WO1996031583A1 - Composition detergente comprenant une enzyme amylase mutante et un decolorant a l'oxygene - Google Patents

Composition detergente comprenant une enzyme amylase mutante et un decolorant a l'oxygene Download PDF

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Publication number
WO1996031583A1
WO1996031583A1 PCT/US1996/003340 US9603340W WO9631583A1 WO 1996031583 A1 WO1996031583 A1 WO 1996031583A1 US 9603340 W US9603340 W US 9603340W WO 9631583 A1 WO9631583 A1 WO 9631583A1
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WIPO (PCT)
Prior art keywords
soaking
composition according
protease
stability
fabrics
Prior art date
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PCT/US1996/003340
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English (en)
Inventor
Lamberto Biscarini
Marina Trani
Original Assignee
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 PL96322590A priority Critical patent/PL322590A1/xx
Priority to US08/930,302 priority patent/US5922083A/en
Priority to AU53084/96A priority patent/AU714425B2/en
Priority to SK1347-97A priority patent/SK134797A3/sk
Priority to MX9707649A priority patent/MX9707649A/es
Priority to BR9604777A priority patent/BR9604777A/pt
Priority to JP8530295A priority patent/JPH11503190A/ja
Publication of WO1996031583A1 publication Critical patent/WO1996031583A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to the cleaning of fabrics in soaking conditions, i.e. in conditions where the fabrics are left to soak in a soaking liquor comprising water and detergent ingredients, either as a first step before a typical washing operation, or as a single step.
  • This laundering process has the advantage that it maximizes the contact time between the fabrics and the key active ingredients of the soaking liquor. It also has the advantage that it reduces or eliminates the need for a typical laundering operation involving the need for mechanical agitation, or that it improves the efficiency of the
  • soaking compositions should comprise a protease as well as an amylase.
  • amylases themselves are subject to proteolytic attack, as the soaking composition is dissolved to form a soaking liquor. This is a particularly acute problem in the context of soaking, where the contact time between the ingredients in general, the amylase and the protease in particular, is generally enormously longer than in typical laundering operation.
  • compositions should comprise an oxygen bleach, preferably a high amount of such a bleach.
  • an oxygen bleach finds suitable conditions for efficacy in a soaking operation where, contact time between the actives of the compositions and the soiled fabrics is maximized.
  • the presence of bleach is also detrimental to the stability of the enzymes throughout the period of the soaking operation. Indeed bleaches, especially at high level tend to denature the quaternary stucture of the enzymes, exposing amylase to an even more aggressive proteolytic attack.
  • soaking compositions should comprise significant amounts of builders. Indeed the presence of builders is necessary to effectively control water hardness. Builders are even more necessary in soaking conditions where contact time between fabrics and wash solution is longer, as compared to normal washes, thus hardness must be controlled for a much longer time. To comply with the peculiarities of the soaking process, soaking compositions must therefore contain high levels of builders. However, the presence of high levels of builders is also detrimental to the action of enzymes. Indeed, these builders tend to bind all the calcium present in the soak solution, amongst other things, while some calcium is needed to ensure appropriate enzyme activity.
  • compositions should comprise significant amounts of an anionic surfactant.
  • a preferred anionic surfactant class for cost and performance reasons is alkylbenzene sulphonate, particularly linear ones. Certain anionic surfactants, linear alkylbenzene sulphonates (LAS) in particular, however appear to be detrimental to enzyme stability.
  • a soaking composition suitable for a soaking operation which comprises an amylase in combination with a protease, a bleaching system, a high amount of a builder, and an anionic surfactant, preferably LAS, wherein said amylase remains active for a long period of time, consitent with the characteristics of a soaking operation.
  • compositions comprising:
  • an anionic surfactant preferably linear allkyl benzene sulphonates
  • the present invention encompasses a process of soaking fabrics, wherein said fabrics are immersed in a soaking liquor comprising water and an effective amount of the composition above/
  • the present invention encompasses a composition and a process of soaking fabrics.
  • the composition hereinafter referred to as the soaking composition is used in the soaking process.
  • the present invention encompasses a composition which comprises a bleach, a builder; an anionic surfactant, a proteolytic enzyme; and an amylolytic enzyme.
  • the compositions herein comprise an oxygen bleach.
  • Suitable oxygen bleaches in the composition may come from a variety of sources such as hydrogen peroxide or any of the addition compounds of hydrogen peroxide, or organic peroxyacid, or mixtures thereof.
  • addition compounds of hydrogen peroxide it is meant compounds which are formed by the addition of hydrogen peroxide to a second chemical compound, which may be for example an inorganic salt, urea or organic carboxylate, to provide the addition compound.
  • the addition compounds of hydrogen peroxide include inorganic perhydrate salts, the compounds hydrogen peroxide forms with organic carboxylates, urea, and compounds in which hydrogen peroxide is clathrated.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the alkali metal salt of percarbonate, perborate or mixtures thereof, are the preferred inorganic perhydrate salts for use herein.
  • Preferred alkali metal salt of percarbonate is sodium percarbonate.
  • oxygen bleaches include persulphates, particularly potassium persulphate K ⁇ O g and sodium persulphate Na 2 S 2 0 8 .
  • Soaking compositions in the present invention may comprise from 1% to 60% by weight of composition of a hydrogen peroxyde source, preferably from 2% to 40% and more preferably from 15% to 40%. 2 -
  • compositions herein comprise a builder, or mixtures thereof, in amounts of from 5 % to 50% by weight of the total composition, preferably 10% to 40%, most preferably 15% to 30%.
  • Suitable builders for use herein include inorganic as well as organic builders.
  • Inorganic or P -containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • the compositions herein function surprisingly well even in the presence of the so-called weak builders (as compared with phosphates) such as citrate, or in the so-called underbuilt situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a SiC>2:Na2 ⁇ ratio in the range 1:6:1 to 3:2:1 and layered silicates, such as the layered sodium silicates described in the U.S. Patent 4,664,839, issued May 12, 1987 to H.P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS- 6").
  • Hoechst commonly abbreviated herein as "SKS- 6"
  • the NaSKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si ⁇ 5 morphology form of layered silicate.
  • SKS- € is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5 , NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na2Si ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321 ,001 , published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • Useful aluminosiiicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosiiicates or synthetically derived.
  • a mtehod for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P(B), Zeolite MAP and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula:
  • x is from about 20 to about 30, especially about 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1 - 10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboyxlate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as dislcosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635, 830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071 , issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboyxlates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates such as 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5- tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Y is a comonomer or comonomer mixture
  • R 1 and R2 are bleach- and alkali-stable polymer-end groups
  • R 3 is H, OH or C ⁇ _ alkyl
  • M is H, alkali metal, alkaline earth metal, ammonium or substituted ammonium
  • p is from 0 to 2
  • n is at least 10, or mixtures thereof.
  • Preferred polymers for use herein fall into two categories.
  • the first category belongs to the class of copolymeric polymers which are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid, mesaconic acid and salts thereof as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C-
  • an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid, mesaconic acid and salts thereof as first monomer
  • an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C-
  • the polymers belonging to said first class are those where p is not 0 and Y is selected from the acids listed hereinabove.
  • Preferred polymers of this class are those according to formula I hereinabove, where Y is maleic acid.
  • R 3 and M are H
  • n is such that the poly
  • the second category of preferred polymers for use herein belongs to the class of polymers in which, referring to formula I hereinabove, p is 0 and R 3 is H or C-]_4 alkyl.
  • n is such that the polymers have a molecular weight of from 1000 to 400 000 atomic mass units.
  • R 3 and M are H.
  • alkali-stable polymer end groups R 1 and R 2 in formula I hereinabove suitably include alkyl groups, oxyalkyl groups and alkyl carboxylic acid groups and salts and esters thereof.
  • n the degree of polymerization of the polymer can be determined from the weight average polymer molecular weight by dividing the latter by the average monomer molecular weight.
  • n 182 (i.e. 15,500 / (116 x 0.3 + 72 x 0.7)).
  • highly preferred polymers for use herein are those of the first category in which n averages from 100 to 800, preferably from 120 to 400.
  • Citrate builders e.g. citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance due to their availability from renewable resources and their biodegradability. Citrates can also be used in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • Useful succinic acid builders include the C5-C20 a'M and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenyisuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2- pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application
  • Fatty acids e.g. C*t2 ⁇ Cl8 monocarboxyiic acids
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane-l-hydroxy-1 , 1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021 ; 3,400,148 and 3,422,137) can also be used.
  • compositions herein comprise an anionic surfactant or mixtures thereof, in amounts of from 0.5% to 20% by weight of the total composition, preferably 3% to 15%, most preferably 5% to 10%.
  • Suitable anionic surfactant for use herein include water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyi having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyi, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quarternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkyl chains of C-12-16 are preferred for
  • Suitable anionic surfactants for use herein are water soluble salts or acids of the formula RO(A) m S ⁇ 3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyi group having a C10- 24 alkyl component, preferably a C12-C2O alkyl or hydroxyalkyi, more preferably C12-C18 alkyl or hydroxyalkyi, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyi group having a C10- 24 alkyl component, preferably a C12-C2O alkyl or
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12-C-J8 alkyl polyethoxylate (1.0) sulfate, C ⁇ i2-Ci8E(1-0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate, C ⁇ 2-Ci8E(2-25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate Ci2-Cl8 E ( 3 0 ). and C12-C18 alkyl polyethoxylate (4.0) sulfate C12- Ci8E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • Other anionic surfactants useful for detersive purposes can also be used herein.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • soap C9-C20 linear alkylbenzenesulfonates, C8-C22 primary or 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 ester sulfonates such as C14.16 methyl ester sulfonates
  • 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 sulfosuccinate (especially saturated and unsaturated C12-C-J8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), acyl sarcosinates, sulfates of alkylpolysaccharide
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • Highly preferred surfactants for use in the compositions herein are the alkyl benzene sulfonates, especially the linear ones.
  • the compositions herein comprise a protease or mixtures thereof.
  • Protease enzymes are usually present in preferred embodiments of the invention at levels sufficient to provide from 0.005 to 0.2 Anson units (AU) of activity per gram of composition.
  • the proteolytic enzyme can be of animal, vegetable or, preferably microorganism preferred origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. Particularly preferred by way of proteolytic enzyme is bacterial serine proteolytic enzyme obtained from Bacillus, Bacillus subtilis and/or Bacillus licheniformis.
  • Suitable commercial proteolytic enzymes include Alcalase ®, Esperase ®, Durazym ®, Savinase ®, Maxatase ®, Maxacal ®, and Maxapem ® 15 (protein engineered Maxacal); Purafect ® and subtilisin BPN and BPN' are also commercially available.
  • Preferred proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme, which is called “Protease A” herein. More preferred is what is called herein “Protease C”, which is a triple variant of an alkaline serine protease from Bacillus in which tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958.4, corresponding to WO 91/06637, Published May 16, 1991 , which is incorporated herein by reference. Genetically modified variants, particularly of Protease C, are also included herein.
  • protease herein referred to as "Protease D” which is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a percursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76 in combination with one or more amino acid residue positions equivalent to those selected from the gorup consisting of +99, +101, +103, +107 and +123 in Bacillus amyloli ⁇ uefaciens subtilisin as described in the concurrently filed patent applications of A. Baeck, C.K. Ghosh, P.P. Greycar, R.R. Bott and L.J.
  • proteolytic enzymes are selected from the group consisting of Savinase ®, Esperase ®, Maxacal ®, Purafect ®, BPN', Protease A and Protease B, and mixtures thereof.
  • Bacterial serine protease enzymes obtained from Bacillus subtilis and or Bacillus licheniformis are preferred. Particularly preferred are Savinase ®, Alcalase ®, Protease A and Protease B.
  • compositions herein comprise an amylase.
  • Engineering of enzymes for improved stability, e.g. oxidative stability is known. See, for example J. Biological Chem., vol. 260, No. 11, June 1985, pp 6518- 6521.
  • Reference amylase hereinafter refers to an amylase outside the scope of the amylase component of this invention and against which stability of any amylase within the invention can be measured.
  • the present invention thus makes use of amylases having improved stability in detergents, especially improved oxidative stability.
  • a convenient absolute stability reference-point against which amylases used in the instant invention represent a measurable improvement is the stability of TERMAMYL (R) in commercial use in 1993 and available from Novo Nordisk A/S.
  • This TERMAMYL (R) amylase is a "reference amylase”.
  • Amylases within the spirit and scope of the present invention share the characteristic of being "stability- enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g.
  • amylases herein can demonstrate further improvement versus more challenging reference amylases, the latter reference amylases being illustrated by any of the precursor amylases of which the amylases within the invention are variants. Such precursor amylases may themselves be natural or be the product of genetic engineering. Stability can be measured using any of the art-disclosed technical tests. See references disclosed in WO 94/02597, itself and documents therein referred to being incorpated by reference.
  • stability-enhanced amylases respecting the invention can be obtained from Novo Nordisk A/S, or from Genencor International.
  • Preferred amylases herein have the commonality of being derived using site- directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus alpha-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • amylases are preferred for use herein. Such amylases are non-limitingly illustrated by the following:
  • Met was substituted, one at a time, in positions 8,15,197,256,304,366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE (R) and SUNLIGHT (R); Such enzymes are commercially available from Genencor under the trade name Plurafact Oxam ®.
  • amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S.
  • amylases do not yet have a tradename but are those referred to by the supplier as QL37+M197T. Such enzymes are commercially available under the trade name SP 703 from Novo.
  • Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases.
  • the soaking composition of the present invention may further comprise a variety of other ingredients.
  • Optional but preferred ingredients for use herein are bleach activators.
  • suitable compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 231.
  • Preferred examples of such compounds are t ⁇ tracetyl ethylene diamine, (TAED), sodium 3, 5, 5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for instance in US 4 818425 and nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS), and acetyl triethyl citrate (ATC) such as described in European patent application 91870207.7.
  • TAED t ⁇ tracetyl ethylene diamine
  • NOBS nonylamide of peroxyadipic acid
  • NOBS n-nonanoyloxybenzenesulphonate
  • ATC acetyl triethyl citrate
  • N-acyl caprolactam selected from the group consisting of substituted or unsubstituted benzoyl caprolactam, octanyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoyl caprolactam.
  • the soaking compositions herein may comprise mixtures of said bleach activators.
  • Preferred mixtures of bleach activators herein comprise n- nonanoyloxybenzenesulphonate (NOBS) together with a second bleach activator having a low tendency to generate diacyl peroxide, but which delivers mainly peracid.
  • Said second bleach activators may include tetracetyl ethylene diamine (TAED), acetyl triethyl citrate (ATC), acetyl caprolactam, benzoyl caprolactam and the like, or mixtures thereof.
  • Said mixtures of bleach activators are preferably used in the embodiment of the present invention where the soaking liquors are controlled to a pH below 9.5.
  • mixtures of bleach activators comprising n- nonanoyloxybenzenesulphonate and said second bleach activators, allow to boost paniculate soil cleaning performance while exhibiting at the same time good performance on diacyl peroxide sensitive soil (e.g. beta-carotene) and on peracid sensitive soil (e.g. body soils).
  • diacyl peroxide sensitive soil e.g. beta-carotene
  • peracid sensitive soil e.g. body soils
  • the soaking compositions herein may comprise from 0% to 15% by weight of the total composition of n-nonanoyloxybenzenesulphonate, preferably from 1% to 10% and more preferably from 3% to 7% and from 0% to 15% by weight of the total composition of said second bleach activator preferably from 1 % to 10% and more preferably from 3% to 7%.
  • Suitable amino carboxylate chelating agents which may be used herein include diethylene triamino pentacetic acid, ethylenediamine tetraacetates (EDTA), N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine hexaacetates, and ethanoldiglycines, alkali metal ammonium and substituted ammonium salts thereof or mixtures thereof.
  • EDTA ethylenediamine tetraacetates
  • N-hydroxyethylethylenediamine triacetates N-hydroxyethylethylenediamine triacetates
  • nitrilotriacetates nitrilotriacetates
  • ethylenediamine tetraproprionates triethylenetetraamine hexaacetates
  • ethanoldiglycines alkali metal ammonium and substituted ammonium salts thereof or mixtures thereof
  • chelating agents include ethylenediamine-N.N * - disuccinic acids (EDDS) or alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof.
  • EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.
  • suitable chelating agents may be the organic phosphonates, including amino alkylene poly(alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • the phosphonate compounds may be present either in their acid form or in the form of their metal alkali salt.
  • the organic phosphonate compounds where present are in the form of their magnesium salt.
  • the soaking compositions in the present invention may accordingly comprise from 0% to 5% by weight of the total compositions of said chelating agents, preferably from 0% to 3%, more preferably from 0.05% to 2%.
  • Soaking compositions in the present invention may further comprise other optional ingredients such as additional surfactants, other than anionics, fillers, optical brighteners, additional enzymes, soil release agents, photoactivated bleaches such as Zn phthalocyanine sulphonate, dyes, dye transfer inhibitors, pigments and perfumes. Said optional ingredients can be added in varying amounts as desired.
  • compositions herein can be manufactured in solid, preferably granular, or liquid form.
  • the present invention encompasses a process of soaking fabrics.
  • process of soaking fabrics refers to the action of leaving fabrics to soak in a soaking liquor comprising water and a composition as described hereinabove, for a period of time sufficient to clean said fabrics.
  • the soaking process can be performed independently from any other process, such as a typical laundering operation, or a first step before a second, typical laundering step.
  • fabrics are left to soak for a period of time ranging from 10 minutes to 24 hours, preferably from 30 min to 24 hours, most preferably 4 hours to 24 hours. After the fabrics have been immersed in said soaking liquor for a sufficient period of time, they can be removed and rinsed with water.
  • the fabrics can also be washed in a normal laundering operation after they have been soaked, with or without having been rinsed inbetween the soaking operation and the subsequent laundering operation.
  • a soaking composition described hereinabove is diluted in an appropriate amount of water to produce a soaking liquor.
  • Suitable doses may range from 45 to 50 grams of soaking composition in 3.5 to 5 liters of water, down to 90 to 100 grams of soaking composition in 20 to 45 liters of water.
  • one dose is 45-50 grams in 3.5 to 5 Lt for a concentrated soak (bucket/sink).
  • the dose is 90-100 grams in about 20 (Europe) to 45 (US) liter of water.
  • the fabrics to be soaked are then immersed in the soaking liquor for an appropriate period of time.
  • compositions are made by mmixing the listed ingredients in the listed proportions. Soaking liquors are formed by diluting each time 45 g of said compositions in between 3.5 lit. to 5.0 lit. of water. 0.5 to 2 Kg of fabrics are then each time immersed in said soaking liquor for a time ranging from 10 minutes to 24 hours. Finally, the fabrics are removed from the soaking liquors, rinsed with water and washed with a regular washing process, handwash or washing machine wash, with a regular detergent, with or without re-using the soaking liquor, then said fabrics are left to dry.

Abstract

La présente invention concerne des compositions de trempe comprenant un décolorant, un adjuvant; un agent tensioactif anionique, une enzyme protéolytique; et une enzyme amylase de stabilité améliorée. L' invention concerne aussi un procédé de trempe de tissus, selon lequel ceux-ci sont immergés dans un liquide de trempe comprenant de l'eau et une quantité efficace de la composition ci-dessus.
PCT/US1996/003340 1995-04-03 1996-03-12 Composition detergente comprenant une enzyme amylase mutante et un decolorant a l'oxygene WO1996031583A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
PL96322590A PL322590A1 (en) 1995-04-03 1996-03-12 Detergent compositions containing an amylase enzyme mutant and peroxide bleaching agent
US08/930,302 US5922083A (en) 1995-04-03 1996-03-12 Detergent composition comprising a mutant amylase enzyme and oxygen bleaching agent
AU53084/96A AU714425B2 (en) 1995-04-03 1996-03-12 Detergent composition comprising a mutant amylase enzyme and oxygen bleaching agent
SK1347-97A SK134797A3 (en) 1995-04-03 1996-03-12 Detergent composition comprising a mutant amylase enzyme and oxygen bleaching agent
MX9707649A MX9707649A (es) 1995-04-03 1996-03-12 Composicion detergente que comprende una enzima amilasa mutante y agente blanqueador de oxigeno.
BR9604777A BR9604777A (pt) 1995-04-03 1996-03-12 Composição detergente compreendendo enzima amilase mutante a agente alvejante de oxigênio
JP8530295A JPH11503190A (ja) 1995-04-03 1996-03-12 変異アミラーゼ酵素および酸素漂白剤を含む洗剤組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP95870031.2 1995-04-03
EP95870031A EP0736597A1 (fr) 1995-04-03 1995-04-03 Compositions pour trempage

Publications (1)

Publication Number Publication Date
WO1996031583A1 true WO1996031583A1 (fr) 1996-10-10

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PCT/US1996/003340 WO1996031583A1 (fr) 1995-04-03 1996-03-12 Composition detergente comprenant une enzyme amylase mutante et un decolorant a l'oxygene

Country Status (16)

Country Link
EP (1) EP0736597A1 (fr)
JP (1) JPH11503190A (fr)
KR (1) KR19980703602A (fr)
CN (1) CN1185800A (fr)
AU (1) AU714425B2 (fr)
BR (1) BR9604777A (fr)
CA (1) CA2217292A1 (fr)
CZ (1) CZ312997A3 (fr)
HU (1) HUP9801760A2 (fr)
MX (1) MX9707649A (fr)
PL (1) PL322590A1 (fr)
RU (1) RU2169176C2 (fr)
SK (1) SK134797A3 (fr)
TR (1) TR199701099T1 (fr)
WO (1) WO1996031583A1 (fr)
ZA (1) ZA962208B (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6180580B1 (en) * 1997-02-27 2001-01-30 The Procter & Gamble Company Soaker compositions
EP0861885B1 (fr) * 1997-02-27 2003-04-16 The Procter & Gamble Company Compositions pour trempage
GB0001388D0 (en) * 2000-01-22 2000-03-08 Coats Viyella Clothing Limited Textile treatment
DK1307547T3 (da) 2000-07-28 2006-03-20 Henkel Kgaa Hidtil ukendt amylolytisk enzym fra Bacillus sp. A 7-7 (DSM 12368) samt vaske- og rengöringsmidler med dette hidtil ukendte amylolytiske enzym
US6569209B2 (en) * 2001-02-27 2003-05-27 The Procter & Gamble Company Method for the use of hydrophobic bleaching systems in cold batch textile preparation
US20100099599A1 (en) * 2008-10-16 2010-04-22 Advanced Biocatalytics Corporation Enhanced performance hydrogen peroxide formulations comprising proteins and surfactants
JP5431896B2 (ja) * 2009-12-11 2014-03-05 花王株式会社 漂白剤組成物
US20220112479A1 (en) * 2018-10-05 2022-04-14 Basf Se Compounds stabilizing amylases in liquids
CN112840021A (zh) * 2018-10-05 2021-05-25 巴斯夫欧洲公司 在液体中稳定水解酶的化合物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011169A (en) * 1973-06-29 1977-03-08 The Procter & Gamble Company Stabilization and enhancement of enzymatic activity
US5030240A (en) * 1986-06-09 1991-07-09 The Clorox Company Enzymatic peracid bleaching system
WO1994002597A1 (fr) * 1992-07-23 1994-02-03 Novo Nordisk A/S Alpha-amylase mutante, detergent, agent de lavage de vaisselle et de liquefaction
WO1994018314A1 (fr) * 1993-02-11 1994-08-18 Genencor International, Inc. Alpha-amylase stable a l'oxydation

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1544393A (fr) * 1966-11-14 1968-10-31 Unilever Nv Compositions détergentes
DE1957890A1 (de) * 1968-11-20 1970-07-09 Procter & Gamble Enzymhaltige Wasch- und Reinigungsmittelmischung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011169A (en) * 1973-06-29 1977-03-08 The Procter & Gamble Company Stabilization and enhancement of enzymatic activity
US5030240A (en) * 1986-06-09 1991-07-09 The Clorox Company Enzymatic peracid bleaching system
WO1994002597A1 (fr) * 1992-07-23 1994-02-03 Novo Nordisk A/S Alpha-amylase mutante, detergent, agent de lavage de vaisselle et de liquefaction
WO1994018314A1 (fr) * 1993-02-11 1994-08-18 Genencor International, Inc. Alpha-amylase stable a l'oxydation

Also Published As

Publication number Publication date
AU5308496A (en) 1996-10-23
MX9707649A (es) 1997-12-31
KR19980703602A (ko) 1998-12-05
PL322590A1 (en) 1998-02-02
EP0736597A1 (fr) 1996-10-09
CZ312997A3 (cs) 1998-02-18
ZA962208B (en) 1996-09-26
SK134797A3 (en) 1998-06-03
CA2217292A1 (fr) 1996-10-10
RU2169176C2 (ru) 2001-06-20
BR9604777A (pt) 1998-07-07
TR199701099T1 (xx) 1998-01-21
HUP9801760A2 (hu) 1998-11-30
CN1185800A (zh) 1998-06-24
AU714425B2 (en) 2000-01-06
JPH11503190A (ja) 1999-03-23

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