EP1000137B1 - Lessive contenant de la glucanase - Google Patents

Lessive contenant de la glucanase Download PDF

Info

Publication number
EP1000137B1
EP1000137B1 EP98943763A EP98943763A EP1000137B1 EP 1000137 B1 EP1000137 B1 EP 1000137B1 EP 98943763 A EP98943763 A EP 98943763A EP 98943763 A EP98943763 A EP 98943763A EP 1000137 B1 EP1000137 B1 EP 1000137B1
Authority
EP
European Patent Office
Prior art keywords
acid
glucanase
weight
detergent
agents
Prior art date
Legal status (The legal status 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 status listed.)
Revoked
Application number
EP98943763A
Other languages
German (de)
English (en)
Other versions
EP1000137A1 (fr
Inventor
Beatrix Kottwitz
Karl-Heinz Maurer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7837327&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1000137(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1000137A1 publication Critical patent/EP1000137A1/fr
Application granted granted Critical
Publication of EP1000137B1 publication Critical patent/EP1000137B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609Protease or amylase in solid compositions only
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38636Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618Protease or amylase in liquid compositions only
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/12Soft surfaces, e.g. textile

Definitions

  • the present invention relates to detergents used to increase their Cleaning performance included ⁇ -glucanase.
  • Enzymes especially proteases, lipases and cellulases, but also amylases can be found extensive use in detergents, washing aids and cleaning agents.
  • proteases, Lipases or amylases are primarily used for the removal of protein, fat or Starch soiling used.
  • a side effect of the dismantling of Cellulose fibrils through cellulases is the deepening of the optical color impression So-called color refreshment, which occurs in the treatment of dyed cotton textiles with cellulases when the resulting from fiber damage, from the Undyed fibrils originating from the fibers can be removed.
  • polysaccharide stains The problem with polysaccharide stains is that naturally occurring polysaccharides, such as those found in foods are included, usually not consist exclusively of starch, but also contain other or otherwise linked saccharides. While for use ⁇ -Amylases provided in detergents are generally very suitable Starch content of polysaccharide stains in water-soluble oligosaccharides hydrolyze, their dirt removal ability may not be sufficient be felt when it comes to soiling from other polysaccharides acts or these make up larger parts of the polysaccharide stains.
  • EP 709 452 A1 describes a xylanase-containing cleaning agent which, as one of numerous other enzymes which can optionally be used additionally, can also contain ⁇ -glucanases.
  • agents are claimed without further elaboration, which, in addition to lipases, can optionally also contain ⁇ -glucanases.
  • EP 747 470 A1 discloses cleaning agents with keratanases, ie proteoglycan-cleaving enzymes, which can optionally also contain ⁇ -glucanases.
  • EP 756 000 A1 discloses washing or cleaning agents which can contain a combination of amylases and certain surfactants and also, as optional constituents, ⁇ -glucanases.
  • washing and Detergents described the plant cell wall-degrading enzymes can also contain lichenases.
  • lichenases from Bacillus species are preferred.
  • a method of determining the ⁇ -glucan-cleaving activity specified which is based on a measurement of the viscosity reduction. Described specifically means with 2.25, 4.5 and 112 of the units of ⁇ -glucanolytic defined in this way Activity per ml of the wash liquor obtained or acting solution.
  • the object of the invention is for the use in laundry suitable detergent, which in addition to usual with this enzyme-compatible ingredients contains a ⁇ -glucanase, whereby there is a glucanolytic activity due to this enzyme is in the range of 0.05 U / g to 1 U / g has.
  • Enzymes from the class of endo-1,3-1,4- ⁇ -D-glucan-4-glucanohydrolases (EC 3.2.1.73; lichenases ) are to be referred to here as ⁇ -glucanases.
  • Endo-1,3- ⁇ -D-glucosidases (EC 3.2.1.39; laminarinases ) are also considered to be ⁇ -glucanases in the sense of the invention.
  • ⁇ -glucanases split mixed glucans, which are linked alternately in 1,3- and 1,4- ⁇ -glucosidic bonds, into oligosaccharides. Such polymeric mixed glucans are contained in different proportions in practically all cereal products.
  • Enzymes which are able to cleave them have so far been used primarily in the food, beverage and animal feed industries, the textile industry and starch processing (R. Borriss, " ⁇ -glucan-cleaving enzymes", in H. Ruttloff, "Industrial Enzymes ", Chapter 11.5, Behr's Verlag, Hamburg, 1994).
  • ⁇ -glucanases are niger microorganisms, for example Achromobacter lunatus, Arthrobacter luteus, Aspergillus aculeatus, Aspergillus, Bacillus subtilis, Bacillus amyloliquefaciens, Disporotrichum dimorphosporum, Humicola insolens, Penicillium emersonii, Penicillium funiculosum or Trichoderma reesei available.
  • a commercially available product is offered, for example, under the name Cereflo® (manufacturer: Novo Nordisk A / S).
  • the preferred ⁇ -glucanases include an enzyme obtainable from Bacillus alkalophilus (DSM 9956) , which is the subject of German patent application DE 197 32 751.
  • ⁇ -glucanase is preferably incorporated into agents according to the invention in amounts such that they have glucanolytic activities in the range from 0.06 U / g to 0.25 U / g.
  • the determination of glucanolytic activity is based on modifications by M. Lever in Anal. Biochem. 47 (1972), 273-279 and Anal. Biochem. 81 (1977), 21-27.
  • a 0.5% by weight solution of ⁇ -glucan (Sigma no. G6513) in 50 mM glycine buffer (pH 9.0) is used for this. 250 ⁇ l of this solution are added to 250 ⁇ l of a solution containing the agent to be tested for glucanolytic activity and incubated at 40 ° C. for 30 minutes.
  • PAHBAH p-hydroxybenzoic acid hydrazide
  • ⁇ -glucanase in one Activity from 0.2 U / l to 4 U / l, in particular from 0.25 V / l to 1 U / l in an aqueous Solution for removing polysaccharide stains on textiles and a Process for removing polysaccharide stains from textiles by the Use of ⁇ -glucanase in the same activity area.
  • the ⁇ -glucanase alone or as a component of a laundry pretreatment agent, in the sense of a Pre-treatment step before washing textiles with polysaccharide stains contaminated textiles are applied.
  • the ⁇ -glucanase is preferably used however, as part of an aqueous cleaning solution, which is also customary Ingredients of wash liquors can be used.
  • aqueous cleaning solution which is also customary Ingredients of wash liquors can be used.
  • glucanolytic Activities in the range of 0.25 U / l to 1 U / l in the aqueous cleaning solution prefers.
  • machine washing processes for example the usual Household laundry using washing machines, must do the above glucanolytic activities are not maintained throughout the wash cycle remain to achieve the desired washing result, as long as it is guaranteed that at least for a short time, for example over 5 to 20 minutes, a glucanolytic Activity occurs in the area mentioned.
  • ⁇ -glucanase can be used especially in particulate agents such as in European patent EP 0 564 476 or in international patent applications WO 94/23005 for other enzymes described, adsorbed on carriers and / or be embedded in coating substances. to prevent them from premature inactivation protect.
  • amylase can be completely dispensed with without sacrificing cleaning performance against polysaccharide stains, which at least partially consist of starch, suffers.
  • a detergent according to the invention preferably contains at least one protease in addition to ⁇ -glucanase.
  • An agent according to the invention in particular has a proteolytic activity in the range from about 100 PE / g to about 7500 PE / g, in particular 500 PE / g to 5000 PE / g. Protease activity is determined according to the standardized procedure described below, as in Tenside 7 (1970).
  • a solution containing 12 g / l casein and 30 mM sodium tripolyphosphate in water with a degree of hardness of 15 ° dH (containing 0.058% by weight CaCl 2 .2H 2 O, 0.028% by weight MgCl 2 6H 2 O and 0.042% by weight NaHCO 3 ) is heated to 70 ° C., the pH is adjusted to 8.5 at 50 ° C. by adding 0.1 N NaOH. 200 ml of a solution of the agent to be tested for proteolytic activity in 2% by weight sodium tripolyphosphate buffer solution (pH 8.5) are added to 600 ml of the substrate solution. The reaction mixture is incubated at 50 ° C for 15 minutes.
  • the reaction is then stopped by adding 500 ml of TCA solution (0.44 M trichloroacetic acid and 0.22 M sodium acetate in 3% acetic acid by volume) and cooling (ice bath at 0 ° C., 15 minutes).
  • TCA-insoluble protein is removed by centrifugation, 900 ml of the supernatant are diluted with 300 ml of 2N NaOH.
  • the absorption of this solution at 290 nm is determined with the aid of an absorption spectrometer, the zero absorption value being obtained by measuring a centrifuged solution which is prepared by mixing 600 ml of the above-mentioned TCA solution with 600 ml of the above-mentioned substrate solution and then adding the enzyme solution determine is.
  • proteolytic activity of a solution which causes an absorption of 0.500 units of optical density (extinction difference compared to the zero value) under the specified measurement conditions, is defined as 10 PE (protease units) per ml.
  • the proteases preferably used in agents according to the invention include the enzymes known from international patent applications WO 91/02792, WO 92/21760 and WO 95/23221.
  • the detergents according to the invention which are in particular powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions can in principle all except the ⁇ -glucanase used according to the invention contain known and common ingredients in such agents.
  • the invention Agents can in particular builder substances, surface-active surfactants, Bleaching agents based on organic and / or in particular inorganic peroxygen compounds, Bleach activators, water-miscible organic solvents, additional Enzymes, sequestering agents, electrolytes, pH regulators and / or other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, as well as dyes and fragrances.
  • the agents according to the invention can contain one or more surfactants, wherein in particular anionic surfactants, nonionic surfactants and mixtures thereof come.
  • Suitable nonionic surfactants are especially alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched Alcohols each with 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10 alkyl ether groups.
  • Suitable anionic surfactants are in particular soaps and those containing sulfate or Contain sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be in a form which is not completely neutralized be used.
  • the surfactants of the sulfate type include the salts of Sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the sulfonate type surfactants that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkane sulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are involved in the implementation Corresponding monoolefins with sulfur trioxide are formed, as well as ⁇ -sulfofatty acid esters. which result from the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are present in the detergents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid and ethylenediaminephosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as the monomer, and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers can be produced in particular by processes. which are described in German patents DE 42 21 381 and DE 43 00 772, and generally have a relative molecular weight between 1,000 and 200,000. Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builder substances can, if desired, in amounts up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight be included. Amounts close to the above upper limit are preferably in paste-like or liquid, in particular water-containing, agents according to the invention used.
  • Alkali silicates in particular come as water-soluble inorganic builder materials and polymeric alkali phosphates, which in the form of their alkaline, neutral or acidic sodium or potassium salts can be considered.
  • Examples include tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate and the corresponding potassium salts respectively Mixtures of sodium and potassium salts.
  • water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid agents used in particular from 1 wt .-% to 5 wt .-%.
  • crystalline sodium aluminosilicates in detergent quality in particular zeolite A, P and optionally X. preferred.
  • Quantities will be close to the upper limit preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and exist preferably at least 80% by weight of particles with a size below 10 ⁇ m. you Calcium-binding capacity. that according to the information in German patent DE 24 12 837 can usually be determined is in the range of 100 to 200 mg CaO per Grams.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Crystalline phyllosilicates of the general formula Na 2 Si x O 2x + 1 .yH 2 O are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O
  • ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171.
  • ⁇ -sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Also made from amorphous alkali silicates.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention.
  • a granular compound of alkali silicate and alkali carbonate is used, as described, for example, in international patent application WO 95/22592 or as is commercially available, for example, under the name Nabion® 15.
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • Builder substances in the detergents according to the invention are preferably in Amounts up to 60 wt .-%, in particular from 5 wt .-% to 40 wt .-%, contain.
  • Organic peracids in particular come as suitable peroxygen compounds peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and among Washing or cleaning conditions Hydrogen peroxide-releasing inorganic Salts such as perborate, percarbonate and / or persilicate. Hydrogen peroxide can also use an enzymatic system, that is an oxidase and its substrate. be generated. Provided solid peroxygen compounds should be used. can be used in the form of powders or granules become. which can also be encased in a manner known in principle.
  • alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate is preferred or hydrogen peroxide in the form of aqueous solutions containing 3% by weight Contain 10 wt .-% hydrogen peroxide used.
  • an inventive Detergent contains peroxygen compounds, these are preferred in amounts of up to 50% by weight, in particular from 5% by weight to 30% by weight, is present.
  • bleach stabilizers such as phosphonates, Borates or metaborates and metasilicates as well as magnesium salts like magnesium sulfate may be useful.
  • bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms. especially 2 up to 4 carbon atoms, and / or optionally substituted perbenzoic acid, be used.
  • Substances containing the O- and / or N-acyl groups are suitable mentioned number of carbon atoms and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED).
  • acylated triazine derivatives especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, Ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German Patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well acetylated sorbitol and mannitol
  • the transition metal compounds in question include in particular known from the German patent application DE 195 29 905 manganese, iron, Cobalt, ruthenium or molybdenum salt complexes and those from the German Patent application DE 196 20 267 known N-analog compounds, which from the German Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum-carbonyl complexes, which are described in German patent application DE 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, - vanadium and Copper complexes with nitrogenous tripod ligands.
  • Combinations of bleach activators and transition metal bleach catalysts are for example from the German patent application DE 196 13 103 and the international patent application WO 95/27775 are known.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V. Ti and / or Ru are used in conventional amounts, preferably in one Amount up to 1 wt .-%, in particular from 0.0025 wt .-% to 0.25 wt .-% and particularly preferably from 0.01% by weight to 0.1% by weight. each based on the whole Medium. used.
  • the enzymes which can be used in the compositions are and the above-mentioned oxidase from the class of proteases, lipases, Cutinases, amylases, pullulanases, cellulases, hemicellulases, xylanases and Peroxidases and mixtures thereof, for example proteases such as Subtilisin BPN ', Properase®, BLAP®, Optimase®, Opticlean®, Maxatase®, Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym®, Everlase® and / or Purafect® G or OxP, amylases such as BAN®, Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lum
  • fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia obtained enzymatic Agents.
  • These optionally additionally used enzymes can also be used, such as Example in European patent specification EP 0 564 476 or in international patent applications WO 94/23005 described, adsorbed on carriers and / or in Envelope substances are embedded to protect them against premature inactivation.
  • the detergents according to the invention preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, with particular preference being given enzymes stabilized against oxidative degradation, such as from international Patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known, can be used.
  • the detergent can be free of amylase or at least contains as much as possible small amounts of amylase as it is usually by using the ⁇ -glucanase it is also possible to remove stains that are amylolytically removable, essentially without loss of performance of textiles.
  • usable organic solvents include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol. Diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and their mixtures and the ethers derived from the compound classes mentioned.
  • water-miscible solvents are in the detergents according to the invention preferably in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents according to the invention cannot be systemic and environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, malic acid, Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, however also mineral acids, especially sulfuric acid, or bases, especially ammonium or Alkali hydroxides included.
  • Such pH regulators are in the invention Average preferably not more than 20 wt .-%, in particular from 1.2 wt .-% to 17% by weight.
  • suitable color transfer inhibitors in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinyl pyrrolidone with vinyl imidazole.
  • Graying inhibitors have the task of being of the hard surface and especially to keep dirt detached from the textile fibers suspended in the liquor.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example Starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or the cellulose or salts of acidic sulfuric acid esters of cellulose or Strength.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose suitable.
  • starch derivatives other than those mentioned above can be used, for example aldehyde starches.
  • Cellulose ethers such as Carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ether, such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, for example in amounts of 0.1 to 5% by weight, based on the funds. used.
  • the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain.
  • diaminostilbenedisulfonic acid or whose alkali metal salts contain.
  • Brighteners of the type of substituted diphenylstyryls may be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned optical Brighteners can be used.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes.
  • the foam inhibitors are preferably, in particular silicone and / or paraffin-containing foam inhibitors. bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.
  • the preparation of solid agents according to the invention is not difficult and can be carried out in a known manner, for example by spray drying or granulation, the ⁇ -glucanase and optionally further enzymes and any other thermally sensitive ingredients such as bleaching agents optionally being added separately later.
  • agents according to the invention with increased bulk density, in particular in the range from 650 g / l to 950 g / l, a method known from European patent EP 486 592 and having an extrusion step is preferred.
  • a further preferred production using a granulation process is described in European patent EP 0 642 576.
  • Liquid or pasty detergents according to the invention in the form of solutions containing conventional solvents are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • the agents according to the invention are each directly comparable composite agents not according to the invention in cleaning performance are significantly superior.

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)
  • Enzymes And Modification Thereof (AREA)

Claims (10)

  1. Lessive contenant, outre les constituants usuels compatibles avec cette enzyme, une β-glucanase, ce qui a pour effet de lui conférer une activité glucanolytique située dans l'intervalle de 0,05 U/g à 1 U/g.
  2. Lessive selon la revendication 1, caractérisée en ce qu'elle présente une activité glucanolytique située dans l'intervalle de 0,06 U/g à 0,25 U/g.
  3. Lessive selon la revendication 1 ou 2, caractérisée en ce qu'elle contient une β-glucanase que l'on peut obtenir à partir de Bacillus alkalophilus (DSM 9956).
  4. Lessive selon une des revendications 1 à 3, caractérisée en ce qu'elle contient en plus de la β-glucanase, au moins une protéase.
  5. Lessive selon la revendication 4, caractérisée en ce qu'elle présente une activité protéolytique située dans l'intervalle de 100 UP/g à 7500 UP/g, en particulier de 500 UP/g à 5000 UP/g.
  6. Lessive selon une des revendications 1 à 5, caractérisée en ce qu'elle est exempte d'amylase.
  7. Utilisation de β-glucanase présentant une activité de 0,2 U/l à 4 U/l, en particulier de 0,25 U/l à 1 U/l dans une solution aqueuse pour éliminer les salissures à base de polysaccharides sur les textiles.
  8. Procédé pour éliminer les salissures à base de polysaccharides sur les textiles, caractérisé en ce que l'on utilise de la β-glucanase présentant une activité de 0,2 U/l à 4 U/l, en particulier de 0,25 U/l à 1 U/l dans une solution aqueuse.
  9. Procédé selon la revendication 8, caractérisé en ce que l'on utilise une β-glucanase comme constituant d'une solution nettoyante aqueuse, qui peut contenir en plus les constituants usuels de lessives.
  10. Procédé selon la revendication 9, caractérisé en ce que la solution nettoyante aqueuse présente une activité glucanolytique située dans l'intervalle de 0,25 U/l à 1 U/l.
EP98943763A 1997-07-30 1998-07-21 Lessive contenant de la glucanase Revoked EP1000137B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19732749 1997-07-30
DE19732749A DE19732749A1 (de) 1997-07-30 1997-07-30 Glucanasehaltiges Waschmittel
PCT/EP1998/004578 WO1999006516A1 (fr) 1997-07-30 1998-07-21 Lessive contenant de la glucanase

Publications (2)

Publication Number Publication Date
EP1000137A1 EP1000137A1 (fr) 2000-05-17
EP1000137B1 true EP1000137B1 (fr) 2002-09-25

Family

ID=7837327

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98943763A Revoked EP1000137B1 (fr) 1997-07-30 1998-07-21 Lessive contenant de la glucanase

Country Status (12)

Country Link
US (1) US6417152B1 (fr)
EP (1) EP1000137B1 (fr)
JP (1) JP2001512175A (fr)
KR (1) KR20010022293A (fr)
CN (1) CN1299404A (fr)
AT (1) ATE224943T1 (fr)
DE (2) DE19732749A1 (fr)
DK (1) DK1000137T3 (fr)
ES (1) ES2183415T3 (fr)
HU (1) HUP0004797A2 (fr)
PL (1) PL338420A1 (fr)
WO (1) WO1999006516A1 (fr)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10019881A1 (de) * 2000-04-20 2001-11-15 Gerhard Miksch Verfahren zur Überexpression und extrazellulären Produktion bakterieller Phytasen in Escherichia coli
EP1307547B1 (fr) 2000-07-28 2005-10-26 Henkel Kommanditgesellschaft auf Aktien Nouvelle enzyme amylolytique issue de bacillus sp. a 7-7 (dsm 12368) et lessive et agent de nettoyage contenant cette enzyme amylolytique
ES2290184T3 (es) * 2000-11-28 2008-02-16 Henkel Kommanditgesellschaft Auf Aktien Ciclodextrina-glucanotransferasa (cgtasa) a partir de bacillus agaradherens (dsm 9948) asi como agentes para el lavado y la limpeiza con esta nueva ciclodextrina-glucanotransferasa.
DE10121463A1 (de) * 2001-05-02 2003-02-27 Henkel Kgaa Neue Alkalische Protease-Varianten und Wasch- und Reinigungsmittel enthaltend diese neuen Alkalischen Protease-Varianten
DE10138753B4 (de) * 2001-08-07 2017-07-20 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel mit Hybrid-Alpha-Amylasen
DE10153792A1 (de) * 2001-10-31 2003-05-22 Henkel Kgaa Neue Alkalische Protease-Varianten und Wasch- und Reinigungsmittel enthaltend diese neuen Alkalischen Protease-Varianten
DE10162728A1 (de) * 2001-12-20 2003-07-10 Henkel Kgaa Neue Alkalische Protease aus Bacillus gibsonii (DSM 14393) und Wasch-und Reinigungsmittel enthaltend diese neue Alkalische Protease
DE10162727A1 (de) * 2001-12-20 2003-07-10 Henkel Kgaa Neue Alkalische Protease aus Bacillus gibsonii (DSM 14391) und Wasch-und Reinigungsmittel enthaltend diese neue Alkalische Protease
DE10163748A1 (de) 2001-12-21 2003-07-17 Henkel Kgaa Neue Glykosylhydrolasen
DE10163884A1 (de) * 2001-12-22 2003-07-10 Henkel Kgaa Neue Alkalische Protease aus Bacillus sp. (DSM 14392) und Wasch- und Reinigungsmittel enthaltend diese neue Alkalische Protease
DE502004009582D1 (en) * 2003-12-13 2009-07-16 Henkel Ag & Co Kgaa Mehrkomponenten-thin-to-thick-system
DE102005049429A1 (de) * 2005-10-15 2007-04-19 Cognis Ip Management Gmbh Verfahren zur Ausrüstung von Textilien
DE102006038448A1 (de) 2005-12-28 2008-02-21 Henkel Kgaa Enzym-haltiges Reinigungsmittel
CN106133135B (zh) * 2014-03-27 2020-06-09 诺维信公司 β-葡聚糖酶变体以及编码它们的多核苷酸
MX2018007485A (es) 2015-12-30 2018-08-01 Novozymes As Variantes de enzimas y polinucleotidos que las codifican.
CN109312270B (zh) 2016-04-08 2022-01-28 诺维信公司 洗涤剂组合物及其用途
CN109312319B (zh) 2016-05-09 2023-05-16 诺维信公司 具有改善的性能的变体多肽及其用途
WO2018206300A1 (fr) 2017-05-08 2018-11-15 Novozymes A/S Variants de mannanase et polynucléotides codant pour ces derniers
CN110741084B (zh) 2017-05-08 2024-04-12 诺维信公司 甘露聚糖酶变体和对其编码的多核苷酸
CN111373036A (zh) 2017-10-02 2020-07-03 诺维信公司 具有甘露聚糖酶活性的多肽和编码它们的多核苷酸
WO2019068713A1 (fr) 2017-10-02 2019-04-11 Novozymes A/S Polypeptides présentant une activité mannanase et polynucléotides codant pour ces polypeptides
WO2019081515A1 (fr) 2017-10-24 2019-05-02 Novozymes A/S Compositions comprenant des polypeptides présentant une activité mannanase
US11535837B2 (en) 2018-03-29 2022-12-27 Novozymes A/S Mannanase variants and polynucleotides encoding same
US11248194B2 (en) * 2019-03-14 2022-02-15 The Procter & Gamble Company Cleaning compositions comprising enzymes
WO2020186028A1 (fr) * 2019-03-14 2020-09-17 The Procter & Gamble Company Compositions de nettoyage comprenant des enzymes
JP7275299B2 (ja) * 2019-03-14 2023-05-17 ザ プロクター アンド ギャンブル カンパニー 綿の処理方法
EP4097226A1 (fr) 2020-01-31 2022-12-07 Novozymes A/S Variants de mannanase et polynucléotides codant pour ceux-ci
JP2023511739A (ja) 2020-01-31 2023-03-22 ノボザイムス アクティーゼルスカブ マンナナーゼバリアント及びそれをコードするポリヌクレオチド
WO2023247348A1 (fr) 2022-06-21 2023-12-28 Novozymes A/S Variants de mannanase et polynucléotides codant pour ceux-ci

Family Cites Families (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE226012C (fr)
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
DK151231C (da) 1973-04-13 1988-07-04 Henkel Kgaa Fremgangsmaade til rensning, herunder vask, forvask og blegende vask, affaste materialer, isaer tekstiler, samt middel til udoevelse af fremgangsmaaden og fremgamgsmaade til fremstiling af midlet
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3417649A1 (de) 1984-05-12 1985-11-14 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von kristallinen natriumsilikaten
FR2597473B1 (fr) 1986-01-30 1988-08-12 Roquette Freres Procede d'oxydation de di-, tri-, oligo- et polysaccharides en acides polyhydroxycarboxyliques, catalyseur mis en oeuvre et produits ainsi obtenus.
GB8629837D0 (en) 1986-12-13 1987-01-21 Interox Chemicals Ltd Bleach activation
DE3718801A1 (de) 1987-06-02 1988-12-15 Desitin Arzneimittel Gmbh Verfahren zur herstellung von e-2-propyl-2-pentensaeure und physiologisch vertraeglichen salzen derselben
GB8908416D0 (en) 1989-04-13 1989-06-01 Unilever Plc Bleach activation
DE3921839A1 (de) 1989-07-03 1991-01-17 Henkel Kgaa Enzymatischer reiniger
ES2055441T3 (es) 1989-08-09 1994-08-16 Henkel Kgaa Obtencion de granulados compactados para detergentes.
DE4010533A1 (de) 1990-04-02 1991-10-10 Henkel Kgaa Tablettierte wasch- und/oder reinigungsmittel fuer haushalt und gewerbe und verfahren zu ihrer herstellung
DE3927758A1 (de) 1989-08-23 1991-02-28 Saarberg Interplan Gmbh Vorrichtung zum verhindern des austretens von fuellgasen waehrend des einfahrens von kohlekuchen in horizontale verkokungskammern
EP0493398B1 (fr) 1989-08-25 1999-12-08 Henkel Research Corporation Enzyme proteolytique alcaline et procede de production
CA2025073C (fr) 1989-10-25 1995-07-18 Gunther Schimmel Procede de production de silicates de sodium
US5229095A (en) 1989-10-25 1993-07-20 Hoechst Aktiengesellschaft Process for producing amorphous sodium silicate
YU221490A (sh) 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
DE4000705A1 (de) 1990-01-12 1991-07-18 Hoechst Ag Verfahren zur herstellung von kristallinen natriumsilikaten
GB9003741D0 (en) 1990-02-19 1990-04-18 Unilever Plc Bleach activation
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
US5041232A (en) 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
ES2100924T3 (es) 1990-05-21 1997-07-01 Unilever Nv Activacion de blanqueador.
US5290474A (en) 1990-10-05 1994-03-01 Genencor International, Inc. Detergent composition for treating cotton-containing fabrics containing a surfactant and a cellulase composition containing endolucanase III from trichoderma ssp
EP0559680B1 (fr) 1990-12-01 1995-07-05 Henkel Kommanditgesellschaft auf Aktien Procede de production hydrothermale de disilicate de sodium cristallin
DE4041752A1 (de) 1990-12-24 1992-06-25 Henkel Kgaa Enzymzubereitung fuer wasch- und reinigungsmittel
JP3293636B2 (ja) 1991-01-10 2002-06-17 日本化学工業株式会社 結晶性層状珪酸ナトリウムの製造方法
JP3299763B2 (ja) 1991-02-14 2002-07-08 日本化学工業株式会社 改質ジ珪酸ナトリウムの製造方法
DE4107230C2 (de) 1991-03-07 1995-04-06 Hoechst Ag Verfahren zur Herstellung von Natriumsilikaten
IT1245063B (it) 1991-04-12 1994-09-13 Ferruzzi Ricerca & Tec Procedimento per l'ossidazione di carboidrati
US5340735A (en) 1991-05-29 1994-08-23 Cognis, Inc. Bacillus lentus alkaline protease variants with increased stability
DE69126778T2 (de) 1991-07-31 1998-01-02 Ausimont Spa Verfahren zur Erhöhung der Bleichwirksamkeit eines inorganischen Persalzes
EP0544490A1 (fr) 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
CA2085642A1 (fr) 1991-12-20 1993-06-21 Ronald Hage Activation de blanchiment
DE4142711A1 (de) 1991-12-21 1993-06-24 Hoechst Ag Verfahren zur herstellung von kristallinen natriumdisilikaten
DE4221381C1 (de) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4203923A1 (de) 1992-02-11 1993-08-12 Henkel Kgaa Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
DE4216774A1 (de) 1992-05-21 1993-11-25 Henkel Kgaa Verfahren zur kontinuierlichen Herstellung eines granularen Wasch und/oder Reinigungsmittels
PT717778E (pt) 1992-07-17 2008-01-16 Genencor Int Serina proteases resistentes a alcalinidade elevada
ATE444356T1 (de) 1992-07-23 2009-10-15 Novozymes As Mutierte -g(a)-amylase, waschmittel und geschirrspülmittel
DE4228786A1 (de) 1992-08-29 1994-03-03 Henkel Kgaa Geschirrspülmittel mit ausgewähltem Builder-System
DE4300772C2 (de) 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4303320C2 (de) 1993-02-05 1995-12-21 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
PL310326A1 (en) 1993-02-11 1995-12-11 Genencor Int Novel oxidation-stable mutants of alpha-amylase as well as detergent and starch liquefaction compositions containing them
DE4310506A1 (de) 1993-03-31 1994-10-06 Cognis Bio Umwelt Enzymzubereitung für Wasch- und Reinigungsmittel
DK39093D0 (da) 1993-04-01 1993-04-01 Novo Nordisk As Enzym
CA2161266C (fr) 1993-05-20 2001-07-17 Alan David Willey Compositions de blanchiment renfermant des activateurs a base de n-acylcaprolactame
ES2119204T3 (es) 1993-05-20 1998-10-01 Procter & Gamble Compuestos de blanqueo que comprenden activadores de blanqueo de benzoil-caprolactama sustituidos.
EP0699229A1 (fr) 1993-05-20 1996-03-06 The Procter & Gamble Company Composes de blanchiment comprenant du n-acyl caprolactame, utiles dans le lavage a la main ou dans d'autres systemes de nettoyage de textiles a faible teneur en eau
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
DK100893D0 (da) 1993-09-09 1993-09-09 Novo Nordisk As Enzym
DE4338922A1 (de) 1993-11-15 1995-05-18 Degussa Aktivatoren für anorganische Persauerstoffverbindungen
GB9323971D0 (en) 1993-11-22 1994-01-12 Toad Innovations Ltd Cleaning formulation
EP0730631B1 (fr) 1993-11-25 1999-07-07 WARWICK INTERNATIONAL GROUP LIMITED (Company No. 2982784) Compositions de blanchiment
US5534196A (en) 1993-12-23 1996-07-09 The Procter & Gamble Co. Process for making lactam bleach activator containing particles
DE4405511A1 (de) 1994-02-22 1995-08-24 Henkel Kgaa Waschmittel mit amorphen silikatischen Buildersubstanzen
US5691295A (en) * 1995-01-17 1997-11-25 Cognis Gesellschaft Fuer Biotechnologie Mbh Detergent compositions
WO1995027775A1 (fr) 1994-04-07 1995-10-19 The Procter & Gamble Company Compositions de blanchiment comprenant des catalyseurs de blanchiment contenant du metal
DE4416438A1 (de) 1994-05-10 1995-11-16 Basf Ag Ein- oder mehrkernige Metall-Komplexe und ihre Verwendung als Bleich- und Oxidationskatalysatoren
DE4417734A1 (de) 1994-05-20 1995-11-23 Degussa Polycarboxylate
NZ289115A (en) * 1994-06-17 1999-02-25 Genencor Int Laundry compositions with cellulase and pectinase enzymes suitable for degrading cell walls of vegetable origin
EP0693550B1 (fr) 1994-07-21 2004-06-16 Ciba SC Holding AG Composition de blanchiment de tissu
EP0709452A1 (fr) * 1994-10-27 1996-05-01 The Procter & Gamble Company Compositions de nettoyage contenant des xylanases
EP0792342B1 (fr) * 1994-11-18 2001-09-05 The Procter & Gamble Company Utilisation de lipases specifiques dans des compositions detergentes
DE4443177A1 (de) 1994-12-05 1996-06-13 Henkel Kgaa Aktivatormischungen für anorganische Perverbindungen
JPH10510516A (ja) 1994-12-07 1998-10-13 ノボ ノルディスク アクティーゼルスカブ アレルゲン性を減らしたポリペプチド
DE19503060A1 (de) * 1995-02-01 1996-08-08 Henkel Ecolab Gmbh & Co Ohg Reinigungsverfahren für Membranfilter
EP0747470A1 (fr) 1995-06-08 1996-12-11 The Procter & Gamble Company Compositions de nettoyage contenant du kératanase
EP0756001A1 (fr) 1995-07-24 1997-01-29 The Procter & Gamble Company Compositions détergentes comprenant une amylase spécifique et un système tensioactif spécifique
DE19529905A1 (de) 1995-08-15 1997-02-20 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
DE19536082A1 (de) 1995-09-28 1997-04-03 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
AR003725A1 (es) * 1995-09-29 1998-09-09 Procter & Gamble Composiciones detergentes liquidas que contienen una amina, un alquilsulfato y un surfactante anionico adicional.
JPH10510721A (ja) * 1995-10-13 1998-10-20 ギスト ブロカデス ベスローテン フェンノートシャップ 菌類セルラーゼ
CZ136098A3 (cs) * 1995-11-17 1998-10-14 The Procter & Gamble Company Detergentní prací prostředek s obsahem lipolytického enzymu a vybraných kvartérních amonných saponátů
DE19605688A1 (de) 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19620411A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19613103A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallkomplex-haltige Systeme als Aktivatoren für Persauerstoffverbindungen
DE19616767A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616769A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616770A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acyllactame als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616693A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19619221A1 (de) 1996-05-13 1997-11-20 Solvay Enzymes Gmbh & Co Kg Enzymgranulat für Wasch- und Reinigungsanwendungen
DE19620267A1 (de) 1996-05-20 1997-11-27 Henkel Kgaa Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden für Persauerstoffverbindungen
US5811381A (en) * 1996-10-10 1998-09-22 Mark A. Emalfarb Cellulase compositions and methods of use
US5990065A (en) 1996-12-20 1999-11-23 The Procter & Gamble Company Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution
DE19732751A1 (de) 1997-07-30 1999-02-04 Henkel Kgaa Neue Beta-Glucanase aus Bacillus

Also Published As

Publication number Publication date
WO1999006516A1 (fr) 1999-02-11
JP2001512175A (ja) 2001-08-21
DK1000137T3 (da) 2003-02-03
CN1299404A (zh) 2001-06-13
PL338420A1 (en) 2000-11-06
DE59805725D1 (de) 2002-10-31
DE19732749A1 (de) 1999-02-04
ES2183415T3 (es) 2003-03-16
HUP0004797A2 (hu) 2001-04-28
US6417152B1 (en) 2002-07-09
KR20010022293A (ko) 2001-03-15
EP1000137A1 (fr) 2000-05-17
ATE224943T1 (de) 2002-10-15

Similar Documents

Publication Publication Date Title
EP1000137B1 (fr) Lessive contenant de la glucanase
EP0975729B1 (fr) Activateurs pour composes peroxyde dans des detergents et des nettoyants
EP1000136B1 (fr) Produit detergent contenant de la glucanase et destine aux surfaces dures
EP0876463B1 (fr) Agents de blanchiment et de lavage avec systeme de blanchiment enzymatique
EP1084222A1 (fr) Detergents contenant une amylase et une protease
DE19914811A1 (de) Enzym- und bleichaktivatorhaltige Wasch- und Reinigungsmittel
EP1084217B1 (fr) Detergents contenant une amylase et des derives d'acetonitrile
DE10037126A1 (de) Cellulasehaltiges Waschmittel
DE69720043T2 (de) Enzymatische bleichmittelzusammensetzung
EP0964911A1 (fr) Detergent contenant de la protease et de l'amylase
EP1084223B1 (fr) Detergents contenant une amylase et un compose de metal de transition activant le blanchiment
EP1084219A1 (fr) Detergents contenant une amylase et un percarbonate
EP1084220A1 (fr) Detergents contenant une amylase et un acide percarboxylique
DE19752844A1 (de) Verstärkung der Reinigungsleistung von Waschmitteln
DE19804656A1 (de) Cellulasehaltiges Waschmittel
EP0850292B1 (fr) Produit detergent inhibant le transfert de couleurs
CZ2000329A3 (cs) Prací prostředek
DE10162646A1 (de) Bleichaktivatorkombination für den Einsatz in Wasch-und Reinigungsmitteln
EP0879875A2 (fr) Oxa-esters d'acides carboxyliques comme activateurs de blanchiment pour compositions détergentes
DE19545727A1 (de) Alkalipercarbonathaltiges Waschmittel
EP0866116A2 (fr) Bisacylacetal dérivés comme activateurs de blanchiment pour les compositions détergentes à lessive
WO1999063039A1 (fr) Detergents contenant une amylase

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20000121

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE DK ES FI FR GB IT NL SE

17Q First examination report despatched

Effective date: 20010424

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE DK ES FI FR GB IT NL SE

REF Corresponds to:

Ref document number: 224943

Country of ref document: AT

Date of ref document: 20021015

Kind code of ref document: T

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 59805725

Country of ref document: DE

Date of ref document: 20021031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20021225

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20030124

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2183415

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20030625

26 Opposition filed

Opponent name: NOVOZYMES A/S

Effective date: 20030625

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20030625

NLR1 Nl: opposition has been filed with the epo

Opponent name: NOVOZYMES A/S

Opponent name: THE PROCTER & GAMBLE COMPANY

REG Reference to a national code

Ref country code: GB

Ref legal event code: 711B

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: GB

Ref legal event code: 711G

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20040704

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20040713

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20040714

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20040910

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050710

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20060201

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: NOVOZYMES A/S

Effective date: 20030625

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20030625

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20070718

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070719

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20070824

Year of fee payment: 10

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20070524

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Free format text: 20070524

BERE Be: lapsed

Owner name: *HENKEL K.G.A.A.

Effective date: 20050731

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070718

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20070730

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070710

Year of fee payment: 10

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO