WO1994004654A1 - LIQUID DETERGENT COMPOSITIONS CONTAINING PROTEASE AND CERTAIN β-AMINOALKYLBORONIC ACIDS AND ESTERS - Google Patents

LIQUID DETERGENT COMPOSITIONS CONTAINING PROTEASE AND CERTAIN β-AMINOALKYLBORONIC ACIDS AND ESTERS Download PDF

Info

Publication number
WO1994004654A1
WO1994004654A1 PCT/US1993/007290 US9307290W WO9404654A1 WO 1994004654 A1 WO1994004654 A1 WO 1994004654A1 US 9307290 W US9307290 W US 9307290W WO 9404654 A1 WO9404654 A1 WO 9404654A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
weight
detergent composition
acid
liquid detergent
Prior art date
Application number
PCT/US1993/007290
Other languages
English (en)
French (fr)
Inventor
David William Bjorkquist
Rajan Keskav Panandiker
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP93918607A priority Critical patent/EP0655085B1/en
Priority to JP6506316A priority patent/JPH08500147A/ja
Priority to DE69311557T priority patent/DE69311557T2/de
Priority to AU48003/93A priority patent/AU4800393A/en
Publication of WO1994004654A1 publication Critical patent/WO1994004654A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions

Definitions

  • This invention relates to a liquid detergent composition
  • a liquid detergent composition comprising certain Naminoalkylboronic acids or esters (see compound structure below) as protease inhibitors, protease, and detersive surfactant.
  • Protease-containing liquid detergent compositions are well known.
  • a commonly encountered problem, particularly with heavy duty liquid laundry detergents, is the degradation by protease enzyme of second enzymes in the composition, such as lipase, amylase and cellulase.
  • the performance of the second enzyme upon storage and its stability in product are thus impaired by the presence of protease in the liquid detergent product.
  • Boronic acids are known to reversibly inhibit protease. This inhibition of protease by boronic acid is reversible upon dilution, as occurs in wash water.
  • subtilisin inhibitors Certain boronic acids are cited as subtilisin inhibitors in Phillip, M. and Bender, M.L., "Kinetics of Subtilisin and Thiosubtilisin", Molecular & Cellular Biochemistry, vol. 51, pp. 5-32 (1983), and in Phillip, M. and S. Maripuri, "Inhibition of Subtilisin by Substituted Arylboronic Acids", FEBS Letters, vol. 133(1), pp. 36-38 (October, 1981). Many of these inhibitors, however, are arylboronic acids, which owing to protodeboronation may not be stable under the slightly alkaline conditions found in many liquid detergents.
  • alkylboronic acids particularly those with atoms other than hydrogen on the ⁇ carbon, may not possess the desired stability due to autoxidation as discussed by Johnson, J., Van Campen, M., and Grummitt, 0., Journal of the American Chemical Society, vol. 60, 111-115 (1938).
  • Known synthetic routes to prepare boronic acid compounds have been reviewed by D. Matteson in The Chemistry of the Metal Carbon Bond, vol. 4, chapter 3, pp. 307-409, edited by F. Hartley (1987) and in Tetrahedron, vol. 45, pp. 1859-1885 (1989). Most of the references cited in Matteson's review articles and in the review on the use of catecholborane by C. Lane and G.
  • the present invention relates to a liquid detergent composition
  • a liquid detergent composition comprising: a. from about 0.001 to 10 weight % of a compound or compounds of the following structure: H R2 OH H R2 0
  • Rl Y Rl Y where Rj , R2, and R3 are independent hydrogen or C1-C4 alkyl ;
  • X is aryl , substituted aryl or Ci-C ⁇ al kyl ;
  • Y is selected from the group consisting of hydrogen, amine protecting group, and amino acid, dipeptide or tripeptide l inked through the C-terminal carboxyl ic acid.
  • b from about 0.0001 to 1.0 weight % of active proteolytic enzyme; and c. from about 1 to 80 weight % of detersive surfactant.
  • Rl Y Rl Y where Rj, R2, and R3 are independently hydrogen or C1-C4 alkyl; n is 2-4; X is aryl, substituted aryl or Ci-C ⁇ alkyl; Y is selected from the group consisting of hydrogen, amine protecting group and amino acid, dipeptide or tripeptide linked through the C-terminal carboxylic acid. Suitable amine protecting groups are described in Protecting Groups in Organic Synthesis, by T.W. Greene and P.G.M. Wuts, pp. 309-405, which is incorporated herein by reference. For example, these could include (in order of preference) any one of the following: 0
  • R4 is C1-C4 alkyl, aryl, or substituted aryl.
  • R4 is C1-C4 alkyl, aryl, or substituted aryl.
  • Compounds named ⁇ - ami noalkyl boronic acid or 0-N-peptidylaminoalkylboronic acid or i-i-aminoalkylboronate ester or 0-N-peptidylaminoalkylboronate ester are described herein.
  • Preferred compounds have the following formula:
  • Ri and R2 are independently hydrogen or methyl;
  • X is aryl, substituted aryl, or C1-C4 alkyl; and
  • Y is an amine protecting group selected from the group consisting of t-butoxycarbonyl (BOC), methoxycarbonyl or benzyloxycarbonyl (CBZ), and
  • R5 is phenyl , substituted phenyl or C1-C4 alkyl.
  • Another preferred compound has the same formula as the above, except that Y is 0
  • R5 is phenyl, substituted phenyl or C1-C4 alkyl.
  • composition of matter having serine protease reversible inhibition properties comprising the compound described herein and serine protease (described below).
  • compositions for use as an effective reversible serine protease inhibitor which comprises as an essential ingredient 0-aminoalkylboronic acid or 0-N-peptidylaminoalkylboronic acid in a liquid medium.
  • Also described herein is a method of reversibly inhibiting serine protease including the steps of:
  • Ri and R2 are independently hydrogens or C1-C4 alkyls; and X is aryl, substituted aryl or Ci-C ⁇ alkyl.
  • Ri and R2 are hydrogen and X is aryl or substituted aryl.
  • This invention also includes a process for synthesizing 0-aminoalkylboronate ester, comprising the steps of:
  • a "third step" (c) follows steps (a) and (b) above:
  • the sulfonating agent of step (c) for the boronic acid or boronate ester is preferably sulfonyl chloride of the structure:
  • R4 i s C1 -C4 al kyl , aryl or substituted aryl .
  • the acylating agent of step (c) is preferably acid chloride of the structure: 0
  • R4-C-0H where each R4 is independently C1-C4 alkyl, aryl or substituted aryl
  • the phosphorylating agent of step (c) preferably has the structure: 0
  • R 4 wherein R4 is C1-C4 alkyl, aryl or substituted aryl.
  • This third step can also be done for the boronate ester: (c) reacting the 0-aminoalkylboronate ester with an amino acid or a dipeptide or a tripeptide to form a J-N-peptidylamino- boronate ester.
  • the amino acids are preferably selected from the group consisting of alanine, valine, leucine, isoleucine, phenylalanine, glycine, and threonine. Most preferred are glanine, glycine, leucine, valine and phenylalanine.
  • Dipeptides or tripeptides are preferred over amino acid and preferably comprise amino acids selected from the group consisting of alanine, valine, leucine, isoleucine, phenylalanine, glycine, threonine, and mixtures thereof.
  • Tripeptides are most preferred and are preferably comprised of amino acids selected from the group consisting of alanine, glycine, leucine, valine, phenylalanine, and mixtures thereof.
  • the compounds herein can be prepared in high yield from the requisite trimethylsilylenamine as demonstrated below: X H R2 OH
  • step (d) dissolving the 3-aminoalkylboronic acid hydrobromide salt in water; and after neutralization with sodium hydroxide extracting the ⁇ -aminoalkylboronic acid into an organic solvent.
  • the preferred reaction temperature for step (a) is between room temperature and the boiling point of the solvent, most preferably from about 35 * C to about 45 ⁇ C (the boiling point of methylene chloride).
  • Preferred solvents for the extraction in step (d) above are methylene chloride, diethylether, and chloroform (most preferred).
  • the preferred substituted silylated enamine in step (a) is: R2
  • R8 Si(CH 3 )3 where X is aryl, substituted aryl, or C1-C4 alkyl, and RQ is Si(CH3>3 or CH3.
  • step (a) The most preferred substituted silylated enamine in step (a) is: H
  • protease-containing liquid detergent compositions containing the compounds described above for the reversible inhibition of serine protease, and stabilization of the protease (i.e. proteolytic enzyme) itself or second enzymes in the composition.
  • liquid laundry detergent composition comprising: (a) from about 0.001 to 10 weight % of a compound or compounds of the following structure: H R2 OH H R2 0 1 1 / I I / ⁇
  • Ri, R2, and R3 are independently hydrogen or C1-C4 alkyl; n is 2-4; X is aryl, substituted aryl or C ⁇ -C6 alkyl; Y is selected from the group consisting of hydrogen, amine protecting group, and amino acid, dipeptide or tripeptir? linked through the C-terminal carboxylic acid.
  • liquid detergent composition comprising: (a) from about 0.001 to 10 weight % of 0-aminoalkylboronic acid or 0-aminoalkylboronate ester or 0-N-peptidylaminoalkyl- boronic acid or 0-N-peptidylaminoalkylboronate ester; (b) from about 0.0001 to 1.0 weight % of active proteolytic enzyme; and
  • An essential ingredient in the present liquid detergent compositions is from about 0.0001 to 1.0, preferably about 0.0005 to 0.5, most preferably about 0.002 to 0.1, weight % of active proteolytic enzyme. Mixtures of proteolytic enzyme are also included.
  • the 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. Particularly preferred is bacterial serine proteolytic enzyme obtained from Bacillus subtilis and/or Bacillus licheniformis.
  • Suitable proteolytic enzymes include Alcalase® (Subtilisin Carlesburg), Esperase ® , Savinase® (preferred); Maxatase ® , Maxacal ® (preferred), and Maxapem 15 ® (protein engineered Maxacal ® ); and subtilisin BPN and BPN' (preferred); which are commercially available.
  • Preferred proteolytic enzymes are also 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 re f ers to a modified bacterial serine proteolytic enzyme which is called "Protease A” herein.
  • Preferred proteolytic enzymes are selected from the group consisting of Subtilisin Carlesburg, protease derived from Bacillus lictieniformis. BPN', Protease A and Protease B, and mixtures thereof. Protease B is most preferred.
  • a preferred ingredient in the present liquid compositions is from about 0.0001 to 1.0, preferably 0.001 to 0.5, weight % on an active basis of a detergent-compatible second enzyme.
  • detergent-compatible is meant compatibility with the other ingredients of a liquid detergent composition, such as detersive surfactant and detergency builder.
  • These second enzymes are preferably selected from the group consisting of lipase, amylase, cellulase, and mixtures thereof.
  • the term “second enzyme” excludes the proteolytic enzymes discussed above, so each composition herein contains at least two kinds of enzyme, including at least one proteolytic enzyme.
  • 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 1.0, more preferably 0.001 to 0.5, weight % on an active basis of these second enzymes are preferably used.
  • enzymes from the same class e.g. lipase
  • two or more classes e.g. cellulase and lipase
  • Purified or non-purified forms of the enzyme may be used.
  • Suitable upases for use herein include those of bacterial and fungal origin. Second enzymes from chemically or genetically modified mutants are included.
  • Suitable bacterial Upases include those produced by Pseudomonas. such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034, incorporated herein by reference.
  • Suitable upases include those which show a positive immunological cross-reaction with the antibody of the lipase produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been described in Japanese Patent Application 53-20487, laid open on February 24, 1978, which is incorporated herein by reference.
  • This lipase is available under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.”
  • Mano-P Lipase P
  • Such upases should show a positive immunological cross reaction with the Amano-P antibody, using the standard and well-known immunodiffusion procedure according to Ouchterlony .Acta. Med. Scan.. 133, pages 76-79 (1950)).
  • These upases, and a method for their immunological cross-reaction with Amano-P are also described in U.S. Patent 4,707,291, Thorn et al., issued November 17, 1987, incorporated herein by reference.
  • Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fraqi FERM P 1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitroreducens var. lipolvticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum. e.g. Chromobacter viscosum var. lipolvticum NRRLB 3673, and further Chromobacter viscosum lipases, and lipases ex Pseudomonas gladioli.
  • Other lipases of interest are Amano AKG and Bacillis Sp lipase (e.g., Solvay enzymes).
  • lipases which are of interest where they are detergent-compatible are those described in EP A 0 399 681, published November 28, 1990, EP A 0385 401, published September 5, 1990, EP A 0 218 272, published April 15, 1987, and PCT/DK 88/00177, published May 18, 1989, all incorporated herein by reference.
  • Suitable fungal lipases include those producible by Humicola lanuoinosa and Thermomvces lanuqinosus. Most preferred is lipase obtained by cloning the gene from Humicola lanuoinosa and expressing the gene in Aspergillus orvzae as described in European Patent Application 0 258 068, incorporated herein by reference, commercially available under the trade name Lipolase®.
  • lipase units of lipase per gram (LU/g) of product can be used in these compositions.
  • a lipase unit is that amount of lipase which produces 1 ⁇ mol of titratable butyric acid per minute in a pH stat, where pH is 7.0, temperature is 30 * C, and substrate is an emulsion tributyrin and gum arabic, in the presence of Ca ++ and NaCl in phosphate buffer.
  • Any cellulase suitable for use in a liquid detergent composition can be used in these compositions.
  • Suitable cellulase enzymes for use herein include those of bacterial and fungal origins. Preferably, they will have a pH optimum of between 5 and 9.5. From about 0.0001 to 1.0, preferably 0.001 to 0.5, weight % on an active enzyme basis of cellulase can be used.
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgaard et al ., issued March 6, 1984, incorporated herein by reference, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea.. particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas. and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander). Any a ylase suitable for use in a liquid detergent composition can be used in these compositions.
  • Amylases include, for example, ⁇ -amylases obtained from a special strain of B.Iicheniforms, described in more detail in British Patent Specification No. 1,296,839.
  • a ylolytic proteins include, for example, RapidaseTM, MaxamylTM and TermamylTM.
  • detersive surfactant is the fourth essential ingredient in the present invention.
  • the detersive surfactant can be selected from the group consisting of anionics, nonionics, cationics, ampholytics, zwitterionics, and mixtures thereof. Anionic and nonionic surfactants are preferred.
  • the benefits of the present invention are especially pronounced in compositions containing ingredients that are harsh to enzymes such as certain detergency builders and surfactants.
  • the anionic surfactant comprises C12-C20 alkyl sulfate, C12 to 0 alkyl ether sulfate and Cg to 20 linear alkylbenzene sulfonate. Suitable surfactants are described below.
  • Heavy duty liquid laundry detergents are the preferred liquid detergent compositions herein.
  • the particular surfactants used can vary widely depending upon the particular end-use envisioned. These compositions will most commonly be used for cleaning of laundry, fabrics, textiles, fibers, and hard surfaces.
  • Alkyl sulfate surfactants are a type of anionic surfactant of importance for use herein.
  • Alkyl sulfates have the general formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof
  • alkyl chains of C12-I6 are preferred for lower wash temperatures (e.g., below about 50 * C) and C16-I8 alkyl chains are preferred for higher wash temperatures (e.g., above about 50 * C).
  • Alkyl alkoxylated sulfate surfactants are another category of useful anionic surfactant.
  • surfactants are water soluble salts or acids typically of the formula RO(A) m S ⁇ 3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperydinium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
  • Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl polyethoxylate (2.25) sulfate, C12- 18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium.
  • Other anionic surfactants useful for detersive purposes can also be included in the compositions hereof.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • soap C9-C20 linear alkylbenzenesulphonates, C8-C22 primary or secondary alkanesulphonates, C8-C24 olefinsulphonates, sulphonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succina ates and sulfosuccinates, monoesters of sulfosuccinate (
  • Nonionic Detergent Surfactants Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants are listed below. 1.
  • alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.
  • alkyl phenol alkoxylates e.g., alkyl phenol ethoxylates
  • the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol.
  • Semi-polar nonionic surfactants are a special category of nomonic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms 31 and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
  • R3(0R4) X N(R5) 2 wherein R is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R* is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R ⁇ IS an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include Cio-Ci ⁇ alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • R*> is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each l is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H where x varies from about 1 to about 3.
  • Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
  • the detergent compositions may preferably comprise from about 3 to 50 weight %, most preferably from about 3% to 30%, of the polyhydroxy fatty acid amide.
  • the polyhydroxy fatty acid amide surfactant component comprises compounds of the structural formula: 0 Rl
  • Rl is ri, C1-C4 hydrocarbyl , 2-hydroxy ethyl, 2-hydroxy propyl, or a mixtL"> thereof, preferably C1-C4 alkyl, more preferably Ci or C2 alkyl, most oreferably Ci alkyl (i.e., methyl); and R 2 is a C5-C31 hydrocarbyl, p> 'erably straight chain C7-C19 alkyl or alkenyl, more preferably strai ⁇ n chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH 2 -(CH0H) n -CH 2 0H, -CH(CH 2 0H)-(CH0H) n . 1 -CH 2 0H, -CH 2 -(CHOH)2(CHOR')(CHOH)-CH2 ⁇ H, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ H.
  • R' can be, for example, N-methyl , N-ethyl, N-oropyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy pi «pyl .
  • R 2 -C0-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxyglucityl , 2-deoxyfructityl , 1-deoxymaltityl , 1-deoxylactityl , 1-deoxygalactityl , 1-deoxymannityl , 1-deoxymalto- triotityl, etc.
  • Arnpholytic surfactants can be incorporated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic ⁇ arivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, 5 sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly
  • Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • weight % detergency builder can be included herein.
  • Inorganic as well as organic builders can be used.
  • Inorganic detergency builders include, but are not limited to, the
  • borate-forming materials that can produce borate under detergent storage or wash conditions (hereinafter, collectively “borate builders”), can also be used.
  • non-borate builders are used in the compositions of the invention intended for use at wash conditions less than about 50 ⁇ , 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.
  • 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.
  • other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for 5 oxygen bleaches, and as a component of suds control systems.
  • 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
  • Aluminosilicate builders are useful in the present invention.
  • Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • Aluminosilicate builders include those having the empirical formula:
  • Preferred aluminosilicates are zeolite builders which have the formula:
  • 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 30 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 a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a 35 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.
  • alkali metals such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates.
  • a number of ether polycarboxylates have been disclosed for use as detergent builders.
  • Examples of useful ether polycarboxylates include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and La berti et al . , U.S. Patent 3,635,830, issued January 18, 1972, both of which are incorporated herein by reference.
  • a specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula:
  • TDS tartrate disuccinic acid
  • 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.
  • ether hydroxypolycar- boxylates represented by the structure:
  • n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C1-4 alkyl or C1-4 substituted alkyl (preferably R is hydrogen).
  • Still other ether polycarboxylates include 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, poly aleic 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 of particular importance for heavy duty liquid detergent formulations, but 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.
  • detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28,
  • Useful succinic acid builders include the C5-C20 alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid.
  • Alkyl succinic acids typically are of the general formula
  • R-CH(C00H)CH2(C00H) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably Ci2 _c 16 ° r wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent
  • useful builders also include sodium and potassium carboxymethyloxymalonate, carboxy ethyloxysuccinate, cis-cyclo- hexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water- soluble polyacrylates (these polyacrylates having molecular weights to above about 2,000 can also be : «ffecitvly utilized as dispersants), and the copoly ers of maleic anhydride with vinyl methyl ether or ethylene.
  • suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al .
  • polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
  • 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.
  • soi . release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties.
  • Liquid detergent compositions which contain these compounds typically contain from about 0.01% to 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine.
  • Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986, incorporated herein by reference.
  • Another group of preferred clay soil removal/anti-redeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984, incorporated herein by reference.
  • clay soil removal/anti-redeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985, all of which are incorporated herein by reference.
  • CMC carboxymethylcellulose
  • Polymeric dispersing agents can advantageously be utilized in the compositions hereof. These materials can aid in calcium and magnesium hardness control. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. Suitable polymeric dispersing agents for use herein are described in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, and European Patent Application No. 66915, published December 15, 1982, both incorporated herein by reference. Brightener
  • any suitable optical brighteners or other brightening or whitening agents known in the art can be incorporated into the detergent compositions hereof.
  • optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in The Production and Application of Fluorescent Brightening Agents, M. Zahradnik, published by John Wiley & Sons, New York (1982), the disclosure of which is incorporated herein by reference. Suds Suppressors
  • compositions hereof will generally comprise from 0% to about 5% of suds suppressor.
  • compositions hereof A wide variety of other ingredients useful in detergent compositions can be included in the compositions hereof, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents , for liquid formulations, bleaches, bleach activators, etc.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • the liquid laundry detergent compositions hereof preferably comprise, as the detergency builder, from about 10% to about 18% by weight of a Cio-Cis alkyl monocarboxylic acid, and from about 0.2% to about 10% by weight of citric acid or a salt thereof.
  • compositions preferably comprise from about 1.5% to about 5% ethylenediamine-N-N'-disuccinic acid or alkali metal, alkaline earth, ammonium or substituted ammonium salts thereof, or mixture thereof.
  • the ethylenediamine-N,N'-disuccinic acid compounent is selected from the group consisting of ethylenediamine-N,N'-disuccinic acid free acid; ethylenediamine-N,N'-disuccinic acid potassium salt; ethylenediamine-N,N'-disuccinic acid ammonium salt; and mixtures thereof.
  • Preferred heavy duty liquid laundry detergent compositions hereof will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and 11.0, preferably between about 7.0 and 8.5,
  • compositions herein preferably have a pH in a 10% solution in water at 20'C of between about 6.5 to 11.0, preferably 7.0 to 8.5.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • This invention further provides a method for cleaning substrate, such as fibers, fabrics, hard surfaces, skin, etc., by contacting the substrate, with a liquid detergent composition comprising detersive surfactant, proteolytic enzyme, a detergent-compatible second enzyme (optional), and the compounds described above.
  • a liquid detergent composition comprising detersive surfactant, proteolytic enzyme, a detergent-compatible second enzyme (optional), and the compounds described above.
  • Agitation is preferably provided for enhancing cleaning.
  • Suitable means for providing agitation include rubbing by hand or preferably with use of a brush, sponge, cloth, mop, or other cleaning device, automatic laundry washing machines, automatic dishwashers, etc.
  • Preferred herein are concentrated liquid detergent compositions.
  • compositions will deliver to the wash the same amount of active detersive ingredients at a reduced dosage.
  • Typical regular dosage of heavy duty liquids is 118 milliliters in the U.S. (about 1/2 cup) and 180 milliliters in Europe.
  • Concentrated heavy duty liquids herein contain about 10 to 100 weight % more active detersive ingredients than regular heavy duty liquids, and are dosed at less than 1/2 cup depending upon their active levels. This invention becomes even more useful in concentrated formulations because there are more actives to interfere with enzyme performance.
  • Compound (3) is prepared by the procedure described in Example I.
  • Compound (11) is synthesized by preparing a solution of (3) (2.06g, 12.5mmoles) in diehloromethane (30 ml) and adding ethylene glycol (0.85 g, 13.7 mmoles). The reaction is shaken for 20 minutes at room temperature and then stirred over solid Na2S ⁇ 4. Removal of the volatiles under reduced pressure affords compound (11).
  • Compound (12) is prepared by the sequential addition of compound (11) (1.5 g, 7.85 mmoles) dissolved in diehloromethane (5 ml), CBZ-Ala (1.75g, 7.88 mmoles) dissolved in diehloromethane (5 ml), and triethylamine (1.75 g, 17 mmoles) also dissolved in diehloromethane (5 ml) to a 100 ml round bottom flask containing diehloromethane (50 ml), and fitted with a gas inlet and a septum. While constantly stirring this solution at room temperature under an inert atmosphere, diethyl cyanophosphonate (1.41 g, 8.64 mmoles) is added slowly.
  • Compound (11) is prepared by the procedure described in Example V.
  • Compound (13) is prepared by the sequential addition of compound (11) (1.0 g, 5.2 mmoles) dissolved in diehloromethane (5 ml), CBZ-Gly-Ala (1.70 g, 6.1 mmoles) dissolved in diehloromethane (5ml), and triethylamine (1.35 g, 13.3 mmoles), which is also dissolved in diehloromethane (5 ml), to a 100 ml round bottom flask containing diehloromethane (30 ml), and fitted with a gas inlet and a septum.
  • Compound (14) is prepared by mixing ethylene glycol (0.17 g, 2.7 mmoles) with the boronic acid (13) (1.06 g, 2.5 mmoles) in methylene chloride (10 ml) by a procedure previously described (see Examples V and VI).
  • the ester, compound (14) (1.07 g, 2.4 mmoles) is dissolved in methanol (60 ml) and placed in a pressure vessel.
  • 10% Palladium on carbon (0.21g) and the vessel is agitated under 50 psi hydrogen for 3 hours at room temperature. After this, the catalyst is removed by filtration and the solvent by heating under reduced pressure. The residue is purified by silica gel chromatography to afford compound (15).
  • Compound (16) is prepared by the sequential addition of compound (15) (0.65 g, 2.0 mmoles) dissolved in diehloromethane (5 ml), N-MOC-Phe (0.48g, 2.2 mmoles) dissolved in diehloromethane (5 ml), and triethylamine (0.52 g, 5.15 mmoles) also dissolved in diehloromethane (5 ml) to a 100 ml round bottom flask containing diehloromethane (50 ml), and fitted with a gas inlet and a septum. While constantly stirring this solution at room temperature under an inert atmosphere, diethylcyanophosphonate (0.42 g, 2.6 mmoles) is added slowly.
  • a liquid laundry detergent base matrix is prepared as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
PCT/US1993/007290 1992-08-14 1993-08-03 LIQUID DETERGENT COMPOSITIONS CONTAINING PROTEASE AND CERTAIN β-AMINOALKYLBORONIC ACIDS AND ESTERS WO1994004654A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP93918607A EP0655085B1 (en) 1992-08-14 1993-08-03 Liquid detergent compositions containing protease and certain beta-aminoalkylboronic acids and esters
JP6506316A JPH08500147A (ja) 1992-08-14 1993-08-03 プロテアーゼおよび特定のβ‐アミノアルキルボロニン酸およびエステルを含有する液体洗剤組成物
DE69311557T DE69311557T2 (de) 1992-08-14 1993-08-03 Protease und bestimmte beta-aminoalkylboronsauren oder -ester enthaltende flussigwaschmittel
AU48003/93A AU4800393A (en) 1992-08-14 1993-08-03 Liquid detergent compositions containing protease and certain beta -aminoalkylboronic acids and esters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/931,190 1992-08-14
US07/931,190 US5354491A (en) 1992-08-14 1992-08-14 Liquid detergent compositions containing protease and certain β-aminoalkylboronic acids and esters

Publications (1)

Publication Number Publication Date
WO1994004654A1 true WO1994004654A1 (en) 1994-03-03

Family

ID=25460354

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/007290 WO1994004654A1 (en) 1992-08-14 1993-08-03 LIQUID DETERGENT COMPOSITIONS CONTAINING PROTEASE AND CERTAIN β-AMINOALKYLBORONIC ACIDS AND ESTERS

Country Status (11)

Country Link
US (1) US5354491A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
EP (1) EP0655085B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPH08500147A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CN (1) CN1041435C (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AU (1) AU4800393A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE69311557T2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ES (1) ES2102668T3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
MX (1) MX9304972A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
PH (1) PH30151A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
TW (1) TW250495B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1994004654A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2264137A1 (en) 2008-01-04 2010-12-22 The Procter and Gamble Company A laundry detergent composition comprising glycosyl hydrolase
WO2011005730A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
WO2011005913A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
EP2365053A1 (en) 2010-03-12 2011-09-14 The Procter & Gamble Company Liquid detergent compositions comprising pH tuneable amido-gellants, and processes for making
EP2365051A1 (en) 2010-03-12 2011-09-14 The Procter & Gamble Company Fluid detergent compositions comprising a di-amido gellant, and process for making
WO2013016371A1 (en) 2011-07-25 2013-01-31 The Procter & Gamble Company Detergents having acceptable color
WO2013039963A1 (en) 2011-09-13 2013-03-21 The Procter & Gamble Company Microcapsule compositions comprising ph tuneable di-amido gellants
EP2716644A1 (en) 2012-10-03 2014-04-09 The Procter and Gamble Company A stable enzyme stabilizer premix
WO2014152674A1 (en) 2013-03-14 2014-09-25 Novozymes A/S Enzyme and inhibitor containing water-soluble films
WO2016001319A1 (en) 2014-07-03 2016-01-07 Novozymes A/S Improved stabilization of non-protease enzyme
EP3067410A2 (en) 2008-02-15 2016-09-14 The Procter and Gamble Company Cleaning compositions
WO2017066510A1 (en) 2015-10-14 2017-04-20 Novozymes A/S Cleaning of water filtration membranes
WO2018202846A1 (en) 2017-05-05 2018-11-08 Novozymes A/S Compositions comprising lipase and sulfite
EP3404088A1 (en) 2008-06-06 2018-11-21 The Procter & Gamble Company Detergent composition comprising a variant of a family 44 xyloglucanase
WO2019002356A1 (en) 2017-06-30 2019-01-03 Novozymes A/S ENZYMATIC SUSPENSION COMPOSITION
EP3461881A1 (en) 2013-05-03 2019-04-03 Novozymes A/S Microencapsulation of detergent enzymes
WO2019086530A1 (en) 2017-11-01 2019-05-09 Novozymes A/S Polypeptides and compositions comprising such polypeptides
WO2019086528A1 (en) 2017-11-01 2019-05-09 Novozymes A/S Polypeptides and compositions comprising such polypeptides
WO2019175240A1 (en) 2018-03-13 2019-09-19 Novozymes A/S Microencapsulation using amino sugar oligomers
EP3647398A1 (en) 2018-10-31 2020-05-06 Henkel AG & Co. KGaA Cleaning compositions containing dispersins v
EP3647397A1 (en) 2018-10-31 2020-05-06 Henkel AG & Co. KGaA Cleaning compositions containing dispersins iv
EP3741848A2 (en) 2014-12-19 2020-11-25 Novozymes A/S Protease variants and polynucleotides encoding same
WO2021123307A2 (en) 2019-12-20 2021-06-24 Novozymes A/S Polypeptides having proteolytic activity and use thereof
EP3950939A2 (en) 2015-07-06 2022-02-09 Novozymes A/S Lipase variants and polynucleotides encoding same
WO2022189521A1 (en) 2021-03-12 2022-09-15 Novozymes A/S Polypeptide variants
WO2024131880A2 (en) 2022-12-23 2024-06-27 Novozymes A/S Detergent composition comprising catalase and amylase

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69217935T2 (de) * 1992-08-14 1997-10-09 Procter & Gamble Alpha-aminoborsäurehaltige flüssige Waschmittel
AU7121394A (en) * 1993-07-09 1995-02-06 Borax Consolidated Ltd Boronic acid or borinic acid derivatives as enzyme stabilizers
US5834415A (en) * 1994-04-26 1998-11-10 Novo Nordisk A/S Naphthalene boronic acids
US5565135A (en) * 1995-01-24 1996-10-15 The Procter & Gamble Company Highly aqueous, cost effective liquid detergent compositions
AU6188096A (en) * 1995-06-13 1997-01-09 Novo Nordisk A/S 4-substituted-phenyl-boronic acids as enzyme stabilizers
MX9800749A (es) * 1996-06-19 1998-04-30 Procter & Gamble Composiciones detergentes que comprenden una amilasa especifica y una proteasa.
EP0814167A1 (en) * 1996-06-21 1997-12-29 Kabushiki Kaisha Kyoto Daiichi Kagaku A method for measuring the concentration of protease inhibitors, kit for use in such a method and method for dissolving a sunstrate
US5770552A (en) * 1997-03-13 1998-06-23 Milliken Research Corporation Laundry detergent composition containing poly(oxyalkylene)-substituted reactive dye colorant
JP3626982B2 (ja) * 1997-08-29 2005-03-09 アークレイ株式会社 タンパク質分解酵素阻害物質の測定方法およびそれに用いる測定キット
US6995124B1 (en) 1998-10-24 2006-02-07 The Procter & Gamble Company Methods for laundering delicate garments in a washing machine
US7185380B2 (en) * 1998-10-24 2007-03-06 The Procter & Gamble Company Methods for laundering delicate garments in a washing machine comprising a woven acrylic coated polyester garment container
US6966696B1 (en) 1998-10-24 2005-11-22 The Procter & Gamble Company Methods for laundering delicate garments in a washing machine
US6699831B2 (en) * 2000-06-07 2004-03-02 Kao Corporation Liquid detergent composition comprising aluminosilicate or crystalline silicate
US20070118998A1 (en) * 2000-08-25 2007-05-31 The Procter & Gamble Company Methods for laundering delicate garments in a washing machine
MXPA04004479A (es) * 2001-11-13 2004-08-11 Procter & Gamble Composiciones topicas que contienen enzimas estabilizadas con inhibidores.
CN102343233A (zh) * 2011-07-31 2012-02-08 韶关市广化科技有限公司 一种多功能环保型硼酸酯表面活性剂的制备方法
AP3789A (en) * 2012-06-13 2016-08-31 Novozymes As Laundry soap bars.
CN108774600B (zh) * 2018-07-24 2020-08-07 山东威高药业股份有限公司 一种内镜清洗保湿剂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0371467A2 (de) * 1988-12-01 1990-06-06 Hoechst Aktiengesellschaft Beta-Amino-Boronsäure-Derivate
EP0478050A1 (en) * 1990-09-24 1992-04-01 Unilever N.V. Detergent composition
WO1992019707A1 (en) * 1991-04-30 1992-11-12 The Procter & Gamble Company Liquid detergents with an aryl boronic acid

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912595A (en) * 1974-02-25 1975-10-14 Us Health Method of purifying enzymes using boronic acids covalently bonded to an insoluble support
US4537707A (en) * 1984-05-14 1985-08-27 The Procter & Gamble Company Liquid detergents containing boric acid and formate to stabilize enzymes
US5187157A (en) * 1987-06-05 1993-02-16 Du Pont Merck Pharmaceutical Company Peptide boronic acid inhibitors of trypsin-like proteases
US4797977A (en) * 1988-05-11 1989-01-17 General Felt Industries, Inc. Picker assembly
AU4724989A (en) * 1988-12-30 1990-07-05 Unilever Plc Enzymatic liquid detergent composition
US5639446A (en) * 1996-09-20 1997-06-17 3V Inc. Derivatives of benzoxazole useful as UV stabilizers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0371467A2 (de) * 1988-12-01 1990-06-06 Hoechst Aktiengesellschaft Beta-Amino-Boronsäure-Derivate
EP0478050A1 (en) * 1990-09-24 1992-04-01 Unilever N.V. Detergent composition
WO1992019707A1 (en) * 1991-04-30 1992-11-12 The Procter & Gamble Company Liquid detergents with an aryl boronic acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
D.N. BUTLER ET AL.: "Synthesis of Functionally Substituted Alkylboronic Acids. Hydroboration of N-Alkenylureas and -carbamates", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 88, no. 3, 5 February 1966 (1966-02-05), pages 484 - 487 *

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2264137A1 (en) 2008-01-04 2010-12-22 The Procter and Gamble Company A laundry detergent composition comprising glycosyl hydrolase
EP3067410A2 (en) 2008-02-15 2016-09-14 The Procter and Gamble Company Cleaning compositions
EP4545638A2 (en) 2008-06-06 2025-04-30 The Procter & Gamble Company Detergent composition comprising a variant of a family 44 xyloglucanase
EP3404088A1 (en) 2008-06-06 2018-11-21 The Procter & Gamble Company Detergent composition comprising a variant of a family 44 xyloglucanase
WO2011005730A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
WO2011005913A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
EP2365053A1 (en) 2010-03-12 2011-09-14 The Procter & Gamble Company Liquid detergent compositions comprising pH tuneable amido-gellants, and processes for making
EP2365051A1 (en) 2010-03-12 2011-09-14 The Procter & Gamble Company Fluid detergent compositions comprising a di-amido gellant, and process for making
WO2011112886A1 (en) 2010-03-12 2011-09-15 The Procter & Gamble Company Fluid detergent compositions comprising a di-amido gellant, and processes for making
WO2011112910A1 (en) 2010-03-12 2011-09-15 The Procter & Gamble Company Liquid detergent compositions comprising ph tuneable amido-gellants, and processes for making
WO2013016371A1 (en) 2011-07-25 2013-01-31 The Procter & Gamble Company Detergents having acceptable color
WO2013039963A1 (en) 2011-09-13 2013-03-21 The Procter & Gamble Company Microcapsule compositions comprising ph tuneable di-amido gellants
WO2014055641A1 (en) 2012-10-03 2014-04-10 The Procter & Gamble Company A stable enzyme stabilizer premix
EP2716644A1 (en) 2012-10-03 2014-04-09 The Procter and Gamble Company A stable enzyme stabilizer premix
WO2014152674A1 (en) 2013-03-14 2014-09-25 Novozymes A/S Enzyme and inhibitor containing water-soluble films
EP3461881A1 (en) 2013-05-03 2019-04-03 Novozymes A/S Microencapsulation of detergent enzymes
WO2016001319A1 (en) 2014-07-03 2016-01-07 Novozymes A/S Improved stabilization of non-protease enzyme
EP3741848A2 (en) 2014-12-19 2020-11-25 Novozymes A/S Protease variants and polynucleotides encoding same
EP3950939A2 (en) 2015-07-06 2022-02-09 Novozymes A/S Lipase variants and polynucleotides encoding same
WO2017066510A1 (en) 2015-10-14 2017-04-20 Novozymes A/S Cleaning of water filtration membranes
WO2018202846A1 (en) 2017-05-05 2018-11-08 Novozymes A/S Compositions comprising lipase and sulfite
WO2019002356A1 (en) 2017-06-30 2019-01-03 Novozymes A/S ENZYMATIC SUSPENSION COMPOSITION
WO2019086528A1 (en) 2017-11-01 2019-05-09 Novozymes A/S Polypeptides and compositions comprising such polypeptides
WO2019086530A1 (en) 2017-11-01 2019-05-09 Novozymes A/S Polypeptides and compositions comprising such polypeptides
EP4379029A1 (en) 2017-11-01 2024-06-05 Novozymes A/S Polypeptides and compositions comprising such polypeptides
WO2019175240A1 (en) 2018-03-13 2019-09-19 Novozymes A/S Microencapsulation using amino sugar oligomers
EP3647398A1 (en) 2018-10-31 2020-05-06 Henkel AG & Co. KGaA Cleaning compositions containing dispersins v
WO2020088958A1 (en) 2018-10-31 2020-05-07 Henkel Ag & Co. Kgaa Cleaning compositions containing dispersins v
WO2020088957A1 (en) 2018-10-31 2020-05-07 Henkel Ag & Co. Kgaa Cleaning compositions containing dispersins iv
EP3647397A1 (en) 2018-10-31 2020-05-06 Henkel AG & Co. KGaA Cleaning compositions containing dispersins iv
WO2021123307A2 (en) 2019-12-20 2021-06-24 Novozymes A/S Polypeptides having proteolytic activity and use thereof
WO2022189521A1 (en) 2021-03-12 2022-09-15 Novozymes A/S Polypeptide variants
WO2024131880A2 (en) 2022-12-23 2024-06-27 Novozymes A/S Detergent composition comprising catalase and amylase

Also Published As

Publication number Publication date
US5354491A (en) 1994-10-11
DE69311557T2 (de) 1998-02-05
MX9304972A (es) 1994-05-31
ES2102668T3 (es) 1997-08-01
CN1087671A (zh) 1994-06-08
CN1041435C (zh) 1998-12-30
AU4800393A (en) 1994-03-15
EP0655085B1 (en) 1997-06-11
TW250495B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1995-07-01
PH30151A (en) 1997-01-21
JPH08500147A (ja) 1996-01-09
DE69311557D1 (de) 1997-07-17
EP0655085A1 (en) 1995-05-31

Similar Documents

Publication Publication Date Title
EP0655085B1 (en) Liquid detergent compositions containing protease and certain beta-aminoalkylboronic acids and esters
EP0655067B1 (en) Beta-aminoalkyl and beta-n-peptidylaminoalkyl boronic acids
US5431842A (en) Liquid detergents with ortho-substituted phenylboronic acids for inhibition of proteolytic enzyme
EP0583383B1 (en) Liquid detergents with an aryl boronic acid
US6162783A (en) Liquid detergents containing proteolytic enzyme and protease inhibitors
US5580486A (en) Liquid detergents containing an α-amino boronic acid
US5468414A (en) Built liquid detergents with boric-polyol complex to inhibit proteolytic enzyme
WO1994004651A1 (en) Liquid detergents containing a peptide aldehyde
EP0511456A1 (en) Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme
US5422030A (en) Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme
WO1998013458A1 (en) Liquid detergents containing proteolytic enzyme and protease inhibitors
EP0929639A1 (en) Liquid detergents containing proteolytic enzyme, peptide aldehyde and calcium ions
US6165966A (en) Liquid detergents containing proteolytic enzyme and protease inhibitors
EP0583535B1 (en) Liquid detergents containing a peptide trifluoromethyl ketone
EP0655068B1 (en) Process for synthesizing a beta-aminoalkylboronic acid and ester thereof
US5576283A (en) Liquid detergents containing a peptide aldehyde
US5840678A (en) Liquid detergents containing a peptide trifluoromethyl ketone

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CZ JP KR PL SK

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1993918607

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1993918607

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA

WWG Wipo information: grant in national office

Ref document number: 1993918607

Country of ref document: EP