferred as a proteolytic enzyme. lichem or is. Suitable commercial proteolytic enzymes that can be considered for inclusion in the compositions of the present invention include fllcalasaR, EsperasaR, Durazyrn, Sav? NasaR, MaxatasaR, Maxacal, and Maxape "15 (Maxacal genetic engineering protein); Pur fectR and subtisine BPN Y 2b BPN '.. Proteolytic enzymes also encompass the bacterial modified protein proteases, such as those described in European Patent Application Ser. No. 87 303761.8, filed on April 28, 1987 (particularly pages 17, 24 and 98), and which are referred to herein "Proteaea B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which relates to a modified bacterial septa proteolytic enzyme designated "Protease A" herein. Preferred is what is termed "Protease C" herein, which is a variant of an alkaline serine protease from Bací 11 us in which the lisi replaced the arginine at position 27, the tyrosma replacing the valma at position 104, sepna replaced asparagm at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958: 4, corresponding to UO 91/06637, published on May 16 of 1991, which is incorporated in the present reference, also include genetically modified variants, particularly of Protease C. Enzymes proteo! Preferred drugs are selected from the group consisting of Savmasa, Esperasa®, Maxacal®, Purafect®, BPN ', Protease A and Protease B, and mixtures thereof. Bacterial serine protease enzymes obtained from Bacillus subtlis and / or Bacillus licheniformi are preferred. A protease especially preferred herein referred to as "Protease D", is a carhonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carboml hydrolase by substituting the amino acid residue in a different amino acid a position in said carbomyl hydrolase equivalent to the position * 76, preferably also in combination with one or more positions of amino acid residues equivalent to those selected from the group consisting of +99, +101, +103, »L04, + 107, +123, +27, +105, +109, +126, + L28, +135, +156, +166, +195, +197, +204, -206, +210, +216, +217, +218, +222, +260, +265, and / or +274, in accordance with Bacillus a yloliquefaciens subtiiism number, as described in the patent application filed concurrently by fl. Baec and others entitled "Protease-Contaimng Cleaning Compositions" that has the US Series. No. 08 / 322,676, filed October 13, 1994, which is hereby incorporated by reference in its entirety.
Surfactants The detergent compositions according to the present invention comprise a system of surfactants wherein the surfactant may be selected from nonionic and / or ammonium and / or cationic and / or ampholytic surfactants and / or zirconium and / or semi-polar surfactants. . The surfactant is typically present at a level of 0.1% to 60% by weight. Preferred levels of incorporation are 1% to 35% by weight, most preferably 1% to % by weight of laundry compositions with machine and fabric softener added in the rinse, according to the invention. The surfactant is preferably formulated to be compatible with the enziotic components present in the composition. In liquid or gel compositions, the surfactant is formulated preferably in a manner that promotes, or at least does not degrade, the stability of any enzyme in these compositions. Preferred surfactant systems without alkylbenzenesulfonate for use in accordance with the invention comprise as the surfactant one or more nonionic and / or ammonium surfactants as described herein. The condensates of polyethylene oxide, polypropylene, and polybutylene of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, the polyether oxide condensates being preterm. 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, either in straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 2 to about 25 moles, more preferably about 3 to about 15 moles, of ethylene oxide per mole of the phenylphenol. The commercially available nonionic surfactants of this type include Igepal ™ CO-630, manufactured by GflF Corporation; and TrUonTM X-45, X-114, X-100 and X-102, all manufactured by Rohm at Haas Cornpany. 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 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 may be straight or branched, primary or secondary, and generally contains from about 8 to about 2? carbon atoms. The condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of oxide are preferred. of ethylene per mole of alcohol. In said condensation products are present from about 2 to about 7 moles of ethylene oxide and preferably from 2 to 5 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitoi ™ 15-S-9 (the linear alcohol condensation product of C11-C15 with 9 moles of ethylene oxide), TergitolJM 24-L-6 NMU (the product of condensation of C12-C14 primary alcohol with 6 moles of ethylene oxide with a narrow molecular weight distribution), both manufactured by Union Carbide Corporation; Neodol ™ 45-9 (the linear alcohol condensation product 0i4 ~ Ci5 with 9 moles of ethylene oxide), NeodolTM 23-3 (the linear alcohol condensation product C12-O13 with 3.0 moles of ethylene oxide), NeodolTM 45-7 (the linear alcohol condensation product of C? &Vt; -C15 with 7 moles of ethylene oxide), NeodolTM 45-5 (the linear alcohol condensation product of C1-C15 with 5 moles of ethylene oxide) manufactured by Shell Chemical Company, Kyro ™ EOB (the condensation product of C13-C15 alcohol with 9 moles of ethylene oxide), manufactured by The Procter Gamble Company, and Genapol Lfl 050 (the condensation product of C12-C14 alcohol with 5 moles of 6x1.0 ethylene), manufactured by Hoechst 'The preferred scale of HLB in these products is from 8 to 11, preferably from R to 10. Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides described in the EUfl Patent. 4,565,647, Filling, issued January 21, 1996., which has a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, v.gr ., a pol iglueoside, a hydrophilic group that Ib it contains from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably still from about 1.3 to about 2.7 units of taking out. Any reducing saccharide containing 5 or 6 carbon atoms can be-? to use, eg, the glucose, galactose and galactosyl portions and galactosi portions or can replace the glucose portions (optionally the hydrophobic group is attached at positions 2-, 3-, 4- etc., thus giving a glucose or galactose as opposed to a glycoside or galactoside). The interscapdoe bonds can be, eg, between the 1-position of the additional saccharide units and the 2-, 3-, 4- and / or 6- positions in the above saccharide units. The preferred alkyl polyglycoses have the formula R20 (C "H2n0) t (gl? Cos? L) x wherein 2 are selected from the group consisting of alkyl, alkyl e, hydroxyalkyl, hydroxyalkyl, and mixtures thereof in which the alkyl groups contain from about 12"to about 18, preferably from about 12 to about 14 atoms of carbon, n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 10; 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 alkyl polyethoxyl ico alcohol is first formed and then reacted with glucose, or a source of glucose, to form the glucoside (link in position i). The additional glycosyl units can then be linked between their position 1 and position 2, 3, 4 and / or 6 of the above glycosyl units, preferably with position 2 predominating. 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 insolubility in water. The addition of polyoxyethyl portions not 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 to the point where the content of polyoxyethylene is about 50% by weight total condensation product, which corresponds to the condensation with up to about 40 moles of ethylene oxide. Compound examples of this type include some of the commercially available Pluronic ™ surfactants available, manufactured by BASF. Also suitable for use as a nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of e-oxide filled with the product resulting from the reaction of propylene oxide and ethylenediarnine. The hydrophobic portion of these 5 products consists of the reaction product of ethylene diamine and excess propylene oxide, and generally has a molecular weight of about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the product of condensation with lene of around 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 some of the commercially available Tetro cTM compounds, manufactured by BASF. Preterms for use as the non-ionic surfactant of the surfactant systems of the present invention are the condensates of polyethylene oxide of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide, to the polypolysaccharides, and mixtures thereof. The preferred moieties are the C 1 -C 4 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C 8 ~ C 8 alcohol ethoxylates (preferably average C 1) having from 2 to 10 ethoxy groups, and mixtures thereof. The highly preferred nonionic surfactants are the polyhydroxy fatty acid amide surfactants of the formula R2 - wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxyl, 2-hydroxyl 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. Preferably, R1 is methyl, R2 is a straight alkyl chain of Cu-15 or a straight chain of or C-β-18 alkenyl such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such co or glucose, fructose, maltose, lactose, in a reductive amination reaction. When laundry detergents are included in said laundry detergent compositions, the nonionic surfactant systems of the present invention act to improve the oily / oily stain removal properties of said detergent compositions over a wide range of laundry conditions. The highly preferred ammonium surfactants of the present invention include alkylsulphate alkoxylated surfactants which are water soluble salts or acids of the formula R0 (fl) mS03M wherein R is an alkyl group or C10-C24 hydrocarbyl. substituted which has an alkyl component of Cj, o-C2", preferably an alkyl or hydroxyalkyl of O12-C20, preferably n-hydroxyalkyl alkyl group of Ci2-C? β > is an ethoxy or propoxy unit, rn is greater than zero, typically between about 0.5 and about 6; most preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a cation of metal Cg.gr., sodium, potassium, lithium, calcium, magnesium, etc.), a ammonium or substituted ammonium cation. The ethoxylated alkyl sulfates as well as propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include methyl-dimethyi, tri-ethyl-arnonium cations and quaternary ammonium cations such as tetramethylamide and dirnethiipiperidime cations and those derivatives of alkylamines such as ethyl acetate, diethylamine, mixtures thereof and Similar. Examples of surfactants are polyethoxylated alkyl sulfate (1.0) of C12-C18 (Ci2 ~ C? ßE (l.0) M), polyethoxylated alkyl sulfate (2.25) of C12-C18 (C12-C? ßE (2.25) M) , polyethoxylated alkylsulfate (3.0) of C12-C18 (C12 -C? ß (3.0) M) and alkyl sulfato pol 1 ethoxylated (4.0) of C12-C18 (Ci2-Ci8E (4.Q) M), where M is conveniently selected from sodium and potassium. The alkyl ester sulphonate surfactants herein include Linear esters of C8-C20 carboxylic acids (ie, fatty acids) which are sulfonated with gaseous so3 according to "The Journal of The American Oil Chernists Society ", 52 ((1975), pp. 323-329) Suitable starting materials would include natural fatty substances such as tallow derivatives, palm oil, etc. The ester surfactant of fonate alquilico preterido, especially for laundry applications , comprises ethersulfonate to chyllic surfactants of the structural formula: 0 R3 - CH - C - OR * SO3 wherein R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or a combination thereof, 4 is a C 1 -Ce hydrocarbyl, preferably an alkyl or a combination thereof, and M is a cation which forms a salt soluble in water with the ester fonate alkyl ico. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations, such as onoethanola ina., diethanola ina and triethanolamine. Preferably, R3 is Cio-Ciß alkyl, and R * is methyl, ethyl or isopropyl. Especially preferred are methyl ester methyl esters in which R 3 is C 1-6 alkyl. Other surfactants am nicos suitable include surfactants sulphate alquilsul which are salts or water-soluble acids of the formula ROSO3M wherein R preferably is hydrocarbyl C10-C24, preferably an alkyl or hydroxyalkyl having an alkyl component of Clo-C20, most preferably alkyl or C18 hydrocarbyl-12, and M is H or a cation, eg, an alkali rnetal (eg, sodium, potassium, lithium), or ammonium or disubstituted ammonium (eg cations rnetii- tell me ll- yt pinetilarnomo and quaternary ammonium cations or cations such co tet rarnetllamón10 and dirnetilpipepdmio and quaternary ammonium cations derived from such co alk or licked as etiiarnma, dietiiarnina, dietilarnina and mixtures thereof, and Similar). Typically, the C12-C16 alkyl chains are preferred at lower wash temperatures (e.g., below about 50 ° C) and Ciß-iß alkyl chains are preferred at higher wash temperatures (e.g. about 50 ° C). Other ammonia tensile agents useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium and substituted, such co salts or ammonium mono-, di- and trietanolamma) of soap, alcansul sulphonates primary or secondary C8-C22, C8 sulphonates olefmsul -C24, sulfonated polycarboxylic acids prepared by sul phonation product p? rolizado metal citrates alcalmoterreo v.gr, as deecribe in the specification of British Patent No. 1,082,179 the, etersul fatos of alquilpoligli C2 ~ Cs al "( containing up to 10 moles of ethylene oxide); sulphonates alkyl alkyl, fatty acyl glyceryl sulphonates, fatty oleyl glyceryl sulphonates, ether sulphurates of the full-fat phenol, parafamous sulphonates, alkyl phosphates, isoethionates such as acyl isethionates, N-acyl taurates, alkyl succinates and sulphonacyanates, sulfosuccinate orthosols ( especially saturated C12-C18 saturated monomers) and sulfosuccinase diesters (especially saturated and unsaturated C6-C12 diesters), acyl sarcosinates, alkylpolysaccharide sulfates such as alkyl polyglucoside sulfates (the non-sulphonated non-ionic compounds are further described above), primary alkyl sulfates and alkylpolyethoxycarboxylates such as those of the formula RO (CH2CH2?)? CH2COO-M + wherein R is a C8-C22 alkyl, 1 'is an integer from 0 to 10, and M is a soluble salt-binding cation. Resin acids and hydrogenated ream acids are also suitable, such as colophonic acids, hydrogenated rosin acids and ream acids and hydrogenated resin acids present in or derived from wood oil. Additional examples are described in "Surface Active fluent and Detergents" (Vol. I and II of Schwartz, Perry and Berch). A variety of such surfactants are also generally described in the U.S. Patent. 3,929,678, issued December 30, 1975 to Laughlin and others in Column 23, line 58 to Column 29, line 13 (incorporated herein by reference). When included, 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 said ammonia agents. The laundry detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and sernipolar surfactants, as well as nonionic and / or ammonic surfactants other than those already described herein. Suitable cationic detersive surfactants for use in the detergent compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants such as alkyldimethylene halide and those surfactants which have the formula: TR2 (0R3) and] [R «(0R3)? 2R5N + X- wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, - CH2CH (CH3) -, -0H2CH (CH20H) -, -CH2CH2CH2- and mixtures thereof; each R * is selected from the group consisting of Ci-C «alkyl, Ci-hydroxyalkyl, benzyl, ring structures formed by the joining of two groups R *, -OH 2 CHOH-CHOHCOR 6CHOHCH 2 OH where 6 is any hexose or hexose polymer having a molecular weight less than about 1,000, hydrogen when and not 0; RS is the ism that * o is an alkyl chain in which the total number of carbon atoms of R2 plus R5 is not greater than about 18; each y is from 0 to approximately 10 and the sum of the values y is from 0 to approximately 15; and X is any compatible amon. The preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula: Ri 2 R3 4 N + X- (1) wherein R1 is C3-Ci6 alkyl, each of R, R3 and R1 is independently Ci-C * alkyl, Ci-C4 hydroxyalkyls, benzyl, and - (C2H.V0)? H where x has a value of 2 to 5, and X is an anion. No more than one of R2, R3 or RA must be benzyl. The preferred alkyl chain length for Ri is C 12-15, particularly wherein the alkyl group is a mixture of chain lengths derived from palm or coconut fat or is synthetically derived by the formation of olefin or by synthesis of 0X0 alcohols. The preferred groups for R2R3 and R "are methyl and hydroxyethy groups and the X anion can be selected from halide ions, rnetosul. fato, acetate and phosphate.
E xplants of suitable quaternary ammonium compounds of formula (i) for use herein are: cocotrimetyl bromide chloride or bromide; cocometylhydroxyethylammonium chloride or bromide; deci 1 chloride 11 ammonium chloride; chloride or bromide of decil di eti Ihydroxieti lamomo; chloride or bromide of di-ethylhydroxyethyl ilamomo of C12-15; chloride or bromide of cocodi etiihidroxiet ilarnonio; rniristyltrirnetilamonium rnetylsulfate; laupldirneti 1 benzyl ammonium chloride or bromide; chloride or bromide laupldimetiKetenoxi amomo; choline ester (compounds of the formula (1) wherein R 1 is alkyl of -CH 2 ~ -0-C (0) -Ci 2 -? "and R 2 3 R 4 are methyl); di -alkyl idazol inae [compounds of the formula (1)]. Other cationic surfactants 1 useful herein are also described in the U.S. Patent. 4,228,044, Carnbre, issued October 14, 1980 and in European Patent Application EP 000,224. When included herein, the laundry detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8% by weight of said cationic surfactants. Ampholytic surfactants are also suitable for use in laundry detergent compositions of the present invention. These surfactants can be broadly described with 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 a water solubilization group, e.g., carboxyl, sulfonate , sulfate. See U.S. Pat. 3,929,678, Laughlm et al., Issued December 30, 1975 in Column 19, lines 18-35, for examples of ampholytic surfactants. When included herein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of said surfactants to follicles. The zwitterionic surfactants are also suitable in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amides, derivatives of heterocyclic secondary and tertiary amines, or quaternary ammonium derivatives, quaternary phosphine or tertiary sulfone compounds. See U.S. Pat. No. 3,929,678 to Laughlm et al., Issued December 30, 1975, in column 19, line 38 to column 22 line 40 (incorporated herein by reference) for examples of surfactants zwi + er oni eos. When included herein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of said zwitterionic surfactants. the semi-polar nonionic surfactants are a special category of nonionic surfactants including water-soluble amine oxides containing an alkyl portion of from about 10 to about 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing about 1 to about 3 carbon atoms; water-soluble fox oxides containing an alkyl portion of from about 10 to about 18 carbon atornoe and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups, containing from about 1 to about 3 carbon atoms; carbon; water-soluble disulfides containing an alkyl portion of from about 10 to about 18 carbon atoms and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of from about 1 to about 3 carbon atoms. The zwitterionic nonionic detergent surfactants include the amine oxide surfactants having the formula O R3 (OR *) xN (0) (RS) 2 wherein R3 is an alkyl, hydroxyalkyl or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R * is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each RS is an alkyl or hydroxyalkyl group which contains from about 1 to about 3 carbon atoms or a polyether oxide group containing from about 1 to about 3 ethylene oxide groups. The RS groups can be attached to each other, eg, through an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular-include C 1 -C 8 Alkyldirnetium oxides and C 8 -C 12 alkoxyethihydroxyethyarnine oxides. When included herein, the detergent compositions of the present invention typically comprise 0.2. % to about 15%, preferably from about 1% to about 10% by weight of said semi-polar nonionic surfactants.
Detergent components The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components and levels of incorporation thereof depends on the physical form of the composition and the nature of the cleaning operation for which they will be used. For example, the compositions of the invention can be formulated as detergent compositions for manual and automatic laundry, including auxiliary compositions for laundry and compositions suitable for use in the tarn ting of dyed fabrics and fabric softening compositions added thereto. rinse. When formulated as compositions suitable for use in a machine washing method, the compositions of the invention preferably contain a surfactant and a builder and additionally one or more detergent components preferably selected from organic compounds, bleaching agents, enzymes. additional, suds suppressors, dispersants, lime soap dispersants, suspending agents and antiredeposition of dirt and corrosion inhibitors. The laundry compositions may also contain softening agents as auxiliary detergent components. If required, the density of the detergent compositions herein ranges from 550 to 1000 g / liter, preferably 600 to 950 g / liter of composition, measured at 20 ° C. The "compact" form of the compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; the inorganic filler salts are conventional ingredients of detergent compositions in powder form; In conventional detergent compositions, the filler salts are present in substantial amounts, typically 17 to 35% by weight of the total composition. In compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, preferably not exceeding 5% by weight of the composition. The inorganic filler salts, as referred to in the present compositions, are selected from the alkaline and alkaline earth metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate.
Optional detergent ingredients The preferred detergent compositions of the present invention may further comprise an enzyme that provides cleaning performance and / or fabric care benefits. Said enzymes include enzymes selected from cellulases, hernicellulases, peroxidases, glyco-arylases, amylases, cutmases, pectones, xylanases, reductases, oxidases, phenoloxidases, lipoxygenase, ligmnases, p-lulanases, tanases, pentosanas, malanases, β-giucanases, arab osidases or mixtures thereof.
A 2 A preferred combination is a detergent composition which has a set of conventional enzymes applicable as an ilasa, cutmase and / or cellulase together with the lipolytic and proteo enzymes! i t ica The cellulases useful in the present invention include both bacterial and fungal cellulase.
Preferably, they have an optimum pH of between 5 and 9.5. Suitable cellulases are described in the U.S. Patent. 4,435,307, Barbesgoard et al., Which describes fungal cellulase produced by Hurnicola solens. Suitable celloses are also described in GB-A-2,075,028; GB-fl-2.09 .275 and DE-OS-2.247.832. Examples of said cellulases are cellulases produced by a strain of Hu icola solens (Humicola grísea var. Therrnoidea), particularly the strain Hurní cola DSM 1800. Other suitable cellulases originated from Húm coLa solens have a molecular weight of approximately 0KDa, an isoelectric point of 5.5 and containing 415 amino acids.
Especially suitable cellules are those that have color care benefits. Examples of said cellulases are described in European Patent Application No. 91202879.2, filed on November 6, 1991 (Novo). Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching solutions", that is, to avoid transfer of dyes or pigments removed from the subst ates during the washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligmnaea and haloperoxy dasa, such as chloroperoxidase and bronoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application UO 89/099813 and in European Patent Application EP No. 91202882.6, filed on November 6, 1991. Said cellulases and / or peroxidases are usually incorporated in the detergent composition at levels of 0.0001% to 2% of an active enzyme by weight of the detergent composition ». Also suitable are CEC 3.1.1.503 cut masses that can be considered as a special type of lipase, especially lipases that do not require interfacial activation. The addition of cut masses to detergent compositions has been described in, e.g., UO-A-88/09367 (Genencor). The cutinases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. They can be included to iiasas (a and / or ß) for elimination of spots based on carbohydrates. Suitable amylases are Termamyl * (Novo Nordisk), Fungamyl * and BflN * (Novo Nordisk). The enzymes mentioned above may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast.
Said enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Other suitable detergent ingredients that may be added are enzyme oxidation scavengers which are described in co-pending European Patent Application No. 92870018.6 filed on January 31, 1992. Examples of said enzyme oxidation scavengers are ethoxylated tetraethylene polyesters. Especially preferred detergent ingredients are combinations with technologies that also provide a kind of color care benefit. Examples of these technologies are metallocatalysts for color conservation. Said metallocatalysts are described in copending European Patent Application No. 92870181.2. Additional optional detergent ingredients that may be included in the detergent compositions of the present invention include bleaching agents such as PBl. , PB4 and percarbonate with a particle size of 400 to 800 microns. These bleaching components may include one or more oxygen bleaching agents and, depending on the bleaching agent chosen, one or more bleach activators. When oxygen bleaching compounds are present, they are typically found at levels from about 1% to about 25%. In general, bleaching compounds are optional in non-liquid formulations, e.g., granular detergents.
The bleach component for use herein may be any of the agents useful for detergent compositions including oxygen bleach, 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. A category of oxygen bleaching agent that can be used comprises percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxy phthalate hexahydrate, the magnesium salt of rneta-chloroperbenzoic acid, 4-non? Lamino-4-oxoperox? Butpic acid and diperoxydecanedioic acid. Said bleaching agents are described in the U.S. Patent. 4,483,781, U.S. Patent Application. 740,446, European Patent Application 0,133,354 and Patent of E.U.A. 4,412,934. Highly preferred bleaching agents also include 6-non? Lam? No-6-oxo? Erox? Caproic acid as described in US Pat.U. 4.4634, 551. Another category of bleaching agents that can be used comprises the halogen bleaching agents. Examples of hypohalite bleaching agents, for example, include trichloroisocyanate acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo-alkanesul fonamides. Said materials are normally added to 0.5-10% by weight of the final product, preferably 1-5% by weight. The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylend a ma (TAED), nonanoyloxybenzenesulphonate (NOBS, described in US 4,412,934), 3,5-tmemethexanolox-benzenesulphonate (ISONOBS, described in US Pat. EP 120,591) or pentaacetylglycerol (PAG), which are perhydrolyzed to form a peracid as the active bleach species, which leads to the improved bleaching effect. Also suitable activators are acylated citrate esters as described in co-pending European Patent Application No. 91870207.7. Useful bleaching agents including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleach compounds for use in Cleaning compositions according to the invention are described in co-pending application USSN 08 / 136,626. The hydrogen peroxide may also be present by adding an enzyme system (i.e., an enzyme and substrate) which is capable of generating hydrogen peroxide at the beginning or during the washing and / or rinsing process. Such enzymatic systems are described in Patent Application EP 91202655.6, filed October 9, 1991. Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. One type of oxygen-free bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocytes. These materials can be deposited on the substrate during the washing process. At the moment of irradiation with light, in the presence of oxygen, such as when clothes are hung to dry in daylight, sulfonated zinc phthalocyamine is activated and, therefore, the substrate is bleached. The preferred zinc phthalocyamine and a photoactivated bleaching process are described in the U.S. Patent. 4,033,718. Typically, the detergent compositions will have about 0.025% to about i.25% by weight of sulfonated zinc phthalocyamine. The compositions according to the present invention may further comprise a detergency builder system. Any conventional detergency builder system is suitable for use herein which includes materials of aluminosilicate, silicates, polycarboxylic acids and fatty acids, materials such as ethenedi amine tetraacetate, metal ion sequestrants such as ammopoliphosphonates., particularly etiiendiaminetetramethylenephosphonic acid and diethylene riaminepentanethylenephosphonic acid. For obvious environmental reasons, phosphate builders, although less preferred, 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 zeolite A, X, B, HS or hydrated MAP. Another suitable inorganic builder material is layered silicate, for example 5KS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (a2 i2? S). Suitable polycarboxylates containing a caryoxyl group include lactic acid, glycolic acid and derivatives The ether of the same as described in Belgian Patents Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, alonic acid, (et? Iend? Ox?) D? Acetic acid, maleic acid, diglycolic acid, acid L5 tartaric, trat romeo acid and furnapco acid, as well as the ether carboxylates described in Offenlegenschpf German 2,446,686, and 2,446,687 and the Patent of E.U.fl. No. 3,935,257 and the sulfide carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing three carboxyl groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxyrnethyloxysuccinates described in British Patent No. 1,379,241, the lactoxysuccinates described in the Country Application. 7205873, and the > 5 oxypolycarboxylate materials such as 2-oxa-l, l, 3-propanecarboxylates, described in British Patent No. 1,387,447. The? Olicarboxylates containing four carboxyl groups include oxydisuccinates described in British Patent No. 1,261,829,1,1,2,2-ethanetetracarboxylates, 1, 1. , 3,3-propanotetracarboxylates and 1,1,2,3-propanotertracarboxylates. Polycarboxylates containing sulfo substitutes include the sulfosuccinate derivatives described in British Patents Nos. 1,398,421 and 1,398,422 and in the US Pat. No. 3,936,448, and the suphonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substitutes are described in British Patent No. 1,439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide-pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1, 2, 3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include methyl acid, pyromellitic acid and the phthalic acid derivatives described in British Patent No. 1,425,343. Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxyl groups per molecule, more particularly citrates.
Preferred builder systems for use in the present compositions include a mixture of a detergent builder. water soluble monosilicate such as zeolite 0 or a layered silicate (SKS / 6), and a water soluble carboxylate chelating agent such as citric acid. A suitable chelator for inclusion in the detergent compositions according to the invention is ethylene glycol-N, N'-d-succinic acid (EDDS) or the salts thereof. alkaline metal, alkaline alkaline, ammonium, or substituted ammonium thereof, or mixtures thereof. The preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of said preferred sodium salts of FDDS include a2E DS and 2 EDDS. Examples of Said preferred magnesium salts of EDDS include MgEDSOs and Mg2 EDDS. Magnesium salts are most preferred for inclusion in compositions according to the invention. Preferred detergent builder systems include a mixture of a detergent builder.
, Water soluble aluminosilicate, such as zeolite fl, and a water soluble carboxylate chelating agent such as citric acid. Other detergent builder materials that can be part of the builder system for use in granular compositions include materials inorganic such as carbonates, bicarbonates, alkali metal silicates and organic materials such as organic phosphonates, amino polyalkylene phosphonates and arnino polycarboxylate. Other suitable water-soluble organic salts are homo or copolyimpe acids or their salts, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by means of not more than two carbon atoms. Polymers of this type are described in GB-fl-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with anhydrous rnalene, such copolymers having a molecular weight of 20,000 to 70,000, especially about 40,000. Builder-detergent salts are usually included in amounts of 10 to 80% by weight of the composition, preferably 20% to 70% and more usually 30% to 60% by weight. Another optional ingredient is a s? Pressor of foams, exemplified by silicones and a mixture of silicon-silica. Silicones can generally be represented by alkylated polystyrene materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of different types. These materials can be incorporated as particles in which the foam suppressant is advantageously and freely incorporated into a waterproof or water-dispersible detergent surfactant detergent vehicle. Alternatively, the foam pressor can be dissolved or dispersed in a liquid vehicle and applied by spraying on one or more of the other components. A preferred silicone foaming agent agent is described in Bartollota et al., U.S. Patent. 3,933,672. Other particularly useful foam suppressors are the self-setting silicone foam suppressors described in the German Patent Application DTOS 2,646,126 published on April 28, 1977. An example of a composite as such is DC-544, commercially available from Dow Corning, which is a siloxane / glycol copolymer. The essentially preferred foam controlling agents are the foam suppressor system comprising a mixture of silicon oils and 2-alkyl alkanols. Suitable 2-alkyl-alkanols are 2-butyl-octanol which are commercially available under the brand name ISO 12 R. Such foam suppressor systems are described in co-pending European Patent Application No. 92870174.7, presented the LO of November 1992. Particularly preferred silicone foam controlling agents are described in co-pending European Patent Application No. 92201649.8. Said compositions may comprise a silicone / silica mixture in combination with nonporous fuming silica such as Aerosil *. The foam suppressors described above are normally employed at levels from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
Other components used in detergent compositions may be employed, such as soil suspending agents, soil release agents, optical brighteners, bleach, bactericides, rust inhibitors, coloring agents and / or encapsulated or non-encapsulated perfumes. Especially suitable encapsulation materials are water soluble capsules consisting of a matrix of polysaccharide and polyhydroxyl compounds as described in GE 1,464,616. Other suitable water-soluble encapsulation materials comprise dextrins derived from non-gelatinized starch acid esters of substituted dicarboxylic acids as described in US 3,455,838. These acid ester dextrues are preferably prepared from said starches such as waxy corn, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulation materials include N-Lok manufactured by National Starch. The N-Lok encapsulation material consists of a modified corn starch and glucose. The starch is modified by adding monofunctional substituted groups such as octe or succinic anhydride. Suitable antiredeposition and soil suspending agents herein include cellulose derivatives such as rilethylcellulose, carboxymethyl cellulose, and hydroxyacetic acid, and homo- or co-polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and copolymers of maleic anhydride-acrylic acid, previously mentioned as detergent enhancers, as well as the copolymers of manganese anhydride with ethylene, methyl vinyl ether or methacrylic acid, the anhydrous rhenalic which constitutes minus 20 mole percent of the copolymer. These materials are normally used at levels of 0.5% to 10% by weight, more preferably from 0.75% to 8%, and preferably from 1% to 6% by weight of the composition. Preferred optical brighteners are essentially ammonia, examples of which are 4,4'-b? S- (2-d? Ethanolarn? No-4-aml? No-s-tpaz? N-6? Lam? No ) are-2: 2'-disodium disulfonate, 4, -4'-bis- (2-morpholino-4-aml? no-st? a? n? -6? larn? noest? lben) -2: -disodium disulfide, 4,4'-b? S- (2,4-d? Aml? No-s-tr? Az? N-6-? Lam? No) est? Lben- 2: 2 '-disodium fonate disodium, 4', 4 '' ~ b? S- (2, 4- diammo-st r? Azm-6? Larnmo) is ibas-2-sulphonate of nonosodium, 4 , 4 '- b? S- (2 -anilmo-4- (N-met? IN-2-hydrox? Et? Iam? No) -st nazi-6-? Lamino lestylben-2, 2' -disulfonate of disodium, 4, 4'-bi e (4-feml-2, 1, 3-1 -ololol-2-yl) -est? lben-2,2'-d? s? fonate of disod or, 4, 4'b? S (2-an? Lmo-4- (l-met? L-2? H? Rox? Et? Lam? No) ~ s-tpaz? N-6-? Lam? No) est? Lben -2,2'-disodium disulfonate, 2 (est? Lb? L-4"~ (naphtho-l ', 2': 4,5) -l, 2, 3-tpazol-2" -sul onate from sodium and 4,4'-b? s (2-sulfostipl) b? sfem Lo. Other useful polydrug materials are polyethylene glycols, particularly those of mole weight. of 1000-10000, particularly 2000 to 8000 and most preferred about 4000. These are used at levels of 0.20% to O 5%, more preferably from 0.25% to 2.5% by weight. These polymers and the abovementioned homo- or co-polyarylene polycarboxylate salts are valuable for improving the preservation of whiteness, deposition of ash in the fabric, and cleaning performance in clay, and protein and oxidizable soils in the presence of metal impurities. of Transition. The soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and / or propylene glycol units in vain arrangements. Examples of said polymers are described in the patents of E.U.A. Commonly assigned Nos. 4116885 and 4711730 and European Published Patent Application No. 0272033. A particular preferred polymer according to EP-A-0 272 033 has the formula (CH3 (PEG 3)? 7d (POH) o.25L "T-PO) 2.8 (T-PEG) o.4] T (PO-H) o.2S ((PEGU3CH3) o.7S where PEG is ~ (0C2H.;) 0-, PO is (OC3H6O) and T is (pcOCeH «CO). Also very useful are modified polyesters such as random copolymers of di ethyl terephthalate, dimethylsulphthalate, ethylene glycol and 1, 2-omega-3-ol, end groups consisting mainly of sulfobenzoate and secondarily of ethylene glycol and / or propanediol monomers. . The aim is to obtain a polymer blocked at both ends by sulfobenzoate groups, "firstly", in the present context, most of said copolymers will be blocked at the ends with sulfobenzoate groups. However, some copolymers will be less than completely blocked at the ends and therefore their end groups may consist of ethylene glycol onoster and / or 1,2-propanediol, which consist "secondarily" of said species. The polyesters selected herein contain about 46% by weight of reftalic dimethylite acid, about 16% by weight of 1,2-propanediol, about 10% by weight of glycerol, about 13% by weight of dimethisol acid. obenzoic and about 15% by weight of sulphonic acid, and have a molecular weight of about 3,000. Polyeeterers and their method of preparation are described in EPA 311 342. Fabric softening agents may also be incorporated into laundry detergent compositions in accordance with the present invention. These agents can be of inorganic type? organic. Inorganic softening agents are exemplified by the smectite clays described in GB-A-1 400 898 and in USP 5,019,292. The organic fabric softening agents include the water soluble tertiary amines as described in GB-A1 514 276 and EP-BO 011 340 and their combination with quaternary salts of C12-C14 rnonoa omo are described in EP-B-0 026 527 and EP-B-0 026 528 and EP-B-0 242 919 disclose long chain diamines. Other useful organic ingredients of fabric softener systems include high molecular weight polyethylene oxide materials as described in EP-A-0 299 575 and 0 313 146. The smectite clay levels are usually in the range of 5 to 1.5%, preferably from 8% to 12% by weight, adding the. material as a dry mix component to the rest of the formulation. Spreading fabric organic agents such as water-insoluble tertiary amines or long double-chain amide materials are incorporated at levels of 0.5% to 5% by weight, usually from 1% to 3% by weight, while High molecular weight polyethylene oxide materials and water soluble cationic materials are added at levels from 0.1% to 2%, usually from 0.15% to 1.5% by weight. These materials are usually added to the portion of the composition that was spray dried, although in some cases it may be more convenient to add them as dry mixed particles, or apply them by spray as a molten liquid over the other solid components of the composition. The present invention also relates to a process for inhibiting the transfer of dye, from one fabric to another, of solubilized and suspended dyes that are encountered during fabric washing operations involving dyed fabrics. The detergent compositions in accordance with the present invention can comprise from 0.001% to 10%, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of poly-epcosal dye-inhibiting agents. Said dye transfer inhibitors are usually incorporated in detergent compositions to inhibit the transfer of dyes from fabrics dyed to fabrics washed therewith. These polymers have the ability to complex with, or adsorb fugitive dyes washed from the dyed fabrics before the dyes have the opportunity to bind to other articles in the wash. Especially suitable polymecopyl dye transfer inhibiting agents are polyarnine N-oxide polymers, N-v? Mlpyrrolidone and N-vi linidazole copolymers, polyvinylpyrrolidone polymers, polyvinyloxyzolidones, polyvinyllimidazoles or mixtures thereof. The polyamide N-oxide polymers suitable for use contain units having the following structural formula: P (I) Ax R where P is a polifiable unit, to which the RNO group can be joined, or where the RN-0 group is part of the polable unit or a combination of both, fl is NC (0), CÜ2, C (O), -O-, -S-, -N-; x is O or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or cyclic aliphatic groups or any combination thereof to which the nitrogen of the group N-0 may be attached or where the nitrogen of the group N-0 is part of these groups. The group N-0 can be represented by the following general structures: 0 0 (R1) X - N- (R2) and --N- (Rl) x (R3) z wherein R1, R2 and R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, "x" and / or "y" and / or "z" is 0 or 1, and wherein the nitrogen of the group N -0 may be joined, or where the nitrogen of group N-0 forms part of these groups. The gr? P > or N-0 can be part of the polimepable unit (P) or it can be attached to the polymeric base structure or a combination of both. Suitable polyarynin N-oxides wherein the group N-0 forms part of the polymerizable unit comprise N-oxides of polyanine wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyacrylate N-oxides comprises the group of polyarynin N-oxides wherein the nitrogen of the group N-0 forms part of the group R. N-preferred polyamine oxides are those wherein R is a group heterocyclic ico such as pyridine, pi rol, imidazole, rrolidine, piperidma, quino! a, acpdma and derivatives thereof. Another class of said polyamine N-oxides comprises the group of polyarnine N-oxides wherein the nitrogen of the group N-0 is attached to the group R. Other suitable polyarnine N-oxides are the polyamine oxides to the which is joined by the group N-0 to the polyfunctional unit. A preferred class of polyarynin N-oxides are the polyarynin N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group wherein the nitrogen of the functional group N-0 is Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pipdine, pyrrole, irnidazole and derivatives of the same. Another preferred class of polyacrylate N-oxides are the polyaxine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the functional group N-0 is attached to said groups.
R. Examples of these classes are polyarnine oxides wherein the R groups can be aromatic such as femlo. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polution base structures are poly vimios, polyalkylene logs, polyesters, polyethers, polya ida, polyimidae, polyaptals and mixtures of the isms. The amine N-oxide polymers of the present invention typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1000000. However, the amount of amine oxide groups present in the polyarnide oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Preferably, the ratio of amine to N-oxide of amine is from 2: 3 to 1: 1000000. Most preferably, from 1: 4 to 1: 000000, most preferably even from 1: 7 to 1: 1000000. The polymers of the present invention actually encompass random or block copolymers in which one type of monomer is an N-oxide of amine and the other type of onornero is either an N-oxide of amine or not. The amine oxide unit of the polyarynin N-oxides have a PKa < 10, preferably PKa < 7, rnuy preferably PKa < 6. The polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical as long as the material has the desired water solubility and the desired dye suspension power. Typically, the average molecular weight is within the range of 500 to 1,000,000; preferably 1,000 to 50,000, most preferably 2,000 to 30,000, rnuy h? I prefer it even from 3,000 to 20,000. The polymers of N-vi lirnidazole and N-vimlpyrrolidone which can be used in the present invention have an average molecular weight scale of 5,000 to 1,000,000, preferably 20,000 to 200,000. Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from copolymers of N-vimlirnidazole and N-vimlpyrrolidone wherein said polymer has an average molecular weight scale of from 5,000 to 50,000, most preferably from 8,000 to 3p, 000, even more preferably 10,000 to 20,000. The average molecular weight scale was determined by light scattering, as described in Barth H.G. and Mays 3.U. Chemical Analysis Vol 113, "Modern Methods of Polyrner Charactepzation. "The highly preferred copolymers of N-vmilirnidazole and N-vi l pyrrola dona have an average molecular weight scale of about 5,000 to 50,000, preferably from 8,000 to 30,000; ,000. The copolymers of N-vimlimidazole and N-vi nilpyrrolidone characterized by having said average molecular weight scale provide excellent dye transfer inhibiting properties and at the same time do not adversely affect the cleaning performance of the detergent compositions formulated with the same. The copolymer of N-vinylipudazole and N-vimlpyrrolidone of the present invention has a molar ratio of N-vinylniridazole to N-vmi lpyrrolidone from 1 to 0.2, most preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4. The detergent compositions herein can also use polyvinyl pyrrolidone ("PVP"), which has an average molecular weight of 2,500 to 400,000, preferably 5,000 to 200,000, preferably 5,000 to 50,000, and preferably even 5,000 to 15,000. . Suitable polyvinylpyrrolidones are commercially available from TSP Corporation, New York, NY and Montreal, Ca ad under the trademarks PVP K-15 (molecular weight of 10,000 viscosity), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinylpyrrolidones that are commercially available from BASF Corporation include Sokalan HP 165 and Sokalan HP 12; Polymer 1 pyrrole and donuts known to those skilled in the detergent field (see, for example, EP-A-262,897 and EP-A-256, 696). The detergent compositions herein can also use polyvinylloxazolidone as a polypnecopic dye transfer inhibiting agent. Said polivi and loxazolidones have an average molecular weight of 2,500 to 400,000, preferably 5,000 to 200,000, preferably 5,000 to 50,000, and most preferably still of 5? ,000 to 15,000. The detergent compositions herein can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylpudazoles preferably have an average molecular weight of 2,500 to 400,000, most preferably 5,000 to 50,000, and even more preferably 5,000 to 15,000.
Washing method The process described herein comprises contacting fabrics with a laundry solution of The usual way, and is exemplified below. The process of the invention is conveniently carried out in the course of the washing process. The washing method is preferably carried out at 5 ° C to 95 ° C, especially between 10 ° C and 60 ° C. The pH of the treatment solution is preferably from 7 to 11, especially from 7.5 to 10.5. The following examples exemplify the compositions of the present invention, but do not necessarily limit or otherwise define the scope of the invention In the detergent compositions, the abbreviated identifications of the components have the following meanings: LAS: 01 Cyl sodium linear sodium benzenesulfonate of C12 TAS Seboaiquilsuifato of sodium XYAS Sodium alkylsulfate of CIX ~ CI? SAS Secondary alkyl (2,3) of C12-C14 in the form of the sodium salt APG: Alkyl poly glycoside surfactant of formula Ci2 ~ (gl? Cos? L)? , where x is 1.5. AEC Alkylpolyglycoside surfactant of formula C12 ethoxy (2) carboxylate Secondary soap surfactant of acid formula 2-but? Loctane? Co 25EY: A predominantly linear primary alcohol of C12-15 condensed with an average of Y moles of oxide of ethylene. 45EY: A linear primary alcohol predominantly of O14-C15 condensed with an average of Y moles of full-oxide. XYEZS; Alkyls? C sodium fato ?? -C ?? condensed with an average of Z moles of ox added of etiol per mole. Non-ionic Ethoxylated fatty alcohol / mixed side of (C13-C1S with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the trade name Plurafax LF404 by- BASF Grnbh CFflfl Alqui l N- C2-C2-C4-C4-C5-C5-C5-C5-C3-C5-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3-C3 : Sodium carbonate anhydrous Phosphate Tripolyphosphate sodium MA / AA: Copolymer of maleic acid / acrylic .1: 4, average molecular weight approximately 80,000 Polyacrylate Oxygen polyacrylate with an average molecular weight of 8,000 sold under the brand name PA30 by BASF GmbH Zeolite A: Hydrated sodium inosilicate alum of formula Nai2 (AIO2SÍO2) i2-27H2O having a primary particle size in the range of 1 to 1.0 microns Citrate: trisodium citrate dihydrate Citric acid: citric acid o Perborate Anhydrous sodium perborate bleach monohydrate, empirical formula NaB? 2.H2? 2 PB «Sodium perborate anhydrous tetrahydrate Percarbonate Anhydrous sodium percarbonate bleach from pyrimic oxide r 2 - 2 C O3.3 H2 O2 TAED Tet raacet i leti lendiarni na For fine Paraffin oil sold under the tradename liong 70 by Uintershall Xylanase Enzyme xylanolitica sold under the tradenames Pulpzyrne HB or SP431 by Novo Nordisk A / S or Lyxasan (Gist-Brocades) or Optip? Lp or Xylañase (Solvay) Protease: Proteolytic enzyme sold under the trademark Savinase by Novo Industries A / S (approximately 2% enzyme activity).
Protease D Proteolytic enzyme which is a vanant of Nuntia N76D / S103A / V104T of Bacillus lentus, in accordance with the subtilisme number of Bacillus a yloliquefaciens Arní lasa Arylolitic enzyme sold under the trade name Lipolase by Novo Nordisk A / S Lipase: Lipolytic enzyme sold under the Lipolase brand by Novo Industries A / S (approximately 2% enzyme activity). Lipasa D96L Vanante from II pass n tLva derived from Hurnicola lan? Gmosa Peroxi dasa Enzyme peroxidase Ceiulase: Cellulose enzyme sold under the brand Carezyrne by Novo Industries A / S. CMC Ca rbox irnetil sodium cellulose. HEDP Acid 1, 1 -h? Dro? Etand? Phosphonium with DETPMP Acid diethylenetriamine pentamethyl methosphenol PVP Polyvinylpyrrolidone polymer EDDS Acid Etiiendiami na-N, N '-disuccin, CS isomer, S] in the form of the sodium salt. Foam suppressant 25% paraffin wax, mf 50 ° C, 17% hydrophobic silica, 58% fine oil Foam suppressor granulated 12% silicone / yes lice, 18% steappyl alcohol, 70% starch n in granulated form SCS Cunensulfonat or sodium bulfate Anhydrous sodium sulfate HMWPEO high molecular weight polyethylene oxide PGM Polyglycerol monostearate which has a trade name Radiasu f 248 TAE 25 Ethoxylated tallow alcohol (25) In the following examples, all indicated levels are expressed as% active enzyme by weight of the composition: EXAMPLE 1 A compact granular composition for cleaning fabrics according to the invention was prepared as follows: 45 AS 9.0 25E3S * 2.3 25E5 4.4 TFAO 1.9 Zeolite fl 14.1 NaSKS ~ 6 11. g Citric acid 3.2 Carbonate 7.1 MA / AA 4.5 CMC 0.4 N-oxide of oli (4-vinylpyridine) / co-polyrne or vinylirnidazoi and vinyipyrrolidone 0.027 Lipasa D96L To give 5000 UL / 1 wash Protease 0.03 Cellulase 0.0006 Arnilasa 0.006 TAED .9 Pe reabonate 22.3 Foam suppressor 3.6 Water / others Up to .1.00% The use of this laundry detergent composition for washing fabrics identified by consumers As a result of the formation of dirt, it resulted in improved cleaning of dirt from these fabrics as compared to the cleaning of dirt achieved using this composition when it only comprises l-96L lipase or protease.
EXAMPLE 2 A granular composition for cleaning fabrics according to the invention was prepared as follows: LAS 10.3 45AS 6.6 25AE3S l.fl Zeolit A 26.3 Carbonate 26.3 PEG 1.7 Polycarbonate 3.2 Na2S04 10.3 23E6.5 0.5 Lipase D96L To give 300 UL / 1 washing Protease D To give 0.1 rng of protease ct i va / 1 of water Water and others Have 100% Fl use of this laundry detergent composition to wash fabrics identified by consumers as having formation of dirt resulted in improved cleaning of dirt from these fabrics against dirt cleaning achieved using this composition when it only comprises lipase D96L or protease D. Similar results can be observed by substituting in this formula lipase D96L with Lipase, or using both lipase as lipase D96L; and replacing with protease, Maxacal.RTM., Protease A, Protease B, or Protease C, or mixtures thereof by D. protease.
EXAMPLE 3 Granular compositions for cleaning fabrics according to the invention were prepared as follows: I II III IV LAS 22.0 22.0 22.0 22.0 Phosphate 23.0 23.0 23.0 23.0 Carbonate 23.0 23.0 23.0 23.0 If li cato 14.0 14.0 14.0 1 .0 Zeolite A 8.2 8.2 8.2 8.2 DETPMP 0.4 0.4 0.4 0.4 Sodium sulfate 5.5 5.5 5.5 5.5 Protease 0.001 0.001 0.001 0.001 Protease D 0.02 0.01 Xi Lanae 0.04 - - - Lipase D96L 0.005 0.002 0.005 L ipasa 0.005 Cell? Lasa 0.001 - - 0.001 A ilasa 0.01 - 0.01 - Pect sa 0.02 - - - Water / others Up to 1 0% EXAMPLE 4 Granular compositions for cleaning fabrics according to the invention were prepared, as follows: I II III IV L S 12.0 12.0 12.0 12.0 ZeoLita A 26.0 26.0 26.0 26.0 S 4.0 4.0 4.0 4.0 SAS 5.0 5.0 5.0 5.0 Cit tiempo 5.0 5.0 5.0 5.0 Sul ato de «sodium 17.0 17.0 17.0 17.0 Perborato 16.0 16.0 16.0 - TAED 5.0 5.0 5.0 - Xilanasa 0.20 - - - Pro tea sa 0.06 0.02 0.08 Protease T) 0.03 0.01 - - Lipase D96L 0.005 0.0003 0.01 0.005 Cellulase 0.001 - - 0.001 Arní lasa 0.01 _ 0.01 - Pect mass 0.02 - - - Water / others Up to 100% EXAMPLE 5 Granular compositions for cleaning fabrics according to the invention were prepared, which are especially useful in washing colored fabrics, as follows: LAS 11.4 10.7 - TAS 1.8 2.4 - TFAA - - 4.0 LC) 45 AS 3.0 3.1 10.0 45E7 4.0 4.0 _ 25E3 3.0 68E11 1.8 1.8 25E5 - - 8.0 Treatment 14.0 15.0 7.0 Carbonate - - 10 Acid Cíp p 3.0 3.0 3.0 Zeoite A 32.5 32.1 25.0 NaSKS-6 9.0 0 MA / AA 5.0 5.0 5.0 DETPMP 1.0 0.2 0.8 Xylanase 0.001 - - Prot 0.01 0.01 Protease D 0.02 5 Lipase D96L 0.0005 0.01 0.00 Arnilasa 00..0033 00..003 0.005 Pect i nasa 0.01 - Cellulasa 0 0..000055 - 0.001 Sili cato 2.0 2.5 Sulphate 3 3..55 5 5..22 3.0 PVP 0.3 0.5 N -poly (4-v? Mi? Pd a) / vi lirnidazole and vi lpyrrolidone cobuii ü.2 Perborate 0.5 1.0 Peroxidase 0.01 0.01 Phenol its L fonate 0.1 0.2 flg? A / ot Up to 100% EXAMPLE 6 Granular compositions for cleaning fabrics according to the invention were prepared as follows: LAS 6.5 8.0 Sulfate 15.0 18.0 Zeolite A 26.0 22.0 Ni t r L l? T sodium acetate 50. 5.0 PVP 0.5 0.7 GAE? 3.0 3.0 Boric acid 4.0 - Perborate 0.5 1.0 Phenol sulfonate 0.1 Pro cess D 0.06 0.02 X li n s 0.01 Sil i cato 5.0 5.0 Carbonate 15.0 15.0 But ida 0.1 - Lipase D96L 0.001 0.005 flr il a 0.01 0.01 Pect mass 0.02 - Cellulase 0.005 0.002 Water / others 100% Haet EXAMPLE 7 Granular compositions were prepared for cleaning fabrics according to the invention that provide "softness by washing" capability, as follows: 45AS 10.0 LAS 7.6 68AS 1.3 45E7 4.0 25E3 - 5.0 Coconut-alkyldirnethi-hydroxyethyl monium chloride 1.4 1.0 Citrate 5-0 3.0 Na-SKS-6 - 11.0 ZeoLite A 15.0 15.0 MA / AA 4.0 4.0 DETPMP 0.4 0.4 Perborate 15.0 - Percarbonate - 15.0 TAED 5.0 5.0 Clay Esrnect ita 10.0 LO.O HMUPEO - 0.1 Pro easa 0.02 0.U1 Lipase D96L 0.002 0.ÜÜ03 Ami lasa 0.03 0.005 Xi wool 0.03 - Cellulase 0.02 0.00 Pecti handle 0.01 - Silicate 3.0 5.0 Carbonate 10.0 10.0 Foam suppressor ranul r 1.0 4.0 CMC 0.2 0.1 Water / others Up to 100% EXAMPLE B Heavy duty liquid fabric cleaning compositions suitable for use in the pretreatment of dyed fabrics were prepared, and for use in a machine laundry method, in accordance with the invention, as follows: 1 II III IV V 24AS 20.0 20.0 20.0 20.0 20.0 S? 5.0 5.0 5.0 5.0 5.0 Cit rato 1.0 1.0 1.0 1.0 1.0 12E3 13.0 13.0 13.0 13.0 13.0 Monetanolamine 2.5 2.5 2.5 2.5 2.5 Xylanase 0.02 - - - - Protease 0.005 0.03 0.02 0.04 0.01 Lipasa D96L 0.002 0.01 0.0005 0.001 0.004 Arnilasa 0.005 0.005 - - 0.004 Cellulase 0.04 - 0.001 - - Pecf 1 nasa 0.02 0.02 - _ _ Water / propylene glycol / ethane K 100: 1: 1) EXAMPLE 9 Heavy duty liquid compositions for cleaning fabrics according to the invention were prepared as follows: I II III IV THE acid form - - 25.0 C12-14 alkenyl succinic acid 3.0 8.0 10.0 Citric acid 10.0 15.0 2.0 2.0 25AS acid form 8.0 8.0 - 15.0 25AE2S acid form - 3.0 - 4.0 25AE7 - 8.0 - 6.0 25AE3 8.0 CFflA - - - 6.0 DETPMP 0.2 - 1.0 1.0 Fatty acid - - 1.0 1.0 Oleic acid 1.8 - 1.0 - Ethanol 4.0 4.0 6.0 2.0 Propanodiol 2.0 2.0 6.0 10.0 Xylanase 0.05 - - - Protease D 0.02 0.02 0.02 0.01 flrnilase 0.005 0.01 0.005 0.01 Lipase D96L 0.005 0.02 0.005 0.01 Cellulase 0.005 - ~ - Pectinase 0.02 - _ - Coalkalkyl di ethylhydroxyethylammonium chloride - 3. .0 Smectite clay - 5. .0 PVP 1.0 2. .0 - Perborate 1, .0 - Phenol s? I fonate 0, .2 - Peroxidase 0, .01 - Water / others Up to 100%

Claims (12)

NOVELTY OF LR INVENTION CLAIMS
1. A laundry detergent composition comprising, (a) a lipase enzyme different from lipolase; (b) a protease enzyme other than Alcalase "; and (c) a surfactant, said compositions comprising levels of enzyme lipase and enzyme protease sufficient to increase the whiteness performance of said compositions
2. A laundry detergent composition comprising (a) a lipase enzyme, D96L variant of the native lipase derived from Humicola lanuginosa, (b) a protease enzyme, and (c) a surfactant, said compositions comprising levels of said enzymes .lipase and protease sufficient to increase performance whiteness of said compositions
3. The laundry detergent solid composition according to claim 2, further characterized in that the protease enzyme is selected from the group consisting of fllcalasaR, Eeperase *, D? razyrn.R, Savinaee.R, Maxatase ", Maxacal.RTM. MaxapernR 15, Purafect *, subtilisin BPN and BPN ', Ptrotease fl, Protease B, Protease C, Protease D, and mixtures thereof.
4. The solid laundry detergent composition according to claim 2 further characterized in that the protease enzyme comprises a protease enzyme derived from a carbonyl hydrolase precursor, replacing a plurality of amino acid residues at a position in said carbomyl hydrolase with a different amino acid. equivalent to the position -76 in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, * -10? , +123. +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222 , +260, +265 and / or +274, in accordance with the Bacillus amyloliquefaciens subtilisin numbering.
5. A laundry detergent composition comprising: (a) a lipase enzyme; (b) a protease enzyme derived from a carbonyl hydrolase precursor by replacing the amino acid residue at the position in said carbonyl hydrolase with a different amino acid equivalent to the +76 position according to the Bacillus amyloliquefactionβ subtyiism number; and (c) a surfactant agent; said compositions comprise levels of enzyme lipase and protease enzyme sufficient to increase the whiteness performance of said compositions.
6. The detergent composition according to claim 5 further characterized in that the enzyme lipase comprises a lipase enzyme selected from the group consisting of lipolase, a variant lipase enzyme D96L of the native lipase derived from Hu icola lanugmosa, and mixtures thereof.
7. The detergent composition for laundry according to claim 5 further characterized in that the protease enzyme comprises a protease enzyme derived from a carbonyl hydrolase precursor by substituting a different amino acid with a plurality of amino acid residues in a position, in said carbonyl hydrolase, equivalent to the position +76 in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, « -105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +126, +217, +218, +222, +260 , +265, and / or +274, in accordance with the subtilisin numbering of Bacillus a yliliquefaciens.
8. A laundry detergent composition comprising (a)? A variant of the lipase enzyme D96L of the native lipase derived from strain DSM 4106 of Humicola lanugmosa; (b) a protease enzyme selected from the group consisting of the subtilisin Hurni tail lanugosa variant N76D / S103A / V104I, in accordance with the subtilisme numbering of Bacillus amyloliquefaciens, Savi ase *, or mixtures thereof; and (c) a surfactant agent; said compositions comprise levels of enzyme lipase and enzyme protease sufficient to increase the whiteness performance of said compositions.
9. A method for washing fabrics to preserve-whiteness and provide dirt cleaning, said method comprises contacting the fabrics in need of whiteness and dirt cleaning with an aqueous solution of a composition comprising enzyme lipase and enzyme profeasa at levels such that the cleaning performance of said composition increases.
10. A method for washing fabrics for preserving-whiteness and providing dirt cleaning, said method comprising contacting the fabrics in need of whiteness and dirt cleaning with an aqueous solution comprising the detergent composition for laundry according to claim 1. n 1.
11. A method for washing fabrics for preserving-whiteness and providing dirt cleaning, said method comprises contacting fabrics in need of whiteness and dirt cleaning with an aqueous solution comprising the laundry detergent composition in accordance with with claim 2.
12. A method for washing fabrics, for preserving-whiteness and providing dirt cleaning, said method comprises contacting the fabrics in need of whiteness and dirt cleaning with an aqueous solution comprising the detergent composition for laundry according to claim 3. 13 »A method for washing fabrics for preserving-blanc For cleaning and providing dirt cleaning, said method comprises contacting the fabrics in need of whiteness and dirt cleaning with an aqueous solution comprising the laundry detergent composition according to claim 4. 14. A method for washing fabrics for conserve-whiteness and provide dirt cleaning, said method comprises contacting the fabrics in need of whiteness and dirt cleaning with an aqueous solution comprising the laundry detergent composition according to claim 5. 15. A method for washing fabrics for preserving whiteness and providing dirt cleaning, said method comprises contacting the fabrics in need of whiteness and dirt cleaning with an aqueous solution comprising the laundry detergent composition according to claim 6. 16. A method for washing of fabrics to conserve-whiteness and provide dirt cleaning, said method it comprises contacting the fabrics in need of whiteness and dirt cleaning with an aqueous solution comprising the laundry detergent composition according to claim i7. 17. A method for washing fabrics for preserving-whiteness and providing dirt cleaning, said method comprises contacting the fabrics in need of whiteness and dirt cleaning with an aqueous solution comprising the laundry detergent composition in accordance with the claim 8
MX9703715A 1994-11-18 1995-11-03 Detergent compositions containing lipase and protease. MX9703715A (en)

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