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WO1994010284A1 - Detergents granulaires contenant une enzyme protease et un agent de blanchiment - Google Patents

Detergents granulaires contenant une enzyme protease et un agent de blanchiment Download PDF

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Publication number
WO1994010284A1
WO1994010284A1 PCT/US1993/009930 US9309930W WO9410284A1 WO 1994010284 A1 WO1994010284 A1 WO 1994010284A1 US 9309930 W US9309930 W US 9309930W WO 9410284 A1 WO9410284 A1 WO 9410284A1
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WIPO (PCT)
Prior art keywords
composition
acid
weight
carbon atoms
protease
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PCT/US1993/009930
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English (en)
Inventor
David Neil Di Giulio
Edward Eugene Getty
Chanchal Kumar Ghosh
Original Assignee
The Procter & Gamble Company
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25510025&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1994010284(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP93924343A priority Critical patent/EP0665876B1/fr
Priority to DE69324261T priority patent/DE69324261T2/de
Priority to JP6511119A priority patent/JPH08502546A/ja
Priority to DK93924343T priority patent/DK0665876T3/da
Priority to PL93308475A priority patent/PL175424B1/pl
Priority to BR9307300A priority patent/BR9307300A/pt
Priority to AU54063/94A priority patent/AU5406394A/en
Priority to KR1019950701554A priority patent/KR950704466A/ko
Publication of WO1994010284A1 publication Critical patent/WO1994010284A1/fr
Priority to GR990401014T priority patent/GR3029922T3/el

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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 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 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.
  • This invention relates to 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 of this invention comprise: a) a bleaching agent which either is from 0.5% to 20% of an organic peroxyacid or is a combination of from 0.5% to 20% of a bleach activator and a peroxygen compound capable of yielding hydrogen peroxide that can react with the activator to form an organic peroxyacid in situ in a bleaching solution formed from the composition; b) from about 0.064 to about 0.64 mg of active protease enzyme per gram of composition wherein the protease enzyme is present in an amount sufficient to provide a ratio of mg of active protease per 100 grams of composition to ppm theoretical Available 02 of the peroxyacid ranging from about 1:1 to about 20:1; and c) from about 1% to about 40% by weight of the composition of a detergent surfactant which can be anionic, nonionic, ampholytic or zwitterionic surfactants or combinations thereof.
  • a detergent surfactant which can be anionic, nonionic, ampholytic or zwitterionic surfact
  • 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 about 3 to about 6.5.
  • the molar ratio of hydrogen peroxide yielded by the peroxygen compound to the activator is greater than about 1.5.
  • the activator can have the formula: (I)
  • Rl . c - N - R2 - C - L wherein R is an alkyl group containing from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbon atoms; R- is an alkyl group containing from about 6 to about 12 carbon atoms; R 2 is an alkylene containing from 1 to about 6 carbon atoms; R ⁇ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms; and L is a leaving group, the conjugate acid of which has a pK a in the range of from about 6 to about 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 solid form, e.g., granules, powders, agglomerates, laundry bars, etc.
  • 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 about 5*C and about 80 * C, preferably between about 10 * C and about 60 * C, for this cleaning benefit.
  • the granular detergent compositions herein contain a bleaching agent, which preferably comprises from about 0.5 to about 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: 0
  • R is an alkyl group containing from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pk a in the range of from about 6 to about 13, preferably from about 7 to about 11, most preferably from about 8 to about 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 general formula: R5 0 0 0 R ⁇ 0
  • R3 0 wherein R ⁇ is an alkylene, arylene, or alkarylene group containing from about 1 to about 14 carbon atoms, R3 is an alkyl chain containing from about 1 to about 8 carbon atoms, R is H or R 3 , and Y is H or a solubi11zing group.
  • Y is preferably selected from the group consisting of --SO3-M+, --C00-M+, --SO4-M+, (--N+R'3)X- and 0 ⁇ -N(R , 3), wherein R' is an alkyl chain containing from about 1 to about 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 --SO3-M+ and --C00-M+. It should be noted that 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:
  • R 3 is as defined above and Y is --SO3-M+ or --C00-M+ wherein M is as defined above.
  • Especially preferred bleach activators are those wherein R 1 is a linear alkyl chain containing from about 6 to about 12 carbon atoms, R 2 is a linear alkylene chain containing from about 2 to about 6 carbon atoms, R 5 is H, and L is selected from the group consisting of:
  • R3 is as defined above, Y is --SO3-M+ or --C00-M+ and M is as defined above.
  • a preferred bleach activator is: 0
  • R is H, alkyl, aryl or alkaryl. This is described in U.S. Patent 4,966,723, Hodge et al, incorporated by reference herein.
  • Preferred bleach activators are:
  • Rl is H or an alkyl group containing from about 1 to about 6 carbon atoms and R2 is an alkyl group containing from about 1 to about 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 about 1 to about 4 carbon atoms, and R 2 is an alkyl group containing from about 1 to about 4 carbon atoms.
  • bleach activators of the above general formula wherein L is as defined in the general formula and Rl is a H are particularly preferred.
  • a more preferred bleach activator is: 0
  • More preferred bleach activators are those of the above general formula wherein R is a linear alkyl chain containing from about 5 to about 9 and preferabiy from about 6 to about 8 carbon atoms and L is selected from the group consisting of:
  • 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 about 5 to about 12 carbon atoms wherein the longest linear portion of the alkyl chain extending from and including the carbonyl carbon is from about 6 to about 10 carbon atoms, and L is selected from the group consisting of:
  • R 2 is an alkyl chain containing from about 1 to about 8 carbon atoms
  • Y is --SO-3M+ or --C00-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 about 5 to about 9 and preferably from about 6 to about 8 carbon atoms and L is selected from the group consisting of: wherein R2 is as defined above and Y is --SO-3M+ or --C00-M+ wherein M is as defined above.
  • the most preferred bleach activators have the formula: 0
  • R is a linear alkyl chain containing from about 5 to about 9 and preferably from about 6 to about 8 carbon atoms and M is sodium or potassium.
  • the level of bleach activator within the compositions of the invention is preferably from about 0.5 to about 20, more preferably from about 1 to about 10, most preferably from about 2 to about 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 about 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 nonanoyl- oxybenzenesulfonate (NOBS) or sodium benzoyloxybenzenesulfonate (BOBS).
  • NOBS nonanoyl- oxybenzenesulfonate
  • BOBS sodium benzoyloxybenzenesulfonate
  • the molar ratio of hydrogen peroxide yielded by the peroxygen bleaching compound to the bleach activator is greater than about 1.5, preferably from about 2.0 to about 10.
  • the detergent compositions herein comprise from about 0.5 to about 20, most preferably from about 1 to about 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 ara 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 about 0.5 to about 20, preferably from about 1 to about 10, most preferably from about 2 to about 7, wt.% of the detergent composition.
  • Preferred organic peroxyacids are selected from the group consisting of 4-nonylamino-4-oxoperoxybutyric acid; 6-(nonyl- amino)-6- oxoperoxycaproic acid; 1,12-diperoxydodecanedioic acid,; heptyl sulfonylperpropionic acid; decylsulphonyl perpropionic acid; and heptyl-, octyl-, nonyl-, decyl-sulphonylperbutyric acids; and mixtures thereof.
  • amidoperoxyacids amide substituted peroxycarboxylic acids
  • 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, both incorporated herein by reference.
  • Suitable amidoperoxyacids are of the formula:
  • Rl is an alkyl group containing from about 6 to about 12 carbon atoms
  • R 2 is an alkylene group containing from 1 to about 6 carbon atoms.
  • Rl is an alkyl group containing from about 8 to about 10 carbon atoms
  • R 2 is an alkylene group containing from about 2 to about 4.
  • peroxyfumarates which are described in U.S. Patent 4,852,989, Burns et al, issued August 1, 1989, incorporated herein by reference
  • sulfone peroxyacids which are described in U.S. Patents 4,758,369, 4,824,591, and 5,004,558, all Dryoff et al, issued July 19, 1988, April 25, 1989, and April 2, 1991, respectively, all incorporated herein by reference.
  • 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 about 3.5 and 6, preferably between about 4 and 5, according to U.S. Patent 4,909,953, Sadlowski et al, issued March 20, 1990, which is incorporated herein by reference.
  • 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 and incorporated herein, can be mixed with the amidoperoxyacid (which has been washed in phosphate buffer) in about a 2:1 peracid:boric acid ratio.
  • 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 about 0.1 to about 260 microns, preferably from about 10 to about 100 microns, and most preferably from about 30 to about 60 microns.
  • Small particle size NAPAA crystals are desired herein. See U.S. Patent 5,055,218, Getty et al, issued October 8, 1991, which is incorporated herein by reference.
  • 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 about 3 and about 12, most preferably between 5 and 7, are preferred.
  • NAPAA nonylamide of £eroxyadipic acid
  • NAPAA 6-(nonylamino)-6- oxoperoxycaproic acid
  • NAPAA CH3(CH2)8N C (CH2)4C00H
  • 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 about 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. Conor. Surface Activity 1. 426, Butterworths, London (1957), incorporated herein by reference. 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:
  • H.L.B. value ⁇ 7 indicates increasing surface-activity and hydrophobicity.
  • a preferred range of H.L.B. values ranges from about 3.0 to about 6.5.
  • a more 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) range from about 4.0 to 6.5.
  • the most preferred range of H.L.B. values (as the carboxylic acid) for the peroxyacids of the present invention (whether added directly as generated in situ) ranges from about 4.0 to about 6.0.
  • the detergent compositions of the present invention also comprise from about 0.064 to about 0.64, preferably from about 0.096 to about 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); Maxatase ® , Maxacal® (preferred), and Maxape 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 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.
  • 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 90915958:4, corresponding to W0 91/06637, Published May 16, 1991, which is incorporated herein by reference. 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 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 preferred range for the ratio of active protease to peroxyacid Av ⁇ 2 (E/B) is from about 1 to about 20.
  • compositions of this invention also include from about 1 to about 40 weight % of peroxyacid-stable, water-soluble detergent surfactant selected from the group consisting of anionics, nonionics, zwitterionics, ampholytlcs, and mixtures thereof. From about 2 to about 25 weight % of detergent surfactant is preferred and from about 5 to about 15 weight % is most preferred. Anionic surfactant is preferred and salts of Cn-13 linear alkyl benzene sulfonate, C12-I6 alkyl sulfate and/or methyl ester sulfonates are more preferred. From about 2 to about 25 wt. % of sodium C12-13 linear alkyl benzene sulfonate and sodium C14-15 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, both incorporated herein by reference. The following are representative examples of detergent surfactants useful in the present compositions.
  • 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 about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl 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 (Cs-Ci ⁇ 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 about 9 to about 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 about 11 to 13, abbreviated as C11-13LAS.
  • 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 onoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12. carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • Water-soluble nonionic surfactants are also useful in the compositions 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 about 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 about 9 to 15 carbon atoms with from about 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 about 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
  • a pholytic 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 about 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 about 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 alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosili- cates.
  • 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 about 50*C, especially less than about 40'C.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ 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, incorporated herein by reference. 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, the disclosure of which is incorporated herein by reference.
  • Aluminosilicate builders are useful in the present invention.
  • Aluminosilicate builders include those having the empirical formula:
  • Preferred aluminosilicates are zeolite builders which have the formula:
  • 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 about 6 to about 21, and salts of phytic acid.
  • Organic detergent builders preferred for the purposes of the present invention include polyearboxylate compounds which have a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarbox late 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, both of which are incorporated herein by reference.
  • ether polycarboxylates useful as builders in the present invention also include those having the general formula:
  • 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, all of which are incorporated herein by reference.
  • 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 ellitic 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, incorporated herein by reference.
  • succinic acid builders include the C5-C20 alk l 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-cyclo- hexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water- soluble polyacrylates, and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • polycarboxylates are the polyacetal car- boxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979, incorporated herein by reference.
  • Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. 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 C10-C20 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.
  • 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 about 0.0001 to about 1.0, more preferably about 0.001 to about 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. F. Other Ingredients
  • 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 about 0.5 to about 5 wt.% of the composition of polyethylene glycol (preferably with molecular weight between 5,000 and 10,000, most preferably 8,000), from about 0.01 to about 0.7 wt.% of fluorescent whitening and/or brightening agents, and from about 0.01 to about 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 1/4 to 1 cup.
  • This invention most preferably provides a nonphosphate granular laundry detergent composition
  • a nonphosphate granular laundry detergent composition comprising, by weight of the composition: a. from about 2 to about 7 weight % of nonanoyloxybenzenesulfonate (NOBS) and from about 2 to about 7 weight % of sodium perborate; b. from about 0.096 to about 0.32 of active Protease C per gram of composition; and c. from about 2 to about 25 weight % of sodium C12-13 linear alkyl benzene sulfonate and sodium C14-15 alkyl sulfate.
  • NOBS nonanoyloxybenzenesulfonate
  • This invention further provides a method for cleaning fabrics in the wash by contacting the fabrics with a wash solution which contains an effective amount of the detergent compositions hereinbefore described. 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 about 500 to about 7000 pp , more preferably from about 1000 to about 3000 ppm.
  • 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 90915958:4) hereinafter referred to as Protease C; and a variant of Protease C hereinafter referred to as Protease CI.
  • 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 5 lbs. of naturally soiled ballast fabrics and 64 liters of 95 * F city water having a hardness of 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 (Av ⁇ 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:
  • 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.
  • EXAMPLE III Several 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 (B0BS)/PB1 and tetra acetyl ethylene diamine (TAED)/PB1 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 CI 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. le
  • 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 N0BS/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 70"F and 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 about 0.064 and about 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 about 0.5 and about 20 wt % of the composition.
  • Sodium carbonate peroxyhydrate can be used instead of sodium perborate in an amount between about 0.5 and about 20 weight % of the composition.
  • a composition of the present invention is as follows:
  • Fluorescent whitening agent, moisture, misc. 11.97 ⁇ denotes mg of active enzyme per gram of composition
  • 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.
  • a laundry bar suitable for hand-washing soild fabrics is prepared by standard extrusion processes and comprises the following: Component
  • ⁇ denotes mg of active enzyme per gram of composition
  • the detergent laundry bars are processed in conventional soap or detergent bar making equipment as commonly used in the art.

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Abstract

L'invention se rapporte à des compositions de détergents granulaires, qui contiennent certains niveaux d'un tensioactif détergent, d'un agent de blanchiment et d'une enzyme protéase. L'agent de blanchiment est constitué par du peroxyacide organique essentiellement insoluble ou par une combinaison constituée par un activateur d'agent de blanchiment et par un composé de blanchiment au peroxygène.
PCT/US1993/009930 1992-10-23 1993-10-18 Detergents granulaires contenant une enzyme protease et un agent de blanchiment WO1994010284A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP93924343A EP0665876B1 (fr) 1992-10-23 1993-10-18 Detergents granulaires contenant une enzyme protease et un agent de blanchiment
DE69324261T DE69324261T2 (de) 1992-10-23 1993-10-18 Granulare waschmittel mit protease
JP6511119A JPH08502546A (ja) 1992-10-23 1993-10-18 プロテアーゼ酵素と漂白剤とを有する粒状洗剤
DK93924343T DK0665876T3 (da) 1992-10-23 1993-10-18 Granulære detergenter med proteaseenzym og blegemiddel
PL93308475A PL175424B1 (pl) 1992-10-23 1993-10-18 Granulowany detergent z enzymem proteolitycznym i środkiem bielącym
BR9307300A BR9307300A (pt) 1992-10-23 1993-10-18 Detergentes granulares com enzima protease e alvejante
AU54063/94A AU5406394A (en) 1992-10-23 1993-10-18 Granular detergents with protease enzyme and bleach
KR1019950701554A KR950704466A (ko) 1992-10-23 1993-10-18 프로테아제 효소와 표백제를 함유하는 과립상 세제(Granular detergents with protease enzyme and bleach)
GR990401014T GR3029922T3 (en) 1992-10-23 1999-04-07 Granular detergents with protease enzyme and bleach.

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US96547892A 1992-10-23 1992-10-23
US07/965,478 1992-10-23

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AT (1) ATE178352T1 (fr)
AU (1) AU5406394A (fr)
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CA (1) CA2147658A1 (fr)
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DE (1) DE69324261T2 (fr)
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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994028106A1 (fr) * 1993-05-20 1994-12-08 The Procter & Gamble Company Composes de blanchiment comprenant des adjuvants au peroxyacide utilises avec des enzymes
WO1995000625A1 (fr) * 1993-06-25 1995-01-05 The Procter & Gamble Company Compositions detergentes granulaires pour la lessive, contenant une lipase et un sulfonate de nonanoyloxybenzene de sodium
WO1995010592A1 (fr) * 1993-10-14 1995-04-20 The Procter & Gamble Company Compositions contenant un agent de blanchiment et des proteases
WO1995029225A1 (fr) * 1994-04-22 1995-11-02 The Procter & Gamble Company Compositions de blanchiment comprenant une enzyme protease
US5679630A (en) * 1993-10-14 1997-10-21 The Procter & Gamble Company Protease-containing cleaning compositions
US5707950A (en) * 1994-11-18 1998-01-13 The Procter & Gamble Company Detergent compositions containing lipase and protease
US5837010A (en) * 1994-11-18 1998-11-17 Procter & Gamble Company Detergent compositions containing a lipase variant at low levels
WO1999013039A1 (fr) * 1997-09-11 1999-03-18 The Procter & Gamble Company Compositions detergentes
WO1999033946A1 (fr) * 1997-12-29 1999-07-08 Colgate-Palmolive Company Produits a action detachante amelioree contenant des enzymes
US6066611A (en) * 1994-10-13 2000-05-23 The Procter & Gamble Company Bleaching compositions comprising protease enzymes
US6369250B1 (en) 1997-08-20 2002-04-09 Procter & Gamble Company Process for preparing and/or purifying amido acid phenyl ester sulfonates
US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9253978B2 (en) 2008-03-28 2016-02-09 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9290448B2 (en) 2008-03-28 2016-03-22 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9540598B2 (en) 2008-03-28 2017-01-10 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9763442B2 (en) 2010-12-29 2017-09-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US12058999B2 (en) 2018-08-22 2024-08-13 Ecolab Usa Inc. Hydrogen peroxide and peracid stabilization with molecules based on a pyridine carboxylic acid
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions
US12203056B2 (en) 2008-03-28 2025-01-21 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents

Families Citing this family (2)

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CN1048279C (zh) * 1995-12-20 2000-01-12 北京洛娃新型化工材料技术开发有限公司 含氧漂白剂的皂粉及其制造方法
CN103196857A (zh) * 2013-04-19 2013-07-10 陈军 洗涤评估用人工污渍样本的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2116046A5 (fr) * 1970-11-27 1972-07-07 Procter Gamble Europ
FR2232590A1 (en) * 1973-06-07 1975-01-03 Procter & Gamble Europ Washing compsn. contg. org. peracids - with surface active agents and enzymes for better stain removal
EP0206418A2 (fr) * 1985-06-28 1986-12-30 The Procter & Gamble Company Composition granulaire contenant un agent de blanchiment sec et une enzyme stable
US4634551A (en) * 1985-06-03 1987-01-06 Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
EP0212976A2 (fr) * 1985-08-21 1987-03-04 The Clorox Company Composition de blanchiment stable, à base de peracide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2116046A5 (fr) * 1970-11-27 1972-07-07 Procter Gamble Europ
FR2232590A1 (en) * 1973-06-07 1975-01-03 Procter & Gamble Europ Washing compsn. contg. org. peracids - with surface active agents and enzymes for better stain removal
US4634551A (en) * 1985-06-03 1987-01-06 Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
EP0206418A2 (fr) * 1985-06-28 1986-12-30 The Procter & Gamble Company Composition granulaire contenant un agent de blanchiment sec et une enzyme stable
EP0212976A2 (fr) * 1985-08-21 1987-03-04 The Clorox Company Composition de blanchiment stable, à base de peracide

Cited By (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994028106A1 (fr) * 1993-05-20 1994-12-08 The Procter & Gamble Company Composes de blanchiment comprenant des adjuvants au peroxyacide utilises avec des enzymes
WO1995000625A1 (fr) * 1993-06-25 1995-01-05 The Procter & Gamble Company Compositions detergentes granulaires pour la lessive, contenant une lipase et un sulfonate de nonanoyloxybenzene de sodium
US6017871A (en) * 1993-10-14 2000-01-25 The Procter & Gamble Company Protease-containing cleaning compositions
WO1995010592A1 (fr) * 1993-10-14 1995-04-20 The Procter & Gamble Company Compositions contenant un agent de blanchiment et des proteases
US5677272A (en) * 1993-10-14 1997-10-14 The Procter & Gamble Company Bleaching compositions comprising protease enzymes
US5679630A (en) * 1993-10-14 1997-10-21 The Procter & Gamble Company Protease-containing cleaning compositions
WO1995029225A1 (fr) * 1994-04-22 1995-11-02 The Procter & Gamble Company Compositions de blanchiment comprenant une enzyme protease
US6066611A (en) * 1994-10-13 2000-05-23 The Procter & Gamble Company Bleaching compositions comprising protease enzymes
US5707950A (en) * 1994-11-18 1998-01-13 The Procter & Gamble Company Detergent compositions containing lipase and protease
US5837010A (en) * 1994-11-18 1998-11-17 Procter & Gamble Company Detergent compositions containing a lipase variant at low levels
US6369250B1 (en) 1997-08-20 2002-04-09 Procter & Gamble Company Process for preparing and/or purifying amido acid phenyl ester sulfonates
WO1999013039A1 (fr) * 1997-09-11 1999-03-18 The Procter & Gamble Company Compositions detergentes
US6689732B1 (en) 1997-09-11 2004-02-10 The Procter & Gamble Company Detergent compositions having a specific hydrophobic peroxyacid bleaching system and anionic surfactant
WO1999033946A1 (fr) * 1997-12-29 1999-07-08 Colgate-Palmolive Company Produits a action detachante amelioree contenant des enzymes
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Also Published As

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MX9306634A (es) 1994-04-29
CZ101595A3 (en) 1996-04-17
ATE178352T1 (de) 1999-04-15
PL175424B1 (pl) 1998-12-31
DE69324261T2 (de) 1999-10-14
DE69324261D1 (de) 1999-05-06
EP0665876B1 (fr) 1999-03-31
JPH08502546A (ja) 1996-03-19
AU5406394A (en) 1994-05-24
CN1090599A (zh) 1994-08-10
ES2131125T3 (es) 1999-07-16
CA2147658A1 (fr) 1994-05-11
DK0665876T3 (da) 1999-06-21
HUT71729A (en) 1996-01-29
PL308475A1 (en) 1995-08-07
EP0665876A1 (fr) 1995-08-09
HU217918B (hu) 2000-05-28
MA23011A1 (fr) 1994-07-01
KR950704466A (ko) 1995-11-20
GR3029922T3 (en) 1999-07-30
HU9501144D0 (en) 1995-06-28
EG20573A (en) 1999-08-30
BR9307300A (pt) 1999-06-01

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