EP1224254A1 - Enzymatic graying inhibitor - Google Patents

Enzymatic graying inhibitor

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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
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.)
Granted
Application number
EP00967895A
Other languages
German (de)
French (fr)
Other versions
EP1224254B1 (en
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/en
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Expired - Lifetime legal-status Critical Current

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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
    • C11D3/38645Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0036Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium 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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Abstract

The invention relates to the use of the K20 cellulase obtained from Melanocarpus sp. or Myriococcum sp. or a cellulase that is by 80 % homologous to said cellulase as a graying inhibitor in detergents and cleaning agents. Said cellulase, especially when combined with an optionally genetically modified protease and/or alkali percabonate reduces the redeposition of dirt particles on washed laundry.

Description

Enzyma ischer Vergrauungsinhibitor Enzymatic graying inhibitor
Die Erfindung betrifft einen bestimmten enzymatischen Vergrauungsinhibitor zum Einsatz in tensidhaltigen Waschmitteln sowie Wasch- und/oder Reinigungsmittel, welche den bestimmten enzymatischen Vergrauungsinhibitor in Kombination mit weiteren speziell ausgewählten Inhaltsstoffen enthalten.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.
In Wasch- und Reinigungsmitteln wird heute zur Bindung der Härtebildner, vor allem Calcium- und/oder Magnesiumionen, im Waschwasser und Schmutz feinteiliger Zeolith, insbesondere Zeolith-NaA, eingesetzt. In beträchtlichem Ausmaß, insbesondere im Rahmen der Textilwaschmittel, werden allerdings sogenannte Cobuilder beziehungsweise Cobuilder-Systeme eingesetzt, insbesondere um unerwünschten Inkrustationen entgegenzuwirken.In detergents and cleaning agents, 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. So-called cobuilders or cobuilder systems are used to a considerable extent, particularly in the context of textile detergents, in particular to counteract undesirable incrustations.
Bei diesen Inkrustationen handelt es sich um Ablagerungen an Innenwänden von Waschmaschinen und insbesondere auf der Wäsche, wie zum Beispiel Kalkseife oder organische Rückstände. Derartige Inkrustationen können den Griff, die äußere Beschaffenheit, den Geruch und das Saugvermögen der Wäsche nachteilig beeinflussen. Die Inkrustationen machen sich insbesondere nach mehrmaligem Waschen bemerkbar.These 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.
Auch das Vergrauen der Wäsche tritt in der Regel erst nach häufigem Waschen auf und zwar insbesondere dann, wenn durch zu geringe Waschmitteldosierung das Schmutztragevermögen der Waschflotte nur ungenügend ist und der von der Wäsche abgelöste Schmutz aus der Flotte auf der Wäsche redeponiert wird.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.
Um die Inkrustationen und die Vergrauung der Wäsche zu vermeiden beziehungsweise möglichst gering zu halten, werden den Waschmitteln die obengenannten Builder beziehungsweise Cobuilder zugesetzt. Die zusätzlich Mitverwendung von Komplexbildnern, zu denen Salze von Aminocarbonsäuren wie Nitrilotriessigsäure und Phosphon- säurederivate gehören, ist bekannt. Cobuilder-Kombinationen dieser Art wirken bei der Anwendung von Wasch- und Reinigungsmitteln der Ausfallung schwerlöslicher Calcium- salze und damit den dadurch hervorgerufenen Inkrustationen auf dem Textil oder sonstigen Oberflächen entgegen. Femer können insbesondere Waschmittel noch zusätzliche Vergrauungsinhibitoren enthalten, welche gezielt der Wiederablagerung von in der Waschlauge suspendierten Schmutzteilchen auf den gewaschenen Textilien entgegenwirken sollen.To avoid incrustations and graying of the laundry or to keep them as low as possible, the above-mentioned builders or cobuilders are added to the detergents. The additional use of 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. Furthermore, 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.
In der deutschen Offenlegungsschrift DE 33 29 400 wird vorgeschlagen, als vergrauungs- verhütenden Zusatz in Zeolith-haltigen Waschmitteln eine Mischung aus Methylcellulose, Carboxymethylcellulose und Copolymeren der (Meth)acrylsäure und Maleinsäure im Mischungsverhältnis von 1 : 1,5 bis 4 : 3 bis 10 zu verwenden, wobei die Celluloseether bestimmte Substitutionsgrade aufweisen müssen.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.
Die europäische Patentanmeldung EP 054 325 beschreibt den Einsatz von ternären Mischungen aus Natrium-Carboxymethylcellulose, einem linearen Polycarboxylat und Cι.3-Alkylcellulose mit Substitutionsgraden von mindestens 0,5 und Polymerisationsgraden bis zu 300 in Waschmitteln zur Vergrauungsinhibierung.European patent application EP 054 325 describes the use of ternary mixtures of sodium carboxymethyl cellulose, a linear polycarboxylate and Cι. 3- alkyl cellulose with degrees of substitution of at least 0.5 and degrees of polymerization up to 300 in detergents to inhibit graying.
In der deutschen Offenlegungsschrift DE 43 25 882 wird vorgeschlagen, Cellulase als Vergrauungsinhibitor in Wasch- oder Reinigungsmitteln zu verwenden.In German published patent application DE 43 25 882 it is proposed to use cellulase as a graying inhibitor in washing or cleaning agents.
Obwohl die in den genannten Druckschriften beschriebenen Maßnahmen in den meisten Fällen durchaus zufriedenstellende Ergebnisse zeigen, besteht dennoch das Bedürfnis, wirksamere Vergrauungsinbibitorsysteme zu entwickeln.Although the measures described in the cited publications show in most cases quite satisfactory results, there is still a need to develop more effective graying indicator systems.
Überraschenderweise wurde nun gefunden, daß die Verwendung einer ganz bestimmten Cellulase eine besonders gute Reduzierung der Wiederablagerung von Schmutzpartikeln auf der gewaschenen Wäsche (Redeposition) und der Vergrauung bewirkt.Surprisingly, it has now been found that the use of a very specific cellulase brings about a particularly good reduction in the redeposition of dirt particles on the washed laundry (redeposition) and graying.
Gegenstand der vorliegenden Erfindung ist die Verwendung von aus Melanocarpus sp. oder Myriococcum sp. erhältlicher 20K-Cellulase als Vergrauungsinhibitor in Wasch- und Reinigungsmitteln. Ein weiterer Gegenstand der Erfindung ist die entsprechende Verwendung in Wasch- oder Reinigungsmitteln, die feinteiligen wasserunlöslichen anorganischen Builder, insbesondere Zeolith, enthalten.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.
Weitere Gegenstände der Erfindung sind Wasch- oder Reinigungsmittel, welche die aus Melanocarpus sp. oder Myriococcum sp. erhältliche 20K-Cellulase in Kombination mit einer gegebenenfalls gentechnisch veränderten Protease aus Bacillus lentus und/oder Alkalipercarbonat enthalten. Bei Einsatz derartiger Kombinationen erhält man eine noch weiter verstärkte vergrauungsinhibierende Wirkung der erfindungsgemäß zu verwendenden Cellulase.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.
Die aus Melanocarpus sp. oder Myriococcum sp. erhältliche 20K-Cellulase ist aus der internationalen Patentanmeldung WO 97/14804 bekannt. Sie besitzt wie dort beschrieben ein Molekulargewicht von etwa 20 kDa und weist bei 50 °C im pH-Bereich von 4 bis 9 mindestens 80 % ihrer maximalen Aktivität auf, wobei noch fast 50 % der maximalen Aktivität bei pH 10 erhalten bleiben. Sie kann, wie ebenfalls dort beschrieben, aus Melanocarpus albomyces isoliert und in gentechnisch hergestellten Trichoderma reseei- Transformanten produziert werden. Im Sinne der vorliegenden Erfindung brauchbar sind auch Cellulasen, die eine Homologie von über 80 % zur 20K-Cellulase aufweisen.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.
Als besonderer weiterer Vorteil der erfindungsgemäß zu verwendenden Cellulase ist zu werten, daß bei ihrem Einsatz ein bei weitem nicht so großer Verlust der Naßreißkraft gewaschener Textilien auftritt als bei Einsatz anderer Cellulasen, obwohl sie in ihrer farbauffrischenden und gewebeweichmachenden Wirkung anderen Cellulasen nicht nachsteht.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 wird vorzugsweise in solchen Mengen verwendet, daß ein fertiges Mittel eine cellulolytische Aktivität von 1 NCU/g bis 500 NCU/g (bestimmbar durch die Hydrolyse von 1 -gewichtsprozentiger Carboxymethylcellulose bei 50 °C und neutralem pH und Bestimmung der dabei freigesetzten reduzierenden Zucker mittels Dinitro- salicylsäure, wie von MJ.Bailey et al. in Enzyme Microb. Technol. 3: 153 (1981) beschrieben; 1 NCU definiert die Enzymmenge, die reduzierenden Zucker in einer Menge erzeugt, die 1 nmol Glukose pro Sekunde entspricht), insbesondere von 2 NCU/g bis 400 NCU/g und besonders bevorzugt von 6 NCU/g bis 200 NCU/g aufweist. Daneben kann das Mittel gegebenenfalls noch weitere Cellulasen enthalten.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. 3: 153 (1981); 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. In addition, the agent may optionally contain other cellulases.
Ein erfindungsgemäßes Mittel enthält vorzugsweise 0,001 mg bis 0,5 mg, insbesondere 0,02 mg bis 0,3 mg an cellulolytischem Protein pro Gramm des gesamten Mittels. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem Bicinchonsäure- Verfahren (BCA-Verfahren, Pierce Chemical Co., Rockford, IL) oder dem Biuret-Verfahren (A.G. Gornall, C.S. Bardawill und M.M. David, J. Biol. Chem. 177, 751-766, 1948) bestimmt werden.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).
Die Protease aus Bacillus lentus ist unter stark alkalischen Bedingungen stabil und aktiv; sie kann wie in der internationalen Patentanmeldung WO 91/02792 beschrieben in Bacillus lentus (DSM 5483) produziert werden. Diese Bacillus lentus alkalische Protease (BLAP) kann durch Fermentation des Bacillus licheniformis erhalten werden, der mit einem Expressionsplasmid transformiert wurde, welches das Gen für BLAP unter der Kontrolle des Promotors aus Bacillus licheniformis ATCC 53926 trägt. Die Zusammensetzung wie auch die räumliche Struktur von BLAP ist bekannt (D.W. Godette et al., J. Mol. Biol. 228, 580-595,1992). Diese Protease ist durch die in der zitierten Literatur beschriebene Sequenz aus 269 Aminosäuren, ein rechnerisches Molekulargewicht von 26 823 Dalton und einen theoretischen isoelektrischen Punkt von 9,7 charakterisiert. Durch Mutation zugängliche Varianten dieser Bacillus lentus DSM 5483 Protease sind in der US-amerikanischen Patentschrift US 5 340735 beschrieben. Unter diesen sind Proteaseenzyme, die bei insbesondere mehrfacher Waschbehandlung von Textilien aus proteinogenen Fasern, beispielsweise textilen Flächengebilden aus Naturseide oder Wolle, ohne Verlust an Reinigungsleistung zu besonders geringen Substanzschädigungen beziehungsweise Zerstörungen der Faserverbände führen.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). This 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.
Zu den erfindungsgemäß brauchbaren Proteasen zählen neben der natürlich vorkommenden Protease aus Bacillus lentus auch gentechnisch veränderte Proteasen des obengenannten BL AP-Typs, bei denen in Position 211 (BLAP-Zählung) die an dieser Stelle in der Wildtyp-Protease vorhandene Aminosäure Leucin (L im gebräuchlichen EinBuchstaben-Code) gegen Asparaginsäure (D) beziehungsweise Glutaminsäure (E) ausgetauscht ist (L211D beziehungsweise L211E). Diese können wie in der internationalen Pa- tentanmeldung WO 95/23221 beschrieben hergestellt werden. Stattdessen oder zusätzlich können weitere Veränderungen gegenüber der ursprünglichen Bacillus lentus-Protease, wie beispielsweise mindestens einer der Aminosäureaustausche S3T, V4I, R99G, R99A, R99S, A188P, V193M und/oder V199I, vorgenommen worden sein. Besonders bevorzugt ist der Einsatz einer Variante, bei welcher mindestens einer der Aminosäureaustausche S3T, V4I , V193M, V199I, oder L211D vorgenommen wurde. Bei der vorstehend beschriebenen Proteasenomenklatur über den Austausch einzelner Aminosäuren ist zu beachten, daß die Numerierung der Aminosäurepositionen in BLAP sich von der häufig anzutreffenden des Subtilisin BPN' unterscheidet. Die Numerierung der Positionen 1 bis 35 ist in Subtilisin BPN' und BLAP identisch; aufgrund fehlender korrespondierender Aminosäuren entsprechen die Positionen 36 bis 54 in BLAP den Positionen 37 bis 55 in BPN', ebenso die Positionen 55 bis 160 in BLAP den Positionen 57 bis 162 in BPN' und die Positionen 161 bis 269 denen von 167 bis 275 in BPN'.In addition to the naturally occurring protease from Bacillus lentus, 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). As in the international pa- tent registration WO 95/23221 can be produced. Instead or in addition, further changes to the original 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. In the above-described 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 '. The numbering of 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 '.
Ein erfindungsgemäßes Mittel weist vorzugsweise eine proteolytische Aktivität im Bereich von etwa 100 PE/g bis etwa 10000 PE/g, insbesondere 300 PE/g bis 8000 PE/g auf. Die Proteaseaktivität wird gemäß dem nachfolgend beschriebenen standardisierten Verfahren, wie in Tenside 7 (1970), 125 beschrieben, bestimmt: Eine Lösung, die 12 g/1 Casein und 30 mM Natriumtripolyphosphat in Wasser des Härtegrades 15 °dH (enthaltend 0,058 Gew.-% CaCl2 2 H2O, 0,028 Gew.-% MgCl2 6 H2O und 0,042 Gew.- % NaHCO3) wird auf 70 °C erwärmt, der pH- Wert wird durch Zugabe von 0,1 N NaOH auf 8,5 bei 50 °C eingestellt. Zu 600 ml der Substratlösung werden 200 ml einer Lösung des zu testenden Enzyms in 2 gewichtsprozentiger Natriumtripolyphosphat-Pufferlösung (pH 8,5) gegeben. Die Reaktionsmischung wird bei 50 °C für 15 Minuten inkubiert. Die Reaktion wird danach durch Zugabe von 500 ml TCA-Lösung (0,44 M Trichloressigsäure und 0,22 M Natriumacetat in 3 volumenprozentiger Essigsäure) und Abkühlen (Eisbad bei 0 °C, 15 Minuten) gestoppt. Das TCA-unlösliche Protein wird durch Zentrifugation entfernt, 900 ml des Überstandes werden mit 300 ml 2 N NaOH verdünnt. Die Absorption dieser Lösung bei 290 nm wird mit Hilfe eines Absorptionsspektrometers bestimmt, wobei der Absorptionsnullwert durch das Messen einer zentrifugierten Lösung, die durch Mischen von 600 ml der obengenannten TCA-Lösung mit 600 ml der obengenannten Substratlösung und anschließender Zugabe der Enzymlösung hergestellt wird, zu bestimmen ist. Die proteolytische Aktivität einer Proteaselösung, die unter den angegebenen Meßbedingungen eine Absorption von 0,500 OD bewirkt, wird zu 10 PE (Protease- Einheiten) pro ml definiert. Vorzugsweise beträgt im erfindungsgemäßen Mittel das Verhältnis der cellulolytischen Aktivität, ausgedrückt in NCU/g, zur proteolytischen Aktivität, ausgedrückt in PE/g, 1:10 000 bis 5:1, insbesondere 1 :1600 bis 4:3.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. 200 ml of a solution of the enzyme to be tested 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). The 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 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. In the agent according to the invention, 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.
Die Enzyme können insbesondere zum Einsatz in teilchenformigen Mitteln, wie zum Beispiel in der europäischen Patentschrift EP 0 564476 oder in der internationalen Patentanmeldung WO 94/23005 für andere Enzyme beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Die erfindungswesentliche Kombination aus bestimmter Cellullase und gegebenenfalls gentechnisch veränderter Protease kann durch Einarbeitung der zwei separaten beziehungsweise in bekannter Weise separat konfektionierten Enzyme oder durch gemeinsam in einem Granulat konfektionierte Cellulase und Protease, wie zum Beispiel aus den internationalen Patentanmeldungen WO 96/00772 oder WO 96/00773 bekannt, in erfindungsgemäßen Mitteln eingesetzt werden.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.
Ein erfindungsgemäßes Mittel enthält vorzugsweise bis zu 50 Gew.-%, insbesondere 5 Gew.-% bis 30 Gew.-% Alkalipercarbonat, wobei Natriumpercarbonat besonders bevorzugt ist. Es kann nach bekannten Verfahren hergestellt und insbesondere zum Einsatz in teilchenformigen Mitteln gewünschtenfalls in granulärer Form konfektioniert beziehungsweise stabilisiert und/oder umhüllt werden, wie es zum Beispiel aus den internationalen Patentanmeldungen 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 oder WO 95/15292 oder den europäischen Patentanmeldungen EP 0459 625, EP 0487256, EP 0 567 140, EP 0 623 553, EP 0 592 969 oder EP 0 748 764 bekannt ist. Aus Stabilitätsgründen bevorzugt setzt man es in Form eines Granulates ein, das mit Hilfe von Erdalkalisulfat, Alkalisulfat, Alkalisilikat, Erdalkalihalogenid, Alkalihalogenid, Alkalicarbonat, Alkalihydrogencarbonat, Alkaliphosphat, Alkaliborat, Alkaliperborat, Borsäure, teilweise hydratisiertem Alumosilikat, Carbonsäuren, Dicarbonsäuren, Polymeren aus ungesättigten Carbon- und/oder Dicarbonsäuren, oder Mischungen aus diesen hergestellt wurde beziehungsweise umhüllt ist. In einer bevorzugten Ausfiihrungsform weist es einen Morphologie-Index (MI), wie in EP 0451 893 definiert, von unter 0,06 auf.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 0 592 969 or EP 0 748 764. For reasons of stability, it is preferably used in the form of 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. In a preferred embodiment, it has a morphology index (MI), as defined in EP 0451 893, of less than 0.06.
Das Verhältnis von erfindungsgemäß zu verwendender Cellulase zu Alkalipercarbonat liegt in einer bevorzugten Ausgestaltung im Bereich von 0,0001 mg bis 0,1 mg, insbesondere von 0,001 mg bis 0,01 mg an cellulolytischem Protein pro Gew.-% an Alkalipercarbonat im Wasch- oder Reinigungsmittel.In a preferred embodiment, 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.
Die Wasch- oder Reinigungsmittel können vorzugsweise bei der Textilwäsche eingesetzte Voll- oder Feinwaschmittel sowie gegebenenfalls in einem Spülgang nach der Wäsche einsetzbarer Weichspüler sein. In einer bevorzugten Ausgestaltung der vorliegenden Erfindung bezieht sich die Verwendung der speziellen Cellulase auf die Verringerung der Redeposition bei der Textilwäsche mit Textilwaschmitteln auf Basis feinteiliger wasserunlöslicher anorganischer Builder-Komponenten, insbesondere Zeolith NaA.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. In a preferred embodiment of the present invention, 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.
Die Cellulase wie auch die gegebenenfalls zusätzlich eingesetzten Enzyme, zu denen neben der genannten Protease insbesondere Amylase, Lipase, Oxidase, Peroxidase, Cutinase, Pullulanase, Xylanase und/oder Hemicellulase sowie gegebenenfalls weitere Cellulasen und/oder Proteasen zu rechnen sind und welche vorzugsweise in Mengen von 0,1 Gew.-% bis 2 Gew.-% im Mittel vorhanden sind, können in Form von Flüssigformulierungen, gegebenenfalls unter Stabilisatorzusatz, in partikeli rmigen Waschmitteln jedoch vorzugsweise in an Trägerstoffen adsorbierter Form, in Hüllsubstanzen eingebettet oder in Form üblicher Granulate mit anorganischen und/oder organischen Trägermaterialien, wie beispielsweise in der deutschen Patentschrift DE 16 17 232, den deutschen Offenlegungsschriften DT 20 32 766 oder DE 40 41 752 oder den europäischen Patentanmeldungen EP 168 526, EP 170 360, EP 270 608 oder EP 304 331 beschrieben, eingesetzt werden. Dabei können die Enzyme in getrennten Partikeln enthalten sein oder in Form eines Mehrenzym-Granulats, wie beispielsweise in den deutschen Patentanmeldungen DE 4422433 oder DE 4422 609 oder den internationalen Patentanmeldungen WO 90/09440 oder WO 90/09428 sowie dem dort zitierten Stand der Technik beschrieben, eingesetzt werden. Die erfindungsgemäßen Wasch- und Reinigungsmittel, die als insbesondere pulverfbrmige Feststoffe, in nachverdichteter Teilchenform, als homogene Lösungen oder Suspensionen vorliegen können, können außer der erfindungsgemäß eingesetzten Kombination im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die erfindungsgemäßen Mittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, Bleichaktivatoren, wassermischbare organische Lösungsmittel, zusätzliche Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren sowie weitere Bleichmittel auf Basis organischer und/oder anorganischer Persauerstoffverbindungen und weitere Hilfsstoffe, wie optische Aufheller, Vergrauungsinhibitoren, Farbübertra- gungsinhibitoren, Schaumregulatoren, Silberkorrosionsinhibitoren sowie Färb- und Duftstoffe enthalten.The 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. In addition to the combination used according to the invention, 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.
Die erfindungsgemäßen Mittel können ein Tensid oder mehrere Tenside enthalten, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische, aber auch kationische, zwitterionische und amphotere Tenside in Frage kommen.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.
Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder Sulfonat-Gruppen enthalten. Als Tenside vom Sulfonat-Typ kommen vorzugsweise C - Cι3-Alkylbenzolsulfonate, Olefinsulfonate, das heißt Gemische aus Alken- und Hydroxy- alkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus Cι2-Cι8- Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C]2-Cι8-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse beziehungsweise Neutralisation gewonnen werden. Geeignet sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), zum Beispiel die α-sulfo- nierten Methylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren, die durch α- Sulfonierung der Methylester von Fettsäuren pflanzlichen und/oder tierischen Ursprungs mit 8 bis 20 C-Atomen im Fettsäuremolekül und nachfolgende Neutralisation zu wasserlöslichen Mono-Salzen hergestellt werden, in Betracht. Vorzugsweise handelt es sich hierbei um die α-sulfonierten Ester der hydrierten Kokos-, Palm-, Palmkern- oder Taigfettsäuren, wobei auch Sulfonierungsprodukte von ungesättigten Fettsäuren, beispielsweise Olsäure, in geringen Mengen, vorzugsweise in Mengen nicht oberhalb etwa 2 bis 3 Gew.-%, vorhanden sein können. Insbesondere sind α- Sulfofettsäurealkylester bevorzugt, die eine Alkylkette mit nicht mehr als 4 C-Atomen in der Estergruppe aufweisen, beispielsweise Methylester, Ethylester, Propylester und Butylester. Mit besonderem Vorteil werden die Methylester der α-Sulfofettsäuren (MES), aber auch deren verseifte Disalze eingesetzt. Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester, welche Mono-, Di- und Triester sowie deren Gemische darstellen, wie sie bei der Herstellung durch Veresterung durch ein Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der Cι2-Cιg-Fettalkohole beispielsweise aus Kokosfettalkohol, Taigfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der Cιo-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlänge bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind Cι2-Cι6- Alkylsulfate und Cι2-Cιs-Alkylsulfate sowie Cι -Ci5-Alkylsulfate insbesondere bevorzugt. Auch 2,3-Alkylsulfate, welche beispielsweise gemäß den US-amerikanischen Patentschriften US 3 234258 oder US 5 075 041 hergestellt werden und als Handelsprodukte der Shell Oil Company unter dem Namen DAN® erhalten werden können, sind geeignete Aniontenside. Geeignet sind auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-C2ι- Alkohole, wie 2-Methylverzweigte C9-Cπ -Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder Cι2-Ci8-Fettalkohole mit 1 bis 4 EO. Sie werden in Waschmitteln aufgrund ihres hohen Schaumverhaltens normalerweise nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt. Zu den bevorzugten Aniontensiden gehören auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden, und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8- bis Ci8-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfo- succinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen. Als weitere anionische Tenside kommen Fettsäure-Derivate von Aminosäuren, beispielsweise von N-Methyltaurin (Tauride) und/oder von N-Methylglycin (Sarkoside) in Betracht. Insbesondere bevorzugt sind dabei die Sarkoside beziehungsweise die Sarkosinate und hier vor allem Sarkosinate von höheren und gegebenenfalls einfach oder mehrfach ungesättigten Fettsäuren wie Oleylsarkosinat. Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind insbesondere gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierten Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkem- oder Taigfettsäuren, abgeleitete Seifengemische. Zusammen mit diesen Seifen oder als Ersatzmittel für Seifen können auch die bekannten Alkenylbernsteinsäuresalze eingesetzt werden.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. Also suitable are alkanesulfonates which are obtained from C] 2 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which have from 8 to by α-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. These are preferably the α-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. In particular, α-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 α-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage. Other 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. As 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. For reasons of washing technology, 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. Also suitable are the 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 Cι 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. 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. Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use 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.
Die anionischen Tenside, einschließlich der Seifen, können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triemanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants, including the soaps, 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.
Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylglykosiden oder linearen oder verzweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von N-Alkyl-aminen, vicinalen Diolen, Fettsäureestern und Fettsäure- amiden, die hinsichtlich des Alkylteils den genannten langkettigen Alkoholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomen im Alkylrest brauchbar.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. Corresponding 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.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxy- lierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durch- schnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C- Atomen, z.B. aus Kokos-, Palm-, Taigfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise Cι2-Cι4-Alkohole mit 3 EO oder 4 EO, C -Cn -Alkohole mit 7 EO, Cι - Cis-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-Cιg- Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus Cι2-Cι - Alkohol mit 3 EO und C|2- C ig- Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind (Talg-) Fettalkohole mit 14 EO, 16 EO, 20 EO, 25 EO, 30 EO oder 40 EO. Insbesondere in Reinigungsmitteln für den Einsatz in maschinellen Geschirrspülverfahren werden üblicherweise extrem schaumarme Verbindungen eingesetzt. Hierzu zählen vorzugsweise Cι2-C18-Alkylpolyethylenglykol-polypropylenglykolether mit jeweils bei zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Man kann aber auch andere bekannt schaumarme nichtionische Tenside verwenden, wie zum Beispiel Cι2-Cιg-Alkylpo- lyethylenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül sowie endgruppenverschlossene Alkylpolyalkylen- glykolmischether. Besonders bevorzugt sind auch die hydroxylgruppenhaltigen alkoxylierten Alkohole, wie sie in der europäischen Patentanmeldung EP 0300305 beschrieben sind, sogenannte Hydroxymischether. Zu den nichtionischen Tensiden zählen auch Alkylglykoside der allgemeinen Formel RO(G) eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl - die als analytisch zu bestimmende Größe auch gebrochene Werte annehmen kann - zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4. Ebenfalls geeignet sind Polyhydroxyfettsäureamide der Formel (I), in der R'CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht: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. However, 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, Cι - Cis alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -Cιg- alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cι 2 -Cι - alcohol with 3 EO and C | 2 - C ig alcohol with 7 EO. 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). In addition to these nonionic surfactants, 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. However, it is also possible to use other known 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. Also particularly preferred are the 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. 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. Also suitable are 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:
R2 R 2
R'-CO-N-fZ] (I)R'-CO-N-fZ] (I)
Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (II),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)
R4-O-R> R 4 -OR >
(II)(II)
R3-CO-N-[Z]R 3 -CO-N- [Z]
in der R3 für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R4 für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R5 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei Cι-C - Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO 95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO 90/13533 beschriebenen Verfahren hergestellt werden. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N.N- dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten „Spacer" voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, daß die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefallen werden unter dem Ausdruck Gemini-Tenside nicht nur derartig „dimere", sondern auch entsprechend „trimere" Tenside verstanden. Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether gemäß der deutschen Patentanmeldung DE 43 21 022 oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate gemäß der deutschen Patentanmeldung DE 195 03 061. Endgruppenverschlossene dimere und trimere Mischether gemäß der deutschen Patentanmeldung DE 195 13 391 zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so daß sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen. Eingesetzt werden können aber auch Gemini- Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide, wie sie in den interna- tionalen Patentanmeldungen WO 95/19953, WO 95/19954 und WO 95/19955 beschrieben werden.in which 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 and 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, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest is available. [Z] is also preferably obtained here by reductive amination of 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. Another class of preferred 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. In exceptional cases, the term 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.
Tenside sind in erfindungsgemäßen Waschmitteln in Mengenanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew.-% bis 30 Gew.-%, enthalten, wohingegen Mittel zur Reinigung harter Oberflächen, insbesondere zur maschinellen Reinigung von Geschirr, niedrigere Tensidgehalte von bis zu 10 Gew.-%, insbesondere bis zu 5 Gew.-% und vorzugsweise im Bereich von 0,5 Gew.-% bis 3 Gew.-% aufweisen.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.
Ein erfindungsgemäßes Mittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den wasserlöslichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, monomere und polymere Aminopolycarbonsäuren, insbesondere Methylglycindiessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessig- säure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylen- phosphonsäure), Emylendiamintetrakis(methylenphosphonsäure) und 1-Hydroxyethan- 1,1-diphosphonsäure, polymere Hydroxyverbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, insbesondere die durch Oxidation von Polysacchariden beziehungsweise Dextrinen zugänglichen Polycarboxylate der europäischen Patentschrift EP 0 625 992 beziehungsweise der internationalen Patentanmeldung WO 92/18542 oder der europäischen Patentschrift EP 0232 202, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative Molekülmasse der Homopolymeren ungesättiger Carbonsäuren liegt im allgemeinen zwischen 3 000 und 200000, die der Copolymeren zwischen 2 000 und 200 000, vorzugsweise 30000 bis 120 000, jeweils bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 30 000 bis 100000 auf. Handelsübliche Produkte sind zum Beispiel Sokalan® CP 5, CP 10 und PA 30 der Firma BASF. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinyl- ethern, wie Vinylmethylethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei ungesät- tigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/oder einem veresterten Vinylalkohol oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethylenisch ungesättigten C3-Cg-Carbonsäure und vorzugsweise von einer C3-C -Monocarbonsäure, insbesondere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C -Cg-Dicarbonsäure, wobei Maleinsäure besonders bevorzugt ist, und/oder ein Derivat einer Allylsulfonsäure, die in 2-Stellung mit einem Alkyl- oder Arylrest substituiert ist, sein. Derartige Polymere lassen sich insbesondere nach Verfahren herstellen, die in der deutschen Patentschrift DE 4221 381 und der deutschen Patentanmeldung DE 43 00 772 beschrieben sind, und weisen im allgemeinen eine relative Molekülmasse zwischen 1 000 und 200000 auf. Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE 43 03 320 und DE 44 17 734 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäure- salze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen können, insbesondere zur Herstellung flüssiger Mittel, in Form wäßriger Lösungen, vorzugsweise in Form 30- bis 50-gewichtsprozentiger wäßriger Lösungen eingesetzt werden. Alle genannten Säuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt.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 oxidation of polysaccharides or dextrins Acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also contain small amounts of polymerizable substances without carboxylic acid functionality can. 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.
Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 Gew.-% bis 8 Gew.- % enthalten sein. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenförmigen oder flüssigen, insbesondere wasserhaltigen, erfindungsgemäßen Mitteln eingesetzt.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.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Alkalisilikate, Alkalicarbonate und Alkaliphosphate, die in Form ihrer alkalischen, neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können, in Betracht. Beispiele hierfür sind Trinatriumphosphat, Tetranatriumdiphosphat, Dinatriumdihydrogendiphosphat, Pentana- triumtriphosphat, sogenanntes Natriumhexametaphosphat, oligomeresParticularly 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
Trinatriumphosphat mit Oligomerisierungsgraden von 5 bis 1000, insbesondere 5 bis 50, sowie die entsprechenden Kaliumsalze beziehungsweise Gemische aus Natrium- und Kaliumsalzen. Als wasserunlösliche, wasserdispergierbare anorganische Buildermateria- lien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-% und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, P und gegebenenfalls X, allein oder in Mischungen, beispielsweise in Form eines Co-Kristallisats aus den Zeolithen A und X (Vegobond® AX, ein Handelsprodukt der Condea Augusta S.p.A.), bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenformigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 μm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 μm. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patentschrift DE 24 12 837 bestimmt werden kann, liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm.Trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts. As 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. Among these, 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 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. 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.
Geeignete Substitute beziehungsweise Teilsubstitute für das genannte Alumosilikat sind kristalline Alkalisilikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können. Die in den erfindungsgemäßen Mitteln als Gerüststoffe brauchbaren Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu SiO unter 0,95, insbesondere von 1:1,1 bis 1:12 auf und können amorph oder kristallin vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na2O:SiO2 von 1:2 bis 1:2,8. Solche mit einem molaren Verhältnis Na2O:SiO2 von 1:1,9 bis 1:2,8 können nach dem Verfahren der europäischen Patentanmeldung EP 0425 427 hergestellt werden. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der allgemeinen Formel Na2SixO2x+ι y H2O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1,9 bis 22, insbesondere 1,9 bis 4 und y eine Zahl von 0 bis 33 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Kristalline Schichtsilikate, die unter diese allgemeine Formel fallen, werden beispielsweise in der europäischen Patentanmeldung EP 0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch f3-Natriumdisilikate (Na2Si2O5 y H2O) bevorzugt, wobei ß-Natriumdisilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO 91/08171 beschrieben ist. δ- Natriumsilikate mit einem Modul zwischen 1,9 und 3,2 können gemäß den japanischen Patentanmeldungen JP 04/238 809 oder JP 04/260 610 hergestellt werden. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1,9 bis 2,1 bedeutet, herstellbar wie in den europäischen Patentanmeldungen EP 0 548 599, EP 0 502 325 und EP 0452428 beschrieben, können in erfindungsgemäßen Mitteln eingesetzt werden. In einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es nach dem Verfahren der europäischen Patentanmeldung EP 0436 835 aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1 ,9 bis 3,5, wie sie nach den Verfahren der europäischen Patentschriften EP 0 164 552 und/oder EP 0 294 753 erhältlich sind, werden in einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel eingesetzt. Kristalline schichtförmige Silikate der oben angegebenen Formel (I) werden von der Fa. Clariant GmbH (Deutschland) unter dem Handelsnamen Na-SKS vertrieben, z.B. Na-SKS-1 (Na2Si22O 5 xH2O, Kenyait), Na- SKS-2 (Na2SiHO29xH2O, Magadiit), Na-SKS-3 (Na2Si87xH2O) oder Na-SKS-4 (Na2Si4O9'xH O, Makatit). Von diesen eignen sich vor allem Na-SKS-5 (α-Na2Si 05), Na-SKS-7 (ß-Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O5 H2O), Na-SKS- 10 (NaHSi2O53H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) und Na-SKS- 13 (NaHSi2O5), insbesondere aber Na-SKS-6 (δ-Na2Si2θ5). Einen Überblick über kristalline Schichtsilikate geben zum Beispiel die im "Hoechst High Chem Magazin 14/1993" auf den Seiten 33 - 38 und in "Seifen-Öle-Fette- Wachse, 116 Jahrgang, Nr. 20/1990" auf den Seiten 805 - 808 veröffentlichten Artikel. In einer bevorzugten Ausgestaltung erfindungsgemäßer Mittel setzt man ein granuläres Compound aus kristallinem Schichtsilikat und Citrat, aus kristallinem Schichtsilikat und oben genannter (co-)polymerer Polycarbon- säure, wie es zum Beispiel in der deutschen Patentanmeldung DE 198 19 187 beschrieben ist, oder aus Alkalisilikat und Alkalicarbonat ein, wie es zum Beispiel in der internationalen Patentanmeldung WO 95/22592 beschrieben ist oder wie es beispielsweise unter dem Namen Nabion® 15 im Handel erhältlich ist.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. Those with a Na 2 O: SiO 2 molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0425 427. Crystalline sheet silicates of the general formula Na 2 Si x O 2x + ι 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. In particular, both β- and f3-sodium disilicate (Na 2 Si 2 O 5 y H 2 O) are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171. δ- 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. Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0452428, can be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent EP 0 164 552 and / or EP 0 294 753, 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 87 xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 'xH O, Makatit). Of these, Na-SKS-5 (α-Na 2 Si 0 5 ), Na-SKS-7 (β-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 (δ-Na 2 Si 2 θ 5 ). An overview of crystalline layered silicates is 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. In a preferred embodiment of agents according to the invention, a granular compound composed of crystalline layered silicate and citrate, of crystalline layered silicate and the (co) polymeric polycarbonic acid mentioned above, as described for example in German patent application DE 198 19 187, or of alkali silicate and alkali carbonate, as described, for example, in international patent application WO 95/22592 or as is commercially available, for example, under the name Nabion® 15.
Buildersubstanzen können in den erfindungsgemäßen Mitteln gegebenenfalls in Mengen bis zu 90 Gew.-% enthalten sein. Sie sind vorzugsweise in Mengen bis zu 75 Gew.-% enthalten. Erfindungsgemäße Waschmittel weisen Buildergehalte von insbesondere 5 Gew.-% bis 50 Gew.-% auf. In erfindungsgemäßen Mitteln für die Reinigung harter Oberflächen, insbesondere zur maschinellen Reinigung von Geschirr, beträgt der Gehalt an Buildersubstanzen insbesondere 5 Gew.-% bis 88 Gew.-%, wobei in derartigen Mitteln vorzugsweise keine wasserunlöslichen Buildermaterialien eingesetzt werden. In einer bevorzugten Ausführungsform erfindungsgemäßer Mittel zur insbesondere maschinellen Reinigung von Geschirr sind 20 Gew.-% bis 40 Gew.-% wasserlöslicher organischer Builder, insbesondere Alkalicitrat, 5 Gew.-% bis 15 Gew.-% Alkalicarbonat und 20 Gew.-% bis 40 Gew.-% Alkalidisilikat enthalten.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. In a preferred embodiment of 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.
Als für den Einsatz in erfindungsgemäßen Mitteln geeignete Persauerstoffverbindungen kommen neben dem bereits genannten Alkalipercarbonat insbesondere organische Persäuren beziehungsweise persaure Salze organischer Säuren, wie Phthalimidopercapronsäure, Perbenzoesäure oder Salze der Diperdodecandisäure, Wasserstoffperoxid und unter den Waschbedingungen Wasserstoffperoxid abgebende anorganische Salze, zu denen Perborate, Persilikate und/oder Persulfate wie Caroat gehören, in Betracht. Sofern feste Persauerstoffverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Falls ein erfindungsgemäßes Mittel Persauerstoffverbindungen enthält, sind diese in Mengen von vorzugsweise bis zu 50 Gew.-%, insbesondere von 5 Gew.-% bis 30 Gew.-%, vorhanden. Der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten beziehungsweise Metaboraten und Metasilikaten sowie Magnesiumsalzen wie Magnesiumsulfat kann zweckdienlich sein.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. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. If 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. The addition of small amounts of known bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may be useful.
Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl- 2,4-dioxohexahydro-l,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und die aus den deutschen Patentanmeldungen DE 196 16693 und DE 196 16 767 bekannten Enolester sowie acetyliertes Sorbitol und Mannitol beziehungsweise deren in der europäischen Patentanmeldung EP 0 525 239 beschriebene Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam, die aus den internationalen Patentanmeldungen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 und WO 95/17498 bekannt sind. Die aus der deutschen Patentanmeldung DE 196 16 769 bekannten hydrophil substituierten Acylacetale und die in der deutschen Patentanmeldung DE 196 16 770 sowie der internationalen Patentanmeldung WO 95/14075 beschriebenen Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch die aus der deutschen Patentanmeldung DE 4443 177 bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige Bleichaktivatoren können im üblichen Mengenbereich, vorzugsweise in Mengen von 0,5 Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 8 Gew.-%, bezogen auf gesamtes Mittel, enthalten sein.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. Preferred are 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 well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN) Sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, WO 94/2979 / WO70 / 94 / WO 94 / WO79 / WO79 / 94, WO 94/94/7979 patent applications 28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are not. The 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.
Zusätzlich zu den oben aufgeführten konventionellen Bleichaktivatoren oder an deren Stelle können auch die aus den europäischen Patentschriften EP 0446982 und EP 0453 003 bekannten Sulfonimine und/oder bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetallkomplexe als sogenannte Bleichkatalysatoren enthalten sein.In addition to the conventional bleach activators listed above or in their place, 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.
Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, neben Wasser verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylen- glykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen nicht über 30 Gew.-%, insbesondere von 6 Gew.-% bis 20 Gew.-%, vorhanden.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.
Zusätzlich können die Mittel weitere in Wasch- und Reinigungsmitteln übliche Bestandteile enthalten. Zu diesen fakultativen Bestandteilen gehören insbesondere Enzymstabilisatoren, Vergrauungsinhibitoren, Farbübertragungsinhibitoren, Schauminhibitoren, und optische Aufheller sowie Färb- und Duftstoffe. Um einen Silberkorrosionsschutz zu bewirken, können in erfindungsgemäßen Reinigungsmitteln für Geschirr Silberkorrosionsinhibitoren eingesetzt werden. Ein erfindungsgemäßes Reinigungsmittel für harte Oberflächen kann darüber hinaus abrasiv wirkende Bestandteile, insbesondere aus der Gruppe umfassend Quarzmehle, Holzmehle, Kunststoffinehle, Kreiden und Mikroglaskugeln sowie deren Gemische, enthalten. Abrasivstoffe sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 5 Gew.-% bis 15 Gew.-%, enthalten.In addition, 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. In order to provide silver corrosion protection, 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.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH- Werts können die erfindungsgemäßen Mittel system- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Basen, insbesondere Ammoniumoder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsgemäßen Mitteln in Mengen von vorzugsweise nicht über 20 Gew.-%, insbesondere von 1,2 Gew.-% bis 17 Gew.-%, enthalten.To set a desired pH value which does not result from the mixture of the other components, 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.
Zu den für den Einsatz in erfindungsgemäßen Textilwaschmitteln in Frage kommenden Farbübertragungsinhibitoren gehören insbesondere Polyvinylpyrrolidone, Polyvinyl- imidazole, polymere N-Oxide wie Poly-(vinylpyridin-N-oxid) und Copolymere von Vinylpyrrolidon mit Vinylimidazol.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.
Auch zusätzliche Vergrauungsinhibitoren können in den erfindungsgemäßen Mitteln vorhanden sein. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise Stärke, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich andere als die obengenannten Stärkederivate verwenden, zum Beispiel Aldehydstärken. Bevorzugt werden Celluloseether, wie Carboxymethylcellulose (Na-Salz), Methylcellulose. Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methyl - hydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische, beispielsweise in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Mittel, eingesetzt.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.
Erfindungsgemäße Textilwaschmittel können als optische Aufheller Derivate der Diaminostilbendisulfonsäure beziehungsweise deren Alkalimetallsalze enthalten. Geeignet sind zum Beispiel Salze der 4,4'-Bis(2-aniHno-4-morpholino-l,3,5-triazinyl-6- amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, zum Beispiel die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-di- phenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten optischen Aufheller können verwendet werden.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.
Insbesondere beim Einsatz in maschinellen Verfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an Cι8-C2 -Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bisfettsäurealkylendiamiden. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, zum Beispiel solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren, insbesondere Silikon- und/oder Paraffin-hakige Schauminhibitoren, an eine granuläre, in Wasser lösliche beziehungsweise dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamid bevorzugt. Die Herstellung erfindungsgemäßer fester Mittel bietet keine Schwierigkeiten und kann auf bekannte Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei die Enzyme und eventuelle weitere thermisch empfindliche Inhaltsstoffe wie zum Beispiel Bleichmittel gegebenenfalls später separat zugesetzt werden. Zur Herstellung erfindungsgemäßer Mittel mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/1 bis 950 g 1, ist ein aus der europäischen Patentschrift EP 0486 592 bekanntes, einen Extrusionschritt aufweisendes Verfahren bevorzugt. Eine weitere bevorzugte Herstellung mit Hilfe eines Granulationsverfahrens ist in der europäischen Patentschrift EP 0 642 576 beschrieben.In particular when used in machine processes, it can be advantageous to add conventional foam inhibitors to the agents. 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. For the production of 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.
Zur Herstellung von erfindungsgemäßen Mitteln in Tablettenform, die einphasig oder mehrphasig, einfarbig oder mehrfarbig und insbesondere aus einer Schicht oder aus mehreren, insbesondere aus zwei Schichten bestehen können, geht man vorzugsweise derart vor, daß man alle Bestandteile - gegebenenfalls je einer Schicht - in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßkräften im Bereich von etwa 50 bis 100 kN, vorzugsweise bei 60 bis 70 kN verpreßt. Insbesondere bei mehrschichtigen Tabletten kann es von Vorteil sein, wenn mindestens eine Schicht vorverpreßt wird. Dies wird vorzugsweise bei Preßkräften zwischen 5 und 20 kN, insbesondere bei 10 bis 15 kN durchgeführt. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Bruch- und Biegefestigkeiten von normalerweise 100 bis 200 N, bevorzugt jedoch über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 10 g bis 50 g, insbesondere von 15 g bis 40 g auf. Die Raumform der Tabletten ist beliebig und kann rund, oval oder eckig sein, wobei auch Zwischenformen möglich sind. Ecken und Kanten sind vorteilhafterweise abgerundet. Runde Tabletten weisen vorzugsweise einen Durchmesser von 30 mm bis 40 mm auf. Insbesondere die Größe von eckig oder quaderförmig gestalteten Tabletten, welche überwiegend über die Dosiervorrichtung beispielsweise der Geschirrspülmaschine eingebracht werden, ist abhängig von der Geometrie und dem Volumen dieser Dosiervorrichtung. Beispielhaft bevorzugte Ausführungsformen weisen eine Grundfläche von (20 bis 30 mm) x (34 bis 40 mm), insbesondere von 26x36 mm oder von 24x38 mm auf. Flüssige beziehungsweise pastöse erfindungsgemäße Wasch- oder Reinigungsmittel in Form von übliche Lösungsmittel enthaltenden Lösungen werden in der Regel durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt. For the preparation of 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. In the case of multi-layer tablets in particular, it can be advantageous if at least one layer is pre-compressed. This is preferably carried out at press forces between 5 and 20 kN, in particular at 10 to 15 kN. In this way, 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. In particular, 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.
BeispieleExamples
Beispiel 1example 1
Zu einem enzymfreien Basiswaschmittel BWl wurden die in Tabelle 1 angegebenen Cellulasen gegeben. Die Cellulasen kamen bezogen auf Protein in jeweils einer solchen Menge zum Einsatz, die einer Einsatzmenge von 0,6 Gew.-% Celluzyme® 0,7T (Hersteller: Novo Nordisk) im jeweils verwendeten Waschmittel entsprach. Die Gewebe- vergrauung - bestimmt über die Remission nach 10 Wäschen - wurde ermittelt, wobei unter den nachfolgenden Bedingungen Waschversuche durchgeführt wurden: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:
Waschmaschine: Miele® W918Washing machine: Miele® W918
Temperatur: 40 °CTemperature: 40 ° C
Waschmittel-Dosierung: 76 gDetergent dosage: 76 g
Wasserhärte: 16 °dHWater hardness: 16 ° dH
Beladung: 2,5 kg saubere Wäsche (Baumwolltestgewebe der WäschforschungsanstaltLoad: 2.5 kg of clean laundry (cotton test fabric from the laundry research institute
Krefeld, Kopfkissenbezüge, Frottierhandtücher, Unterhemden und Küchenhandtücher)Krefeld, pillowcases, terry towels, undershirts and kitchen towels)
Anschmutzung: Bei jeder Wäsche wurden 5 Strängchen Baumwolle mit standardisierterSoiling: 5 strands of cotton with standardized
Staub/Hautfett-Anschmutzung hinzugegebenDust / skin fat soiling added
Die nach der Wäsche mit den angegebenen Rezepturen erhaltenen Zahlenwerte für die Vergrauung (angegeben als % Remission, Durchschnittswerte über alle Textilien) sind in der nachfolgenden Tabelle 1 zusammengestellt, wobei der Remissionsanfangswert vor den Wäschen und der Wert für das enzymfreie Basiswaschmittel zum Vergleich ebenfalls angegeben sind.The numerical values for graying obtained after washing with the specified recipes (given as% remission, average values for all textiles) are summarized in Table 1 below, the initial remission value before the washes and the value for the enzyme-free basic detergent are also given for comparison ,
Tabelle 1Table 1
a) Cellulase gemäß WO 96/34108 a) Cellulase according to WO 96/34108
Man erkennt, daß bei Einsatz der erfindungsgemäß zu verwendenden Cellulase eine bessere Vergrauungsinhibierung auftritt als bei Einsatz anderer Celluasen.It can be seen that when the cellulase to be used according to the invention is used, better graying inhibition occurs than when other celluases are used.
Beispiel 2Example 2
Beispiel 1 wurde wiederholt, wobei abweichend von dem dort beschriebenen Vorgehen 11 Wäschen durchgeführt wurden und ein Basiswaschmittel BW2 zum Einsatz kam, das im Unterschied zu BWl 1,2 Gew.-% eines die Protease BLAP enthaltenden Enzymgranulats mit einer Aktivität von 200000 PE/g enthielt.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.
Tabelle 1Table 1
a) Cellulase gemäß WO 96/34108a) Cellulase according to WO 96/34108
Man erkennt, daß ein erfindungsgemäßes Mittel eine bessere vergrauungsinhibierende Wirkung aufweist als ein Mittel, das statt der erfindungsgemäß zu verwendenden Cellulase eine andere Celluase enthält. It can be seen that 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.

Claims

Patentansprüche claims
1. Verwendung von aus Melanocarpus sp. oder Myriococcum sp. erhältlicher 20K- Cellulase oder solcher, die eine Homologie von über 80 % dazu aufweist, als Vergrauungsinhibitor in Waschmitteln.1. Use of Melanocarpus sp. or Myriococcum sp. Available 20K cellulase or those which have a homology of more than 80%, as a graying inhibitor in detergents.
2. Verwendung von aus Melanocarpus sp. oder Myriococcum sp. erhältlicher 20K- Cellulase oder solcher, die eine Homologie von über 80 % dazu aufweist, als Vergrauungsinhibitor in Waschmitteln, die feinteiligen wasserunlöslichen anorganischen Builder, insbesondere Zeolith, enthalten.2. Use of Melanocarpus sp. or Myriococcum sp. Available 20K cellulase or those which have a homology of over 80% to it, as graying inhibitor in detergents which contain finely divided water-insoluble inorganic builders, in particular zeolite.
3. Verwendung von aus Melanocarpus sp. oder Myriococcum sp. erhältlicher 20K- Cellulase oder solcher, die eine Homologie von über 80 % dazu aufweist, zur Verringerung der Redeposition bei der Textilwäsche mit Textilwaschmitteln auf Basis feinteiliger wasserunlöslicher anorganischer Builder-Komponenten3. Use of Melanocarpus sp. or Myriococcum sp. Available 20K cellulase or those which have a homology of over 80% to reduce the redeposition in textile washing with textile detergents based on finely divided water-insoluble inorganic builder components
4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Waschmittel als Builder 10 Gew.-% bis 50 Gew.-%, insbesondere 10 Gew.-% bis 40 Gew.-% wasserunlösliches, wasserdispergierbares anorganisches Buildermaterial in Waschmittelqualität, insbesondere kristallines Alkalisilikat, kristallines und/oder amorphes Alkalialumosilikat, insbesondere Zeolith A, Zeolith P und/oder Zeolith X, enthält.4. Use according to one of claims 1 to 3, characterized in that the detergent as a builder 10 wt .-% to 50 wt .-%, in particular 10 wt .-% to 40 wt .-% water-insoluble, water-dispersible inorganic builder material in detergent quality , in particular crystalline alkali silicate, crystalline and / or amorphous alkali alumosilicate, in particular zeolite A, zeolite P and / or zeolite X, contains.
5. Wasch- oder Reinigungsmittel, welches die aus Melanocarpus sp. oder Myriococcum sp. erhältliche 20K-Cellulase oder eine Cellulase, die eine Homologie von über 80 % dazu aufweist, in Kombination mit einer gegebenenfalls gentechnisch veränderten Protease aus Bacillus lentus und/oder Alkalipercarbonat enthält.5. Detergent or cleaning agent, which from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase or a cellulase, which has a homology of over 80%, in combination with an optionally genetically modified protease from Bacillus lentus and / or alkali percarbonate.
6. Mittel nach Anspruch 5, dadurch gekennzeichnet, daß es eine auf die aus Melanocarpus sp. oder Myriococcum sp. erhältliche 20K-Cellulase oder eine Cellulase, die eine Homologie von über 80 % dazu aufweist, zurückgehende cellulolytische Aktivität von 1 NCU/g bis 500 NCU/g, insbesondere von 5 NCU/g bis 400 NCU/g aufweist.6. Composition according to claim 5, characterized in that there is one on the Melanocarpus sp. or Myriococcum sp. Available 20K cellulase or a cellulase that has over 80% homology to declining has cellulolytic activity from 1 NCU / g to 500 NCU / g, in particular from 5 NCU / g to 400 NCU / g.
7. Mittel nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß in der gentechnisch veränderten Protease aus Bacillus lentus mindestens einer der Aminosäureaustausche S3T, V4I , V193M, V199I, oder L211D vorgenommen wurde.7. Composition according to claim 5 or 6, characterized in that at least one of the amino acid exchanges S3T, V4I, V193M, V199I, or L211D was made in the genetically modified protease from Bacillus lentus.
8. Mittel nach einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, daß das Verhältnis der cellulolytischen Aktivität, ausgedrückt in NCU/g, zur proteolytischen Aktivität, ausgedrückt in PE/g, im Bereich von 1:10 000 bis 5:1, insbesondere von 1:600 bis 4:3 liegt.8. Composition according to one of claims 5 to 7, characterized in that the ratio of cellulolytic activity, expressed in NCU / g, to proteolytic activity, expressed in PE / g, in the range from 1:10 000 to 5: 1, in particular from 1: 600 to 4: 3.
9. Mittel nach einem der Ansprüche 5 bis 8, dadurch gekennzeichnet, daß es 50 Gew.- %, insbesondere 5 Gew.-% bis 30 Gew.-% Alkalipercarbonat, insbesondere Na- triumpercarbonat enthält.9. Composition according to one of claims 5 to 8, characterized in that it contains 50% by weight, in particular 5% by weight to 30% by weight, of alkali percarbonate, in particular sodium percarbonate.
10. Mittel nach einem der Ansprüche 5 bis 9, dadurch gekennzeichnet, daß es 0,0001 mg bis 0,1 mg, insbesondere 0,001 mg bis 0,01 mg an cellulolytischem Protein pro Gew.-% an Alkalipercarbonat enthält. 10. Composition according to one of claims 5 to 9, characterized in that it contains 0.0001 mg to 0.1 mg, in particular 0.001 mg to 0.01 mg of cellulolytic protein per wt .-% of alkali percarbonate.
EP00967895A 1999-10-29 2000-10-20 Enzymatic graying inhibitor Expired - Lifetime EP1224254B1 (en)

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