EP1224254A1 - Inhibiteur enzymatique de grisaillement - Google Patents

Inhibiteur enzymatique de grisaillement

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Publication number
EP1224254A1
EP1224254A1 EP00967895A EP00967895A EP1224254A1 EP 1224254 A1 EP1224254 A1 EP 1224254A1 EP 00967895 A EP00967895 A EP 00967895A EP 00967895 A EP00967895 A EP 00967895A EP 1224254 A1 EP1224254 A1 EP 1224254A1
Authority
EP
European Patent Office
Prior art keywords
cellulase
weight
acid
alkali
ncu
Prior art date
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Granted
Application number
EP00967895A
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German (de)
English (en)
Other versions
EP1224254B1 (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
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Henkel AG and Co KGaA
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Publication of EP1224254A1 publication Critical patent/EP1224254A1/fr
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the invention relates to a specific enzymatic graying inhibitor for use in detergents containing surfactants as well as detergents and / or cleaning agents which contain the specific enzymatic graying inhibitor in combination with other specially selected ingredients.
  • fine-particle zeolite in particular zeolite-NaA, is used to bind the hardness formers, especially calcium and / or magnesium ions, in the washing water and dirt.
  • hardness formers especially calcium and / or magnesium ions
  • cobuilders or cobuilder systems are used to a considerable extent, particularly in the context of textile detergents, in particular to counteract undesirable incrustations.
  • incrustations are deposits on the inside walls of washing machines and especially on laundry, such as lime soap or organic residues. Such incrustations can adversely affect the feel, appearance, smell and absorbency of the laundry. The incrustations are particularly noticeable after repeated washing.
  • the graying of the laundry also usually only occurs after frequent washing, in particular when the detergent solution's dirt-carrying capacity is insufficient due to insufficient detergent dosing and the detached dirt from the liquor is repositioned on the laundry.
  • the above-mentioned builders or cobuilders are added to the detergents.
  • complexing agents to which salts of aminocarboxylic acids such as nitrilotriacetic acid and phosphonic acid acid derivatives are known.
  • Cobuilder combinations of this type counteract the precipitation of poorly soluble calcium salts when using detergents and cleaning agents and thus counteract the incrustations caused on the textile or other surfaces.
  • detergents in particular can also contain additional graying inhibitors which are intended to counteract the redeposition of dirt particles suspended in the wash liquor on the washed textiles.
  • German Offenlegungsschrift DE 33 29 400 proposes a mixture of methyl cellulose, carboxymethyl cellulose and copolymers of (meth) acrylic acid and maleic acid in a mixing ratio of 1: 1.5 to 4: 3 to 10 as an anti-graying additive in zeolite-containing detergents to use, the cellulose ethers must have certain degrees of substitution.
  • European patent application EP 054 325 describes the use of ternary mixtures of sodium carboxymethyl cellulose, a linear polycarboxylate and C ⁇ . 3- alkyl cellulose with degrees of substitution of at least 0.5 and degrees of polymerization up to 300 in detergents to inhibit graying.
  • German published patent application DE 43 25 882 it is proposed to use cellulase as a graying inhibitor in washing or cleaning agents.
  • the present invention relates to the use of Melanocarpus sp. or Myriococcum sp. Available 20K cellulase as a graying inhibitor in washing and cleaning agents.
  • Another object of the invention is the corresponding Use in detergents or cleaning agents which contain finely divided water-insoluble inorganic builders, in particular zeolite.
  • Further objects of the invention are detergents or cleaning agents which are derived from Melanocarpus sp. or Myriococcum sp. 20K cellulase available in combination with an optionally genetically modified protease from Bacillus lentus and / or alkali percarbonate. When such combinations are used, the graying-inhibiting effect of the cellulase to be used according to the invention is increased still further.
  • the from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase is known from international patent application WO 97/14804. As described there, it has a molecular weight of about 20 kDa and has at least 80% of its maximum activity at 50 ° C. in the pH range from 4 to 9, with almost 50% of the maximum activity remaining at pH 10. As also described there, it can be isolated from Melanocarpus albomyces and produced in genetically engineered Trichoderma reseei transformants. Cellulases which have a homology of over 80% to 20K cellulase can also be used for the purposes of the present invention.
  • a particular further advantage of the cellulase to be used according to the invention is that, when used, there is by far not as much a loss in the wet tensile strength of washed textiles as when using other cellulases, although their color-refreshing and fabric-softening effect is not inferior to that of other cellulases.
  • K20 cellulase is preferably used in amounts such that a finished agent has a cellulolytic activity of 1 NCU / g to 500 NCU / g (determinable by the hydrolysis of 1% by weight carboxymethyl cellulose at 50 ° C. and neutral pH and determination of the reducing substances released in the process Sugar using dinitrosalicylic acid, as described by MJ.Bailey et al. In Enzyme Microb. Technol.
  • 1 NCU defines the amount of enzyme that produces reducing sugars in an amount that corresponds to 1 nmol of glucose per second) , in particular from 2 NCU / g to 400 NCU / g and particularly preferably from 6 NCU / g to 200 NCU / g.
  • the agent may optionally contain other cellulases.
  • An agent according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg, of cellulolytic protein per gram of the total agent.
  • the protein concentration can be determined using known methods, for example the bicinchonic acid method (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem. 177 , 751-766, 1948).
  • the protease from Bacillus lentus is stable and active under strongly alkaline conditions; it can be produced as described in international patent application WO 91/02792 in Bacillus lentus (DSM 5483).
  • This Bacillus lentus alkaline protease (BLAP) can be obtained by fermentation of the Bacillus licheniformis which has been transformed with an expression plasmid which carries the gene for BLAP under the control of the promoter from Bacillus licheniformis ATCC 53926.
  • the composition as well as the spatial structure of BLAP is known (D.W. Godette et al., J. Mol. Biol. 228, 580-595, 1992).
  • protease is characterized by the sequence of 269 amino acids described in the cited literature, a calculated molecular weight of 26,823 daltons and a theoretical isoelectric point of 9.7. Variants of this Bacillus lentus DSM 5483 protease accessible by mutation are described in US Pat. No. 5,340,735. These include protease enzymes which, in particular when washing textiles made of proteinogenic fibers, for example textile fabrics made of natural silk or wool, result in particularly low substance damage or destruction of the fiber dressings without loss of cleaning performance.
  • the proteases which can be used according to the invention also include genetically modified proteases of the abovementioned BL AP type, in which, in position 211 (BLAP count), the amino acid leucine (L im usual one-letter code) is replaced by aspartic acid (D) or glutamic acid (E) (L211D or L211E).
  • BLAP count the amino acid leucine
  • E glutamic acid
  • WO 95/23221 can be produced.
  • Bacillus lentus protease such as at least one of the amino acid exchanges S3T, V4I, R99G, R99A, R99S, A188P, V193M and / or V199I, may have been made. It is particularly preferred to use a variant in which at least one of the amino acid exchanges S3T, V4I, V193M, V199I, or L211D has been carried out.
  • protease nomenclature on the exchange of individual amino acids it should be noted that the numbering of the amino acid positions in BLAP differs from that which is frequently found for the subtilisin BPN '.
  • positions 1 to 35 is identical in subtilisin BPN 'and BLAP; due to the lack of corresponding amino acids, positions 36 to 54 in BLAP correspond to positions 37 to 55 in BPN ', likewise positions 55 to 160 in BLAP correspond to positions 57 to 162 in BPN' and positions 161 to 269 correspond to those from 167 to 275 in BPN '.
  • An agent according to the invention preferably has a proteolytic activity in the range from about 100 PE / g to about 10000 PE / g, in particular 300 PE / g to 8000 PE / g.
  • the protease activity is determined according to the standardized method described below, as described in Tenside 7 (1970), 125: A solution containing 12 g / 1 casein and 30 mM sodium tripolyphosphate in water of 15 ° dH hardness (containing 0.058% by weight CaCl 2 2 H 2 O, 0.028% by weight MgCl 2 6 H 2 O and 0.042% by weight NaHCO 3 ) is heated to 70 ° C., the pH is adjusted to 8 by adding 0.1 N NaOH. 5 set at 50 ° C.
  • the absorption of this solution at 290 nm is determined with the aid of an absorption spectrometer, the absorption zero 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.
  • the proteolytic activity of a protease solution which causes an absorption of 0.500 OD under the specified measurement conditions, is defined as 10 PE (protease units) per ml.
  • the ratio of the cellulolytic activity, expressed in NCU / g, to the proteolytic activity, expressed in PE / g is preferably 1:10 000 to 5: 1, in particular 1: 1600 to 4: 3.
  • the enzymes can, in particular for use in particulate compositions, as described for example in European patent EP 0 564476 or in international patent application WO 94/23005 for other enzymes, be adsorbed on carriers and / or be embedded in coating substances in order to prevent them from being inactivated prematurely to protect.
  • the combination of certain cellulase and optionally genetically modified protease, which is essential to the invention, can be achieved by incorporating the two separate or, in a known manner, separately packaged enzymes or by cellulase and protease packaged together in a granulate, as for example from international patent applications WO 96/00772 or WO 96 / Known 00773 can be used in agents according to the invention.
  • An agent according to the invention preferably contains up to 50% by weight, in particular 5% by weight to 30% by weight, of alkali percarbonate, sodium percarbonate being particularly preferred. It can be produced according to known processes and, if desired, in particular for use in particulate compositions, in granular form, if necessary, made up or stabilized and / or coated, as described, for example, in international patent applications WO 91/15423, WO 92/17400, WO 92/17404, WO 93/04159, WO 93/04982, WO 93/20007, WO 94/03553, WO 94/05594, WO 94/14701, WO 94/14702, WO 94/24044, WO 95/02555, WO 95/02672, WO 95/06615, WO 95/15291 or WO 95/15292 or the European patent applications EP 0459 625, EP 0487256, EP 0 567 140, EP 0 623 553, EP 0 592
  • granules which, with the aid of alkaline earth metal sulfate, alkali metal sulfate, alkali metal silicate, alkaline earth metal halide, alkali metal halide, alkali metal carbonate, alkali metal hydrogen carbonate, alkali metal phosphate, alkali metal borate, alkali metal perborate, boric acid, partially hydrated alumino-silicate carboxylic acids, carboxylic acids, carboxylic acids, carboxylic acids - And / or dicarboxylic acids, or mixtures of these was prepared or is enveloped.
  • it has a morphology index (MI), as defined in EP 0451 893, of less than 0.06.
  • the ratio of cellulase to be used according to the invention to alkali percarbonate is in the range from 0.0001 mg to 0.1 mg, in particular from 0.001 mg to 0.01 mg, of cellulolytic protein per% by weight of alkali percarbonate in the washing or Cleaning supplies.
  • the detergents or cleaning agents can preferably be heavy-duty or mild detergents used in textile washing and, if appropriate, fabric softener that can be used in a rinse cycle after washing.
  • the use of the special cellulase relates to the reduction of the redeposition in textile washing with textile detergents based on finely divided water-insoluble inorganic builder components, in particular zeolite NaA.
  • cellulase as well as the optionally additionally used enzymes, to which, in addition to the protease mentioned, in particular amylase, lipase, oxidase, peroxidase, cutinase, pullulanase, xylanase and / or hemicellulase and, if appropriate, further cellulases and / or proteases are to be included and which are preferably in amounts from 0.1% by weight to 2% by weight are present in the form of liquid formulations, optionally with the addition of stabilizer, in particulate detergents, but preferably in the form adsorbed on carriers, embedded in coating substances or in the form of conventional granules inorganic and / or organic carrier materials, as described, for example, in German patent specification DE 16 17 232, German patent application DT 20 32 766 or DE 40 41 752 or European patent applications EP 168 526, EP 170 360, EP 270 608 or EP 304 331 , are used.
  • the enzymes can be contained in separate particles or in the form of a multi-enzyme granulate, as described, for example, in German patent applications DE 4422433 or DE 4422 609 or international patent applications WO 90/09440 or WO 90/09428 and the prior art cited therein , are used.
  • the washing and cleaning agents according to the invention which can be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions, can in principle contain all of the known ingredients customary in such agents.
  • the agents according to the invention can in particular builder substances, surface-active surfactants, bleach activators, water-miscible organic solvents, additional enzymes, sequestering agents, electrolytes, pH regulators as well as further bleaching agents based on organic and / or inorganic peroxygen compounds and further auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors , Foam regulators, silver corrosion inhibitors and dyes and fragrances.
  • the agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • the surfactants of the sulfonate type are preferably C 3 -C 3 -alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 2 -C 8 monoolefins having an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C] 2 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which have from 8 to by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of ⁇ -sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C 2 -C-fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 -C 20 oxo alcohols and those half esters secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 2 -C 6 alkyl sulfates and C 2 -C alkyl sulfates and C -C 5 alkyl sulfates are particularly preferred.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7 -C 2 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 2 -alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ⁇ 2 - Ci8 fatty alcohols with 1 to 4 EO. Because of their high foaming behavior, they are normally used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 - to C 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfo succinate contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which are non-ionic surfactants.
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Fatty acid derivatives of amino acids for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants.
  • the sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triemanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • alkyl glycosides and ethoxylation and / or propoxylation products of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid amides which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and also of alkyl phenols with 5 to 12 carbon atoms in the alkyl radical, can be used.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and On average, 1 to 12 moles of ethylene oxide (EO) are used per mole of alcohol, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position or can contain linear and methyl-branched radicals in the mixture, as is usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, -C 2 -C 4 alcohols with 3 EO or 4 EO, C -Cn alcohols with 7 EO, C ⁇ - Cis alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C ⁇ g- alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ⁇ 2 -C ⁇ - alcohol with 3 EO and C
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • Extremely low-foaming compounds are usually used in particular in cleaning agents for use in machine dishwashing processes. These preferably include C 2 -C 18 alkyl polyethylene glycol polypropylene glycol ether, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • low-foam nonionic surfactants such as, for example, C 2 -C 8 alkylpolyethylene glycol polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, and also end group-capped alkyl polyalkylene glycol mixed ethers.
  • hydroxyl-containing alkoxylated alcohols as described in European patent application EP 0300305, so-called hydroxy mixed ethers.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G), in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - and also the quantity to be determined analytically can take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in which R'CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
  • R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 8 -alkyl or phenyl radicals being preferred
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • non-ionic surfactants that used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO 90/13533.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-NN-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are generally separated from one another by a so-called “spacer”.
  • This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another.
  • Such surfactants are distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • gemini surfactants is understood to mean not only such "dimeric” but also correspondingly "trimeric” surfactants.
  • Surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis- and trimeral alcohol tris-sulfates and ether sulfates according to German patent application DE 195 03 061.
  • End group-blocked dimer and trimeric mixed ethers according to German patent application DE 195 13 391 yourself in especially by their bi- and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides, such as those used in the interna- tional patent applications WO 95/19953, WO 95/19954 and WO 95/19955 are described.
  • Surfactants are present in detergents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, whereas agents for cleaning hard surfaces, in particular for machine cleaning of dishes , have lower surfactant contents of up to 10% by weight, in particular up to 5% by weight and preferably in the range from 0.5% by weight to 3% 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 as well as polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphinylphosphonic acid), methylenediamine methacrylate (methylenediamine), methylenediamine (1) methylenediamonic acid, methylenediamine (1) 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of European patent EP 0 625 992 or of international patent application WO 92/18542 or European patent EP 0232 202, which are accessible by oxid
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 30,000 to 100,000.
  • Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • 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, the monomers being two unsaturated Contained acids and / or their salts and, as a third monomer, vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -Cg carboxylic acid and preferably from a C 3 -C monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C -Cg 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 patent DE 4221 381 and German patent application 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 have 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, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing agents according to the invention.
  • Particularly suitable water-soluble inorganic builder materials are alkali silicates, alkali carbonates and alkali phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric
  • a water-insoluble, water-dispersible inorganic builder material In particular, crystalline or amorphous alkali alumosilicates are used, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid compositions, in particular from 1% by weight to 5% by weight.
  • the crystalline sodium aluminosilicates in detergent quality in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA), are preferred , Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • Their calcium binding capacity which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram.
  • 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 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 sheet silicates of the general formula Na 2 Si x O 2x + ⁇ y H 2 O, in which x, the so-called modulus, is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 22, especially 1.9 to 4 and y is a number from 0 to 33 and are preferred values for x 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.
  • both ⁇ - and f3-sodium disilicate Na 2 Si 2 O 5 y H 2 O
  • ⁇ -sodium disilicate being able to 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.
  • 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.
  • Crystalline layered silicates of the formula (I) given above are sold by Clariant GmbH (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na 2 Si 22 O 5 xH 2 O, Kenyait), Na- SKS-2 (Na 2 Si H O 29 xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O ⁇ 7 xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 'xH O, Makatit).
  • Na-SKS for example Na-SKS-1 (Na 2 Si 22 O 5 xH 2 O, Kenyait), Na- SKS-2 (Na 2 Si H O 29 xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O ⁇ 7 xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 'xH O, Makatit).
  • Na-SKS-5 ( ⁇ -Na 2 Si 0 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 H) are particularly suitable 2 O), Na-SKS-10 (NaHSi 2 O 5 3H 2 O, Kanemit), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), in particular but Na-SKS-6 ( ⁇ -Na 2 Si 2 ⁇ 5 ).
  • crystalline layered silicates are given, for example, in "Hoechst High Chem Magazine 14/1993" on pages 33 - 38 and in "Soap-oil-fat-waxes, 116 year, No. 20/1990" on pages 805 - 808 published articles.
  • Builder substances can optionally be present in the agents according to the invention in amounts of up to 90% by weight. They are preferably in amounts up to 75% by weight. contain. Detergents according to the invention have builder contents of in particular 5% by weight to 50% by weight. In agents according to the invention for cleaning hard surfaces, in particular for machine cleaning of dishes, the builder substance content is in particular 5% by weight to 88% by weight, with such agents preferably not using any water-insoluble builder materials.
  • agents according to the invention for in particular machine cleaning of dishes 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, 5% by weight to 15% by weight of alkali carbonate and 20% by weight to Contain 40 wt .-% alkali disilicate.
  • Suitable peroxygen compounds for use in agents according to the invention include, in addition to the alkali percarbonate already mentioned, in particular organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing conditions, to which perborates, persilicate and / or include persulfates such as caroate.
  • organic peracids or peracidic salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing conditions, to which perborates, persilicate and / or include persulfates such as caroate.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granul
  • an agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may be useful.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic acid polyhydric triethyl anhydride , 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE 196 16693 and DE 196 16 767 as
  • hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 4443 177 can also be used.
  • Bleach activators of this type can be present in the customary quantitative range, preferably in amounts of 0.5% by weight to 10% by weight, in particular 1% by weight to 8% by weight, based on the total agent.
  • the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 and EP 0453 003 may also be present as so-called bleaching catalysts.
  • the organic solvents which can be used in the agents according to the invention, in particular if they are in liquid or pasty form, in addition to water include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms -Atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and those derivable from the compound classes mentioned Ether.
  • Such water-miscible solvents are preferably present in the agents according to the invention in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents can contain further constituents customary in washing and cleaning agents.
  • These optional components include, in particular, enzyme stabilizers, graying inhibitors, color transfer inhibitors, foam inhibitors, and optical brighteners, and colorants and fragrances.
  • silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
  • a cleaning agent according to the invention for hard surfaces can also contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic materials, chalks and micro-glass balls and mixtures thereof. Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.
  • the agents according to the invention can contain system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides.
  • Such pH regulators are present in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • the color transfer inhibitors that are suitable for use in textile detergents according to the invention include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.
  • Additional graying inhibitors can also be present in the agents according to the invention.
  • 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 cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Starch derivatives other than those mentioned above can also be used, for example aldehyde starches.
  • Cellulose ethers such as carboxymethyl cellulose (Na salt) and methyl cellulose are preferred.
  • Hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition, are used.
  • Textile detergents according to the invention can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-aniHno-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type can also 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 also be used.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 8 -C 2 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and also 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 in particular silicone- and / or paraffin-hooked foam inhibitors, are preferably 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 enzymes and any further 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 / 1 to 950 g 1, a process known from European patent EP 0486 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.
  • agents according to the invention in tablet form, which can consist of one or more phases, of one color or of more than one color and in particular of one layer or of more than one, in particular of two layers
  • the procedure is preferably such that all constituents - optionally one layer each - are combined in one Mixer mixed together and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range from about 50 to 100 kN, preferably at 60 to 70 kN.
  • break-resistant tablets which nevertheless dissolve sufficiently quickly under application conditions, are obtained with breaking and bending strengths of normally 100 to 200 N, but preferably over 150 N.
  • a tablet produced in this way preferably has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
  • the shape of the tablets is arbitrary and can be round, oval or angular, intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of angular or cuboid tablets which are mainly introduced via the metering device, for example the dishwasher, depends on the geometry and the volume of this metering device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or of 24x38 mm.
  • Liquid or pasty washing or cleaning agents according to the invention in the form of solutions containing customary solvents are generally produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • the cellulases listed in Table 1 were added to an enzyme-free basic detergent BWI.
  • the cellulases were used in an amount based on protein that corresponded to an amount of 0.6% by weight Celluzyme® 0.7T (manufacturer: Novo Nordisk) in the detergent used in each case.
  • the tissue graying - determined by the reflectance after 10 washes - was determined, washing tests being carried out under the following conditions:
  • Soiling 5 strands of cotton with standardized
  • Example 1 was repeated, in a departure from the procedure described there, 11 washes were carried out and a basic detergent BW2 was used which, in contrast to BWI, 1.2% by weight of an enzyme granulate containing the protease BLAP with an activity of 200,000 PU / g contained.
  • an agent according to the invention has a better graying-inhibiting effect than an agent which contains a different celluase instead of the cellulase to be used according to the invention.

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  • 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne l'utilisation de la cellulase K20 obtenue à partir de melanocarpus sp. ou de myriococcum sp. ou d'une cellulase présentant plus de 80 % d'homologie avec la précédente, comme inhibiteur de grisaillement dans des détergents et des nettoyants. Cette cellulase, utilisée notamment en combinaison avec une protéase éventuellement modifiée par génie génétique et/ou du percarbonate alcalin, induit une diminution de la redéposition de particules de salissures sur le linge lavé.
EP00967895A 1999-10-29 2000-10-20 Inhibiteur enzymatique de grisaillement Expired - Lifetime EP1224254B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19952457 1999-10-29
DE19952457A DE19952457A1 (de) 1999-10-29 1999-10-29 Enzymatischer Vergrauungsinhibitor
PCT/EP2000/010328 WO2001032817A1 (fr) 1999-10-29 2000-10-20 Inhibiteur enzymatique de grisaillement

Publications (2)

Publication Number Publication Date
EP1224254A1 true EP1224254A1 (fr) 2002-07-24
EP1224254B1 EP1224254B1 (fr) 2004-03-31

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EP00967895A Expired - Lifetime EP1224254B1 (fr) 1999-10-29 2000-10-20 Inhibiteur enzymatique de grisaillement

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EP (1) EP1224254B1 (fr)
JP (1) JP2003514069A (fr)
KR (1) KR20020041832A (fr)
AR (1) AR026261A1 (fr)
AT (1) ATE263229T1 (fr)
AU (1) AU7789400A (fr)
CA (1) CA2324767A1 (fr)
DE (2) DE19952457A1 (fr)
DK (1) DK1224254T3 (fr)
ES (1) ES2218229T3 (fr)
PL (1) PL354454A1 (fr)
TN (1) TNSN00208A1 (fr)
WO (1) WO2001032817A1 (fr)

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JP2009149775A (ja) * 2007-12-20 2009-07-09 Lion Corp 洗濯槽用洗浄剤組成物
DE102014226293A1 (de) * 2014-12-17 2016-06-23 Henkel Ag & Co. Kgaa Waschmittel mit verbesserter Fleckentfernung

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Publication number Priority date Publication date Assignee Title
GB2094826B (en) * 1981-03-05 1985-06-12 Kao Corp Cellulase enzyme detergent composition
DE4325882A1 (de) * 1993-08-02 1995-02-09 Henkel Kgaa Enzymatischer Vergrauungsinhibitor
DE19520101A1 (de) * 1995-06-01 1996-12-05 Henkel Kgaa Vergrauungsinhibitorsystem auf enzymatischer Basis
EP0857216B1 (fr) * 1995-10-17 2014-09-10 AB Enzymes Oy Cellulases, genes les codant et utilisation de ces cellulases

Non-Patent Citations (1)

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Title
See references of WO0132817A1 *

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TNSN00208A1 (fr) 2002-05-30
AR026261A1 (es) 2003-02-05
PL354454A1 (en) 2004-01-12
DE19952457A1 (de) 2001-05-03
JP2003514069A (ja) 2003-04-15
CA2324767A1 (fr) 2001-04-29
DE50005928D1 (de) 2004-05-06
EP1224254B1 (fr) 2004-03-31
WO2001032817A1 (fr) 2001-05-10
ATE263229T1 (de) 2004-04-15
DK1224254T3 (da) 2004-07-26
KR20020041832A (ko) 2002-06-03
ES2218229T3 (es) 2004-11-16
AU7789400A (en) 2001-05-14

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