EP0665876B1 - Granulare waschmittel mit protease - Google Patents

Granulare waschmittel mit protease Download PDF

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Publication number
EP0665876B1
EP0665876B1 EP93924343A EP93924343A EP0665876B1 EP 0665876 B1 EP0665876 B1 EP 0665876B1 EP 93924343 A EP93924343 A EP 93924343A EP 93924343 A EP93924343 A EP 93924343A EP 0665876 B1 EP0665876 B1 EP 0665876B1
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Prior art keywords
composition
acid
weight
protease
carbon atoms
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EP93924343A
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EP0665876A1 (de
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David Neil Di Giulio
Edward Eugene Getty
Chanchal Kumar Ghosh
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds

Definitions

  • the present invention relates to methods of cleaning fabrics with granular detergent compositions comprising certain levels of bleaching agent, protease enzyme, and detergent surfactant.
  • the bleaching agent is substantially water-insoluble organic peroxyacid or a combination of certain bleach activators and peroxygen bleaching compound capable of yielding hydrogen peroxide.
  • EP-A-0 359 087 published March 21, 1990, describes an activated oxidant system for in situ generation of peracid in aqueous media comprising protease and a specified ester substrate, along with a source of peroxygen.
  • EP-A-0 212 976 published March 4, 1987, describes stabilised peracid bleaching compositions containing a peracid, preferably enzyme and exotherm control agents. Improved stability of peracid and enzyme is said to result from a careful control of the water level present and the ratio of exotherm control agent to diperacid.
  • EP-A-0 206 418 published December 30, 1986, relates to a granular composition
  • a granular composition comprising a homogeneously mixed granulate of enzymes and alkaline buffer salt to protect the enzymes from deactivation when mixed with a strong peroxyacid bleach granulate.
  • This composition can also contain commonly used detergent ingredients such as surfactants and builder salts.
  • FR-A-2,232,590 discloses detergent compositions demonstrating improved global cleaning performance, containing water-soluble peracid or its precursors, nonionic surfactant and an enzyme having an isoelectrical point equal or superior to 9.5.
  • This invention relates to a method of cleaning fabrics with granular detergent compositions which provide especially effective surface cleaning of textiles. This invention also relates to methods for cleaning fabrics using such detergent compositions.
  • the granular detergent compositions used in this invention comprise:
  • the peracid which is in the composition, or which is formed by the combination of activator and peroxygen compound, has a corresponding carboxylic acid that has a Hydrophobic-Lipophilic Balance value which ranges from 3 to 6.5.
  • the molar ratio of hydrogen peroxide yielded by the peroxygen compound to the activator is greater than 1.5.
  • the activator has the formula: or wherein R is an alkyl group containing from 5 to 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from 6 to 10 carbon atoms; R 1 is an alkyl group containing from 6 to 12 carbon atoms; R 2 is an alkylene containing from 1 to 6 carbon atoms; R 5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms; and L is a leaving group, the conjugate acid of which has a pK a in the range of from 6 to 13.
  • the granular detergent compositions herein are preferably nonphosphate granular (powder) laundry detergents which contain both bleach and enzyme for good cleaning of soiled laundry.
  • granular refers to detergent compositions in any suitable particulate form, e.g., granules, powders or agglomerates.
  • Granular laundry detergent compositions herein provide effective and efficient surface cleaning of textiles, particularly grass stains, over a wide range of laundry washing temperatures.
  • Laundry wash solutions are preferably at temperatures between 5°C and 80°C, preferably between 10°C and 60°C, for this cleaning benefit.
  • the granular detergent compositions herein contain a bleaching agent, which comprises from 0.5 to 20 wt.% of the detergent composition.
  • the bleaching agent is either a substantially insoluble, preferably solid, organic peroxyacid, or a bleach activator and a peroxygen bleaching compound capable of yielding hydrogen peroxide, or a combination of both.
  • the bleach activator has the following structure: wherein R is an alkyl group containing from 5 to 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from 6 to 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pk a in the range of from 6 to 13, preferably from 7 to 11, most preferably from 8 to 11.
  • L can be essentially any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion. This, the perhydrolysis reaction, results in the formation of the percarboxylic acid.
  • a group to be a suitable leaving group it must exert an electron attracting effect. This facilitates the nucleophilic attack by the perhydroxide anion.
  • the L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize. These characteristics are generally paralleled by the pKa of the conjugate acid of the leaving group, although exceptions to this convention are known.
  • Preferred bleach activators are those of the aeneral formula: wherein R 1 is an alkyl group containing from 6 to 12 carbon atoms, R 2 is an alkylene containing from 1 to 6 carbon atoms, R 5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is selected from the group consistina of: and wherein R 6 is an alkylene, arylene, or alkarylene group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from about 1 to about 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group.
  • Y is preferably selected from the group consisting of -SO 3 - M + , -COO - M + , -SO 4 - M + , (-NR 3 ' + )X - and O ⁇ N(R' 3 ), wherein R' is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
  • X is an anion selected from the group consisting of halide, hydroxide, methylsulfate, and acetate anions.
  • Y is -SO 3 - M + and -COO - M + .
  • bleach activators with a leaving group that does not contain a solubilizing group should be well dispersed in the bleach solution in order to assist in their dissolution. Preferred is: wherein R 3 is as defined above and Y is -SO 3 - M + or -COO - M + wherein M is as defined above.
  • Especially preferred bleach activators are those wherein R 1 is a linear alkyl chain containing from 6 to 12 carbon atoms, R 2 is a linear alkylene chain containing from 2 to 6 carbon atoms, R 5 is H, and L is selected from the group consisting of: wherein R 3 is as defined above, Y is -SO 3 - M + or -COO - M + and M is as defined above.
  • a preferred bleach activator is: wherein R is H, alkyl, aryl or alkaryl. This is described in U.S. Patent 4,966,723, Hodge et al.
  • Preferred bleach activators are: wherein R 1 is H or an alkyl group containing from 1 to 6 carbon atoms and R 2 is an alkyl group containing from 1 to 6 carbon atoms and L is as defined above.
  • Preferred bleach activators are also those of the above general formula wherein L is as defined in the general formula, and R 1 is H or an alkyl group containing from 1 to 4 carbon atoms, and R 2 is an alkyl group containing from 1 to 4 carbon atoms.
  • a more preferred bleach activator is:
  • More preferred bleach activators are those of the above general formula wherein R is a linear alkyl chain containing from 5 to 9 and preferably from 6 to 8 carbon atoms and L is selected from the group consisting of: wherein R, R 2 , R 3 and Y are as defined above.
  • Particularly preferred bleach activators are those of the above general formula wherein R is an alkyl group containing from 5 to 12 carbon atoms wherein the longest linear portion of the alkyl chain extending from and including the carbonyl carbon is from 6 to 10 carbon atoms, and L is selected from the group consisting of: wherein R 2 is an alkyl chain containing from 1 to 8 carbon atoms, and Y is -SO 3 - M + or -COO - M + wherein M is an alkali metal, ammonium or substituted ammonium cation.
  • Especially preferred bleach activators are those of the above general formula wherein R is a linear alkyl chain containing from 5 to 9 and preferably from 6 to 8 carbon atoms and L is selected from the group consisting of: wherein R 2 is as defined above and Y is -SO 3 - M + or -COO - M + wherein M is as defined above.
  • the most preferred bleach activators have the formula: wherein R is a linear alkyl chain containing from 5 to 9 and preferably from 6 to 8 carbon atoms and M is sodium or potassium.
  • the level of bleach activator within the compositions for use in the method of the invention is from 0.5 to 20, preferably from 1 to 10, more preferably from 2 to 7, wt.% of the composition.
  • the bleaching mechanism generally, and the surface bleaching mechanism in particular, are not completely understood. However, it is generally believed that the bleach activator undergoes nucleophilic attack by a perhydroxide anion, which is generated from the hydrogen peroxide evolved by the peroxygen bleach, to form a peroxycarboxylic acid. This reaction is commonly referred to as perhydrolysis.
  • wash solutions wherein the pH of such solution is between 8.5 and 10.5 and preferably between 9.5 and 10.5 in order to facilitate the perhydrolysis reaction.
  • pH can be obtained with substances commonly known as buffering agents, which are optional components of the bleaching compositions herein.
  • the bleach activator herein is sodium nonanoyloxybenzenesulfonate (NOBS) or sodium benzoyloxybenzenesulfonate (BOBS).
  • the molar ratio of hydrogen peroxide yielded by the peroxygen bleaching compound to the bleach activator is greater than 1.5, preferably from 2.0 to 10.
  • the detergent compositions herein comprise from 0.5 to 20, most preferably from 1 to 10, wt.% of the peroxygen bleaching compound.
  • Salts of perborate and percarbonate are preferred peroxygen bleaching compounds for use herein.
  • Sodium perborate and sodium carbonate peroxyhydrate are most preferred.
  • peroxyacids are formed in situ in the laundry wash water by the combination of the peroxygen bleaching compound and the bleaching activator.
  • the peroxyacid herein comprises from 0.5 to 20, preferably from 1 to 10, most preferably from 2 to 7, wt.% of the detergent composition.
  • Preferred organic peroxyacids are selected from the group consisting of 4-nonylamino-4-oxoperoxybutyric acid; 6-(nonylamino)-6-oxoperoxycaproic acid; 1,12-diperoxydodecanedioic acid,; heptyl sulfonylperproplonic acid; decylsulphonyl perpropionic acid; and heptyl-, octyl-, nonyl-, decyl-sulphonylperbutyric acids; and mixtures thereof.
  • amidoperoxyacids are preferred.
  • Suitable amidoperoxyacids for use herein are described in U.S. Patents 4,634,551 and 4,686,063, both Burns et al, issued January 6, 1987 and August 11, 1987, respectively.
  • Suitable amidoperoxyacids are of the formula: wherein R 1 is an alkyl group containing from 6 to 12 carbon atoms, and R 2 is an alkylene group containing from 1 to 6 carbon atoms.
  • R 1 is an alkyl group containing from 8 to 10 carbon atoms
  • R 2 is an alkylene group containing from 2 to 4.
  • peroxyfumarates which are described in U.S. Patent 4,852,989, Burns et al, issued August 1, 1989
  • sulfone peroxyacids sulfone peroxycarboxylic acids
  • Example I of U.S. Patent 4,686,063 contains one description of the synthesis of NAPSA, from column 8, line 40 to Column 9, line 5, and NAPAA, from column 9, line 15 to column 9, line 65.
  • the reaction is quenched with water, filtered, washed with water to remove some excess sulfuric acid (or other strong acid with which the peroxyacid was made), and filtered again.
  • amidoperoxyacid wet cake thus obtained can be contacted with a phosphate buffer solution at a pH between 3.5 and 6, preferably between 4 and 5, according to U.S. Patent 4,909,953, Sadlowski et al, issued March 20, 1990.
  • amidoperoxyacid can be added to the amidoperoxyacid before incorporation into the final product.
  • boric acid an exotherm control agent disclosed in U.S. Patent 4,686,063, Burns, issued August 11, 1987
  • the phosphate buffer washed amidoperoxyacid can also be mixed with appropriate amounts of dipicolinic acid and tetrasodium pyrophosphate, a chelating stabilization system.
  • Chelants can optionally be included in the phosphate buffer before contact with the wet cake.
  • the wet cake is preferably made up of particles with an average particle diameter of from 0.1 to 260 microns, preferably from 10 to 100 microns, and most preferably from 30 to 60 microns. Small particle size NAPAA crystals are desired herein. See U.S. Patent 5,055,218, Getty et al, issued October 8, 1991.
  • NAPAA filter cake herein is preferably washed twice in phosphate buffer. It has been found that two successive phosphate buffer washes lend optimal stability to NAPAA.
  • Particulate solid
  • organic peroxyacids with a theoretical AvO (available oxygen) of between 3 and 12, most preferably between 5 and 7, are preferred.
  • NAPAA nonylamide of peroxyadipic a cid
  • NAPAA 6-(nonylamino)-6-oxoperoxycaproic acid.
  • the chemical formula for NAPAA is: The molecular weight of NAPAA is 287.4.
  • Detergent compositions and bleaching compositions containing NAPAA provide extremely effective and efficient surface bleaching of textiles. Stains and/or soils are removed from the textiles. These compositions are particularly effective at removing dingy soils from textiles.
  • NAPAA's polar amide or substituted amide moiety results in a peroxyacid which has a very low vapor pressure and thus possesses a low odor profile as well as excellent bleaching performance. It is believed that the polarity of the amide group results in a reduction of vapor pressure of the peroxyacid, and an increase in melting point.
  • NAPAA can be used directly as a bleaching agent. It has a reduced vapor pressure and a good odor profile in laundry applications.
  • NAPAA can be prepared by, for example, first reacting NAAA (monononyl amide of adipic acid), sulfuric acid, and hydrogen peroxide. The reaction product is quenched by addition to ice water followed by filtration, washing with distilled water, and final suction filtration to recover the wet cake. Washing can be continued until the pH of the filtrate is neutral.
  • NAAA nononyl amide of adipic acid
  • sulfuric acid sulfuric acid
  • hydrogen peroxide hydrogen peroxide
  • NAPAA pH (10% solids in water) be between 4.2 and 4.8. Surprisingly, this pH results in more thermally stable particles.
  • the present invention is based on the use of relatively hydrophobic (lipophilic) peracids (from activators or as preformed peroxyacids) which are thought to concentrate at the soil/fabric interface and enhance the performance benefits from protease enzymes.
  • a method that can be used to characterize the selected peroxyacids (from activators or as preformed peroxyacids) which are useful in the present invention is the "H.L.B. Scale" such as that described in Davies, J.T., Proc. 2nd Internat. Congr. Surface Activity 1 , 426, Butterworths, London (1957). Such an H.L.B.
  • H.L.B. values can be used as an indication of the lipophilic (hydrophobic) character of the active bleaching species in the wash (i.e., the ability of the peroxyacid to partition out of the wash liquor and concentrate at the soil/fabric interface).
  • H.L.B. values which have been calculated for selected peroxyacids (as the corresponding carboxylic acids).
  • the equation used to calculate the H.L.B. values can be set forth as: HLB - Sum (Hydrophilic Group Numbers) - Sum (Hydrophobic Group Numbers) + 7.
  • an H.L.B. value >7 indicates that the material is preferentially water soluble and an H.L.B. value ⁇ 7 indicates increasing surface-activity and hydrophobicity.
  • the range of H.L.B. values (as the carboxylic acid) for the peroxyacids used in the present invention (whether added directly or generated in situ) ranges from 3.0 to 6.5.
  • a preferred range of H.L.B. values (as the carboxylic acid) for the peroxyacids useful in the present invention (whether added directly or generated in situ) ranges from 4.0 to 6.5.
  • the most preferred range of H.L.B. values (as the carboxylic acid) for the peroxyacids used in the present invention (whether added directly or generated in situ) ranges from 4.0 to 6.0.
  • the detergent compositions for used in the method of the present invention also comprise from 0.064 to 0.64, preferably from 0.096 to 0.32, mg of active protease enzyme per gram of composition.
  • proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of this enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants.
  • Suitable proteases include Alcalase®, Esperase®, Savinase® (preferred) ; Naxatase®, Maxacal® (preferred), and Maxapem 15® (protein engineered Maxacal®); and subtilisin BPN and BPN' (preferred); which are commercially available. Also suitable are modified bacterial serine proteases, such as those described in European Patent Application Number 0 251 446, 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.
  • Protease C 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-A-0 451 244, corresponding to WO-A-91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
  • Preferred proteolytic enzymes are selected from the group consisting of Savinase®, Maxacal®, BPN', Protease A, Protease B, Protease C, and mixtures thereof. Protease B and Protease C are most preferred. Bacterial serine protease enzymes obtained from Bacillus subtilis and/or Bacillus licheniformis are preferred.
  • the enzymes for use in the method of the present invention provide effective and efficient removal of stains and/or soils on textiles.
  • the enzymes are particularly efficient at removing protein based stains and/or soils from textiles. While not wishing to be bound by theory, it is believed that surface active bleaches are required since the enzymes of the present invention remove stains and/or soils from the fabric surface, thereby reducing the stain and/or soils load at the fabric surface and resulting in efficient use of both bleach and enzyme.
  • the improved cleaning performance provided by the present invention is believed to result from a synergistic effect between a relatively hydrophobic peracid and protease enzymes, it is possible to express the preferred concentrations of protease enzyme and peroxyacid (whether added directly or generated in situ) as a range of ratios as well as concentration ranges for the protease and bleach individually.
  • a preferred manner of expressing this ratio is [mg active protease per 100 grams of composition/ppm Active Oxygen (ppm Av02) from the peroxyacid in the wash liquor] and will be referred to as the Enzyme to Bleach ratio (E/B ratio).
  • the range for the ratio of active protease to peroxyacid AvO 2 (E/B) used in the present invention is from 1 to 20.
  • compositions for use in the method of this invention also include from 1 to 40 weight % of peroxyacid-stable, water-soluble detergent surfactant selected from the group consisting of anionics, nonionics, zwltterlonlcs, ampholytics, and mixtures thereof. From 2 to 25 weight % of detergent surfactant is preferred and from 5 to 15 weight % is most preferred. Anionic surfactant is preferred and salts of C 11-13 linear alkyl benzene sulfonate, C 12-16 alkyl sulfate and/or methyl ester sulfonates are more preferred. From 2 to 25 wt. % of sodium C 12-13 linear alkyl benzene sulfonate and sodium C 14-15 alkyl sulfate are most preferred.
  • Detergent surfactants useful herein are listed in U.S. Patents 3,664,961, Norris, issued May 23, 1972, and 3,919,678, Laughlin et al, issued December 30, 1975. The following are representative examples of detergent surfactants useful in the present invention.
  • Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyls is the alkyl portion of acyl groups.
  • this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C 11-13 LAS.
  • anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
  • Water-soluble nonionic surfactants are also useful in the method of the invention.
  • Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 15 carbon atoms, in either a straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 4 to 8 moles of ethylene oxide per mole of alcohol.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from 8 to 18 carbon atoms.
  • weight % of detergency builder can optionally be, and preferably is, included herein.
  • Inorganic as well as organic builders can be used.
  • Inorganic detergency builders include, but are not limited to, the alkali metal, ammonium and alkanolammnium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions hereinafter, collectively “borate builders"
  • non-borate builders are used in the compositions of the invention intended for use at wash conditions less than 50°C, especially less than 40°C.
  • silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. However, other silicates may also be useful.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate 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 include those having the empirical formula: M z (zAlO 2 ⁇ ySiO 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2; and y is 1; this material having a magnesium ion exchange capacity of at least 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate.
  • Preferred aluminosilicates are zeolite builders which have the formula: Na z [(AlO 2 ) z (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
  • polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from 6 to 21, and salts of phytic acid.
  • Organic detergent builders preferred for the purposes of the present invention include polycarboxylate compounds which have 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 encompasses the ether polycarboxylates.
  • useful ether polycarboxylates include oxydisuccinate, as disclosed 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.
  • a specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula: CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A is H or OH; B is H or -O-CH(COOX)-CH 2 (COOX); and X is H or a salt-forming cation.
  • Suitable examples of these builders are disclosed in U.S. Patent 4,663,071, issued to Bush et al., on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • detergency builders include the ether hydroxypolycarboxylates and the copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.
  • Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, and nitrilotriacetic acid.
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders which can also be used in granular compositions.
  • carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973.
  • succinic acid builders include the C 5 -C 20 alkyl succinic acids and salts thereof.
  • the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
  • useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates, and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979.
  • Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • organic builders known in the art can also be used.
  • monocarboxylic acids, and soluble salts thereof, having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps.” Chain lengths of C 10 -C 20 are typically utilized.
  • the hydrocarbyls can be saturated or unsaturated.
  • the detergency builder herein is selected from the group consisting of the salts, preferably the sodium salt, of carbonate, silicate, sulfate, phosphate, aluminosilicate, and citric acid and mixtures thereof.
  • ingredients include second enzymes, particularly peroxidase, cellulase, and mixtures thereof.
  • second enzyme is meant one or more enzymes in addition to protease which are also added to the composition.
  • the amount of second enzyme used in the composition varies according to the type of enzyme and the use intended. In general, from 0.0001 to 1.0, more preferably 0.001 to 0.5, weight % of the composition on an active basis of these second enzymes are preferably used.
  • Enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants.
  • ingredients suitable for use in the present compositions such as water, perfume, brightener, conditioners such as fumed silica, polyethylene glycol, dyes and colorants, and peroxyacids, can be included.
  • Preferred ingredients are from 0.5 to 5 wt.% of the composition of polyethylene glycol (preferably with molecular weight between 5,000 and 10,000, most preferably 8,000), from 0.01 to 0.7 wt.% of fluorescent whitening and/or brightening agents, and from 0.01 to 1.0 wt.% of perfume.
  • compositions of the present invention do not need to contain quaternary ammonium salts to delay active oxygen production or to achieve suitably high levels of active oxygen in bleaching solution. Accordingly, such compositions may be substantially free of quaternary ammonium salts.
  • the granular detergent composition is added to the wash, usually at levels of 0,059 to 0,2365 cm 3 (1/4 to 1 cup).
  • a most preferred composition useful in the method of the present invention is a nonphosphate granular laundry detergent composition comprising, by weight of the composition:
  • Agitation is preferably provided in the washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer.
  • An effective amount of the granular detergent composition in the washing machine is preferably from 500 to 7000 ppm, more preferably from 1000 to 3000 ppm.
  • the wash performance of several proteases is evaluated in the presence of a n-nonanoyloxybenzenesulfonate (NOBS)/sodium perborate (PB1) bleach system in non-phosphate detergent granules prepared according to the following composition: Material Wt.% Sodium C 11-13 linear alkyl benzene sulfonate 15.33 Sodium C 14-15 alkyl sulfate 6.57 Sodium aluminosilicate 31.52 Sodium carbonate 12.93 Sodium sulfate, moisture, and miscellaneous 30.92
  • NOBS n-nonanoyloxybenzenesulfonate
  • PB1 sodium perborate
  • proteases are added to the bleach-containing detergent granules at a level of 64 mg active enzyme per 100 gram of product: Maxacal® ex IBIS; 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 (described in EP-A-0 451 244) hereinafter referred to as Protease C; and a variant of Protease C hereinafter referred to as Protease C1.
  • the bleaching performance of n-nonanoyloxybenzenesulfonate and the enzymatic performance of protease are determined in a series of experiments comparing the fabric whitening and stain removal of a treatment containing alkaline detergent granules (composition above) alone, with a treatment containing the detergent granules plus peroxyacid, with a treatment containing detergent granules plus protease, with a treatment containing detergent granules plus peroxyacid plus protease.
  • each of four top-loading automatic washing machines is added 2,3 kg (5 lbs.) of naturally soiled ballast fabrics and 64 liters of 35°C (95°F) city water having a hardness of 102,66 mg/l (6 gr/gal).
  • To one machine is added 87 g of detergent granules only.
  • To the second machine is added 87 g of detergent granules and sufficient N0BS/PB1 to result in an available oxygen (AvO 2 ) level of 4.2 ppm in the wash solution.
  • To the third machine is added 87 g detergent granules and protease at a level of 64 mg of active enzyme per 100 g of the final product.
  • To the fourth machine is added 87 g detergent granules and the same amount of bleach and protease as in the second and third machine, respectively.
  • the E/B ratio for each of the treatments is 15.2.
  • the fabrics and swatches are arranged under suitable lighting for comparison of soil and stain removal.
  • Three qualified graders compare the extent of removal of the soils and stains using the following scale:
  • proteases at a level of 32 mg active enzyme per 100 g of the bleach-containing detergent product are tested as in Example I.
  • the E/B ratio for these treatments is 7.6.
  • the results are shown in Table 2.
  • Table 2A shows that, according to this wash performance test, the bleach + protease sample (D) performs significantly better than the added single contributions of the bleach sample (B) and the protease sample (C) for the proteases tested.
  • proteases were tested in the presence of different bleach systems in the same detergent composition as Example I.
  • Protease C at a level of 32 mg active enzyme per 100 g of the final product is tested in the presence of benzoyloxybenzenesulfonate (BOBS)/PB1 and tetra acetyl ethylene diamine (TAED)/PBl bleach systems (E/B ratio of 7.6).
  • Protease C is also tested at a level of 6.4 mg active enzyme per 100 g of the final product in the presence of the nonyl amide of monoperoxy adipic acid (NAPAA) (E/B ratio of 1.5).
  • NAPAA nonyl amide of monoperoxy adipic acid
  • Protease Cl is evaluated in the presence of NAPAA at a level of 64 mg active enzyme per 100 g of the product (E/B ratio of 15.2). In this testing, a sufficient amount of bleach is added to result in an available oxygen level of 4.2 ppm. Performance data on grass stain is presented in Table 3.
  • Table 3A shows that, according to this wash performance test, the bleach and protease sample (D) performs significantly better than the additive contributions of the bleach sample (B) (except TAED) plus the protease sample (C) for the proteases tested.
  • Protease C is tested at a level of 12.8 mg active enzyme per 100 g of the product (same procedure and same detergent composition as in Example I) in a reduced NOBS/PB1 level (2.7 ppm AvO) and at a lower temperature.
  • the E/B ratio for this example is 4.7.
  • the wash performance is carried out at 21,1°C (70°F) and 136,88 mg/l (8 gr/gal) hardness. The results are reported in Table 4.
  • Table 4A shows that, according to this wash performance test, the bleach and protease sample (D) performs significantly better than the additive contributions of the bleach sample (B) plus the protease sample (C).
  • proteases such as Protease B, Maxacal, and BPN' can be interchanged with Protease C.
  • Protease levels can be varied between 0.064 and 0.64 mg of active enzyme per gram of composition.
  • bleaching agents can be interchanged with NOBS, such as BOBS, NAPAA, the nonylamide of peroxysuccinic acid (NAPSA), and the phenyl sulfonate salt of 6-nonylamino-6-oxycaproicacid and other NAPAA-like activators.
  • the level of bleaching agent can be varied between 0.5 and 20 wt % of the composition.
  • Sodium carbonate peroxyhydrate can be used instead of sodium perborate in an amount between 0.5 and 20 weight % of the composition.
  • a composition suitable for use in the method of the present invention is as follows: Material Wt % Sodium C 11 -C 13 linear alkylbenzene sulfonate 10.36 Sodium C 14 -C 15 alkyl sulfate 2.96 Sodium C 14 -C 15 alkyl ethoxy sulfate 1.48 Sodium aluminosilicate 21.30 Sodium carbonate 25.30 Citric acid 3.00 Sodium n-nonanoyloxybenzene sulfonate 4.73 Sodium perborate monohydrate 3.54 Protease C 0.11 Polyethyleneglycol 1.06 Sodium polyacrylate 2.72 Sodium silicate 1.85 Fluorescent whitening agent, moisture, misc. 11.97
  • bleaching agents can be substituted for NOBS, such as BOBS, NAPAA, and NAPSA (all defined above).
  • Other proteases such as Protease B, Maxacal® and BPN' can be substituted for Protease C.

Claims (12)

  1. Verfahren zum Reinigen von Textilien in der Wäsche durch Kontaktieren der Textilien mit einer Waschlösung, welche eine wirksame Menge einer granulären Waschmittelzusammensetzung enthält. welche eine besonders wirksame Oberflächenreinigung von Textilien ergibt, welche Zusammensetzung umfaßt:
    A. 0,5 bis 20 Gew.-% der Zusammensetzung eines Bleichmittels, das eine im wesentlichen unlösliche, organische Peroxysäure ist, deren korrespondierende Carbonsäure einen Hydrophil-Lipophil-Gleichgewichtswert im Bereich von 3 bis 6,5, vorzugsweise 4.0 bis 6.5, aufweist;
    B. 0.064 bis 0,64 mg, vorzugsweise 0,096 bis 0,32 mg, aktives Proteaseenzym. pro Gramm der Zusammensetzung; und
    C. 1 bis 40 Gew.-% der Zusammensetzung eines Waschmitteltensids, gewählt aus anionischen, nichtionischen, ampholytischen und zwitterionischen Tensiden und Kombinationen hiervon; vorzugsweise 2 bis 20 Gew.-% eines anionischen Tensids,
    wobei das Proteaseenzym weiterhin in einer ausreichenden Menge vorliegt, um ein Verhältnis von mg aktive Protease pro 100 Gramm der Zusammensetzung zu ppm theoretisch verfügbarem O2 aus der Peroxysäure in der Waschflotte im Bereich von 1:1 bis 20:1 vorzusehen.
  2. Verfahren nach Anspruch 1, wobei
    A. die organische Peroxysäure aus 4-Nonyl-amino-4-oxoperoxybuttersäure; 6-(Nonylamimo)-6-oxoperoxycapronsäure: 1,12-Diperoxydodecandisäure: Heptylsulfonylperpropionsäure; Decylsulfonylperpropionsäure; Heptyl-, Octyl-, Nonyl- und Decylsulfonylperbuttersäure; und Kombinationen dieser Peroxysäuren gewählt wird;
    B. das aktive Proteaseenzym modifiziertes bakterielles Serinproteaseenzym umfaßt, erhalten aus Bazillus subtilis oder Bazillus licheniformis;
    C. das anionische Tensid aus den Salzen von linearem C11-13-Alkylbenzolsulfonat, C12-16-Alkylsulfat, Methylestersulfonat und Kombinationen dieser Tenside gewählt wird; und
    D. die Zusammensetzung weiterhin 20 bis 70 Gew.-% der Zusammensetzung eines Waschmittelbuilders umfaßt.
  3. Verfahren zum Reinigen von Textilien in der Wäsche durch Kontaktieren der Textilien mit einer Waschlösung, welche eine wirksame Menge einer granulären Waschmittelzusammensetzung enthält, welche eine besonders wirksame Oberflächenreinigung von Textilien ergibt, wobei die Zusammensetzung umfaßt:
    A. eine Bleichmittelkomponente, welche 0.5 bis 20, vorzugsweise 1 bis 10 Gew.-% der Zusammensetzung, eines Bleichaktivators umfaßt, welcher Aktivator in Kombination mit einer Persauerstoffverbindung vorliegt, welche fähig ist, Wasserstoffperoxid zu erzielen, welches mit dem Aktivator reagieren kann, um in situ eine organische Peroxysäure in der aus der Zusammensetzung gebildeten Bleichlösung zu bilden; wobei
    1) der Bleichaktivator eine Formel aufweist, gewählt aus
    Figure 00390001
    Figure 00390002
    und
    Figure 00390003
    worin R eine Alkylgruppe mit 5 bis 18 Kohlenstoffatomen ist, worin die längste lineare Alkylkette, welche sich vom Carbonylkohlenstoff erstreckt und diesen beinhaltet, 6 bis 10 Kohlenstoffatome enthält; R1 eine Alkylgruppe mit 6 bis 12 Kohlenstoffatomen ist; R2 ein Alkylen mit 1 bis 6 Kohlenstoffatomen ist; und R5 H oder Alkyl, Aryl oder Alkaryl mit 1 bis 10 Kohlenstoffatomen ist; und L eine Abgangsgruppe ist, deren konjugierte Säure einen pKa im Bereich von 6 bis 13 aufweist;
    ii) das Molverhältnis von durch die Persauerstoffverbindung erzieltem Wasserstoffperoxid zu dem Aktivator größer als 1,5 ist; und
    iii) der Hydrophil-Lipophil-Gleichgewichtswert der zu der Peroxysäure korrespondierenden Carbonsäure, welche in situ gebildet wird, im Bereich von 3 bis 6,5, vorzugsweise 4,0 bis 6.5, liegt; und
    B. 0,064 bis 0.64 mg, vorzugsweise 0.096 bis 0,32 mg, aktives Proteaseenzym, pro Gramm der Zusammensetzung; und
    C. 1 bis 40 Gew.-% der Zusammensetzung eines Waschmitteltensids, gewählt aus anionischen, nichtionischen, ampholytischen und zwitterionischen Tensiden und Kombinationen hiervon, vorzugsweise 2 bis 25 Gew.-% der Zusammensetzung eines anionischen Tensids,
    wobei das Proteaseenzym weiterhin in einer ausreichenden Menge vorliegt, um ein Verhältnis von mg an aktiver Protease pro 100 Gramm der Zusammensetzung zu ppm theoretisch verfügbarem O2 aus der Peroxysäure in der Waschflotte im Bereich von 1:1 bis 20:1 vorzusehen.
  4. Verfahren nach Anspruch 3, wobei, wenn der Aktivator die Struktur B aufweist, dann in dieser Struktur R eine Alkylgruppe mit 5 bis 12 Kohlenstoffatomen ist, worin der längste lineare Teil der Alkylkette, welcher sich von dem Carbonylkohlenstoff erstreckt und diesen beinhaltet, 6 bis 10 Kohlenstoffatome umfaßt, und L aus der Gruppe gewählt ist, bestehend aus:
    Figure 00400001
    worin R2 eine Alkylkette mit 1 bis 8 Kohlenstoffatomen ist, und Y -SO3 -M+ oder -COO-M+ ist, worin M ein Alkallmetall, Ammonium- oder substituiertes Ammoniumkation ist.
  5. Verfahren nach Anspruch 3, wobei, wenn der Aktivator die Struktur II oder III aufweist, dann in diesen Strukturen die Abgangsgruppe L gewählt ist aus:
    Figure 00400002
    Figure 00400003
    Figure 00410001
    Figure 00410002
    Figure 00410003
    und
    Figure 00410004
    worin R6 eine Alkylen-, Arylen- oder Alkarylengruppe mit 1 bis 14 Kohlenstoffatomen ist, R3 eine Alkylkette mit 1 bis 8 Kohlenstoffatomen ist, R4 H oder R3 ist, und Y H oder eine solubilisierende Gruppe ist.
  6. Verfahren nach Anspruch 5. wobei in den Strukturen für die Abgangsgruppe Y aus der Gruppe gewählt ist, bestehend aus -SO3 - M+, -COO- M+, -SO4 - M+, (-NR'3 +) X- und O←N(R'3), worin R' eine Alkylkette mit 1 bis 4 Kohlenstoffatomen ist, M ein Alkalimetall-, Ammonium- oder substituiertes Ammoniumkation ist, und X ein Anion ist. gewählt aus der Halogenid-, Hydroxid-, Methylsulfat- und Acetatanionen umfassenden Gruppe.
  7. Verfahren nach Anspruch 3, wobei
    A. der Aktivator aus Natriumnonanoyloxybenzolsulfonat und Natriumbenzoyloxybenzolsulfonat gewählt ist;
    B. die Persauerstoffverbindung aus Natriumperborat und Natriumcarbonatperoxyhydrat gewählt ist und in einer Menge von 1 bis 10 Gew.-% der Zusammensetzung vorliegt;
    C. das Molverhältnis von durch die Persauerstoffverbindung erzieltem Wasserstoffperoxid zu Bleichaktivator 2,0 zu 10 trägt;
    D. das aktive Proteaseenzym modifiziertes bakterielles Serinproteaseenzym, erhalten aus Bazillus subtilis oder Bazillus licheniformis, umfaßt;
    E. das anionische Tensid aus den Salzen von linearem C11-13-Alkylbenzolsulfonat, C12-16-Alkylsulfat, Methylestersulfonat und Kombinationen dieser Tenside gewählt ist; und
    F. die Zusammensetzung weiterhin 20 bis 70 Gew.-% der Zusammensetzung eines Waschmittelbuilders umfaßt.
  8. Verfahren nach Anspruch 1, wobei die Zusammensetzung umfaßt:
    A. 1 bis 7 Gew.-% der Zusammensetzung eines im wesentlichen unlöslichen, organischen Peroxysäure-Bleichmittels, gewählt aus der 4-Nonylamino-4-oxoperoxybuttersäure: 6-(Nonylamino)-6-oxoperoxycapronsäure: 1,12-Diperoxydodecandisäure: Heptylsulfonylperpropionsäure; Decylsulionylperpropionsäure; Heptyl-, Octyl- Nonyl- und Decylsulfonylperbuttersäuren; und Kombinationen solcher Peroxysäuren umfassenden Gruppe, vorzugsweise das Nonylamid von Peroxyadipinsäure oder 1,2-Diperoxydodecandisäure;
    B. 0,096 bis 0,32 mg pro Gramm der Zusammensetzung eines proteolytischen Serinenzyms bakteriellen Ursprungs; und
    C. 2 bis 25 Gew.-% der Zusammensetzung eines Waschmitteltensids, gewählt aus anionischen Tensiden, nichtionischen Tensiden und Kombinationen hiervon;
  9. Verfahren nach Anspruch 3 wobei die Zusammensetzung umfaßt:
    A. 1 bis 10 Gew.-% der Zusammensetzung einer Persauerstoff-Bleichmittelverbindung, gewählt aus Natriumperborat, Natriumcarbonat, Peroxyhydrat und Kombinationen hiervon;
    B. 1 bis 10 Gew.-% der Zusammensetzung eines Bleichaktivators, gewählt aus Natriumnononoyloxybenzolsulfonat und Natriumbenzoyloxybenzolsulfonat;
    C. 0,096 bis 0,32 mg pro Gramm der Zusammensetzung eines proteolytischen Serinenzyms bakteriellen Ursprungs; und
    D. 2 bis 25 Gew.-% der Zusammensetzung eines Waschmitteltensids, gewählt aus anionischen Tensiden, nichtionischen Tensiden und Kombinationen hiervon;
  10. Verfahren nach Anspruch 8 oder Anspruch 9, wobei
    A. das proteolytische Enzym aus Savinase®, Maxacal®, BPN', Protease A, Protease B, Protease C oder Kombinationen hiervon gewählt ist; und
    B. das Waschmitteltensid aus linearen Alkylbenzolalkahmetallsulfonaten, Alkalimetallalkylethylenoxidethersulfaten, Alkalimetallalkylethylenoxidethersulfaten, Alkalimetallalkylsulfaten oder Kombinationen dieser Tenside gewählt ist.
  11. Verfahren nach mindestens einem der Ansprüche 8, 9 oder 10, wobei die Zusammensetzung weiterhin 20 bis 70 Gew.-% der Zusammensetzung eines Waschmittelbuilders umfaßt, gewählt aus Carbonaten, Silicaten, Sulfaten, Phosphaten, Aluminosilicaten, Citraten und Kombinationen hiervon.
  12. Verfahren nach Anspruch 9, wobei die granuläre Wäschewaschmittelzusammensetzung kein Phosphat enthält und umfaßt:
    a. 2 bis 7 Gew.-% der Zusammensetzung Nonanoyloxybenzolsulfonat und 2 bis 7 Gew.-% der Zusammensetzung Natriumperborat;
    b. 0,096 bis 0,32 mg aktive Protease C pro Gramm der Zusammensetzung: und
    c. 2 bis 25 Gew.-% der Zusammensetzung lineares C12-13-Alkylbenzolnatriumsulfonat und Natrium-C14-15-alkylsulfat.
EP93924343A 1992-10-23 1993-10-18 Granulare waschmittel mit protease Revoked EP0665876B1 (de)

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WO1994010284A1 (en) 1994-05-11
JPH08502546A (ja) 1996-03-19
CA2147658A1 (en) 1994-05-11
CZ101595A3 (en) 1996-04-17
PL175424B1 (pl) 1998-12-31
MX9306634A (es) 1994-04-29
EG20573A (en) 1999-08-30
GR3029922T3 (en) 1999-07-30
ATE178352T1 (de) 1999-04-15
EP0665876A1 (de) 1995-08-09
BR9307300A (pt) 1999-06-01
HU9501144D0 (en) 1995-06-28
ES2131125T3 (es) 1999-07-16
HU217918B (hu) 2000-05-28
MA23011A1 (fr) 1994-07-01
DE69324261D1 (de) 1999-05-06
AU5406394A (en) 1994-05-24
PL308475A1 (en) 1995-08-07
CN1090599A (zh) 1994-08-10
DE69324261T2 (de) 1999-10-14
DK0665876T3 (da) 1999-06-21
KR950704466A (ko) 1995-11-20
HUT71729A (en) 1996-01-29

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