WO2001032818A1

WO2001032818A1 - Enzyme-containing high-viscosity liquid detergents

Info

Publication number: WO2001032818A1
Application number: PCT/EP2000/010337
Authority: WO
Inventors: Dieter Nickel; Theodor Völkel
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-11-03
Filing date: 2000-10-20
Publication date: 2001-05-10
Also published as: CA2325159A1; AU7789500A; DE19953057A1

Abstract

The invention relates to enzyme-containing high viscosity liquid detergents. The aim of the invention is to improve the stability of aqueous, high-viscosity liquid detergents that contain a tenside and 0.1 % by weight to 5 % by weight of a polymer thickener and other conventional ingredients. To this end, the inventive detergents contain a tenside on the basis of saccharide, at least one enzyme from the group comprising cellulase, amylase and protease and an enzyme stabilizer system that consists of the components a) a boron compound and/or a sodium formiate and b) a polyvalent alcohol.

Description

Enzyme-containing, higher-viscosity liquid detergents

The present invention relates to liquid detergents containing enzymes and surfactants which, due to the use of a thickener and an enzyme stabilization system, are stable in storage and viscosity under a wide variety of climatic conditions, are not subject to phase separation and have color stability even when exposed to light.

Higher viscosity detergents and cleaning agents as well as cosmetics have become increasingly popular in recent years, with such products with a gel-like consistency being widely accepted by consumers. In the field of liquid detergents, higher-viscosity gel products have the advantage that less non-aqueous solvents can be used and the product can be applied specifically to the stains without running. Conventional liquid detergents are usually used through the use of thickeners such as agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose and other cellulose ethers such as hydroxyethyl and -propyl cellulose, powdered meal ether, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides. Polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas are converted into higher-viscosity products. The use of these thickeners to increase viscosity in a wide variety of liquids has long been state of the art. The use of polymers in liquid detergents is also well known.

The incorporation of the thickeners mentioned does not necessarily lead to stable gels in liquid detergents. Gel formation is usually only possible by coordinating the type and amount of the individual ingredients with the thickener used, some of the thickeners being incompatible with the ingredients of a liquid detergent. After a few weeks of storage, such products show an agglomerate formation, which becomes apparent when the formulation becomes opaque ("cloud formation"). In addition, the viscosity of such products drops drastically during storage. As a rule, higher-viscosity liquid detergents to underline the aesthetic characteristics in transparent bottles are offered, it is also necessary that the thickeners used are stable to light, since otherwise a radical decomposition of the polymers occurs, which is reflected in the destruction of the product color and undesirable "cloud formation".

Liquid detergents with viscosities between 500 to 20,000 mPas, preferably from 2,000 to 10,000 mPas, in which lamellar surfactant droplets are dispersed in an aqueous electrolyte phase are described in European patent application EP 0 691 399. These compositions contain 10 to 45% by weight of surfactant (s), at least one builder and 0.01 to 5% by weight of a mercapto-terminated polymer with an average molecular weight of between 1500 and 50,000 gmol ^"1 .

The use of boron compounds in aqueous liquid detergents is described in European patent application EP 0 381 262. These liquid detergents contain boron compounds and a polyol as an enzyme stabilization system for a mixture of proteolytic and lipolytic enzymes, preferred stabilization systems consisting of a sorbitol / borax mixture. Nothing is said in this document about the viscosity and stability of liquid detergents.

Liquid, aqueous detergent concentrates which maintain or increase their viscosity when diluted with water are described in European patent application EP 0 724 013. This effect is achieved through the use of two surfactants with different resistance to electrolytes and the addition of a dissolved electrolyte, whereby the concentrate has a viscosity of less than 2500 mPas and loses its micellar structure in favor of the formation of a lamellar phase when diluted with water.

International patent application WO 96/01305 describes an aqueous cleaning and liquid detergent which, when diluted with at least twice the amount of water, forms a microemulsion which has particle sizes of 10 to 100 nm. The composition contains 20 to 70% by weight of water, 15 to 40% by weight of a surfactant system which contains at least one nonionic surfactant from the group of the alkoxylated alcohols and not more than 20 % By weight of anionic, cationic, ampho- or zwitterionic surfactant contains 5 to 30% by weight of solvent and 5 to 20% by weight of water-insoluble oil.

From the German patent application DE 197 52 165 aqueous, higher-viscosity liquid detergents are known, containing surfactant (s) and other usual ingredients of detergents and cleaning agents, the agents as a thickening system, based in each case on the total agent, 0.1 to 5% by weight. -% of a polymeric thickener, 0.5 to 7 wt .-% of a boron compound and 1 to 8 wt .-% of a complexing agent. The agents known from this publication are stable in viscosity, do not tend to agglomerate or phase separation and have no reduction in color stability under the influence of light. The document contains no information on the possible stability of enzymes contained in such agents.

None of the cited documents deals with the problem of providing higher-viscosity enzyme-containing liquid detergents which guarantee a stable viscosity, if possible suffer no loss of enzymatic activity when stored, do not lead to agglomerate formation (so-called “cloud formation”) or phase separation and do not reduce the color stability The present invention seeks to solve this problem.

It has now been found that enzyme-containing liquid detergents with the property profile mentioned can be prepared if a polymeric thickener, a special enzyme stabilizer system and a specific surfactant are incorporated into the detergents.

The invention therefore relates to enzyme-containing, aqueous, highly viscous liquid detergents, containing surfactant and 0.1 to 5% by weight of polymeric thickener, and further conventional ingredients of detergents and cleaning agents, the agents being characterized in that they contain surfactant based on saccharide, contain at least one enzyme from the group comprising cellulase, amylase and protease and an enzyme stabilizer system from the components a) boron compound and / or sodium formate and b) polyhydric alcohol. The use of the polymeric thickener makes it possible to produce higher-viscosity liquid detergents which are free from the disadvantages mentioned. According to the invention, it is possible to produce concentrated, higher-viscosity liquid detergents which have surfactant contents above 35% by weight.

An agent according to the invention contains at least one protease. Cellulase or amylase, preferably at least two of these enzymes and particularly preferably all three enzymes being present. In preferred embodiments, the agents according to the invention contain protease and amylase, protease and cellulase, amylase and cellulase or protease, amylase and cellulase. If desired, more than one representative from one of the enzyme classes mentioned can also be present.

In addition to the proteases obtainable or genetically modified from various Bacillus species, such as Alcalase®, Esperase®, Savinase®, Durazym® or Everlase®, the proteases preferably used include the protease from Bacillus lentus, which is stable and active under 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 Bacillus licheniformis transformed with an expression plasmid which carries the gene for BLAP under the control of the Bacillus licheniformis ATCC 53926 promoter. The composition as well as the spatial structure of BLAP is known (DW 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. In addition to the naturally occurring protease from Bacillus lentus, the proteases which can be used according to the invention also include genetically modified ones Proteases of the abovementioned BLAP type, in which the amino acid leucine (L in the customary one-letter code) present at this point in the wild-type protease in position 211 (BLAP count) is replaced by aspartic acid (D) or glutamic acid (E) is (L21 1D or L21 1E). These can be produced as described in international patent application WO 95/23221. 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 VI 991, 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 L21 1D 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 '. An agent according to the invention preferably contains Savinase® and / or an optionally genetically modified protase from Bacillus lentus.

Amylases have the task of facilitating the removal of starchy soiling by the catalytic hydrolysis of the starch polysaccharide and for this purpose have been used for a long time in detergents for dishes, but also in detergents for use in textile washing. In the agents according to the invention, both amylases of the Termamyl® type and genetically modified amylases, that is to say those having an amino acid sequence which has been modified in comparison to naturally occurring amylases with the aid of genetic engineering methods, can be used, as described, for example, in international patent applications WO 94/18314 or WO 95/21247 are known.

The cellulase which can be used according to the invention belongs to the enzymes which can be obtained from bacteria or fungi and which preferably have a pH optimum of almost neutral to have a weakly alkaline pH range from 6 to 9.5. Such cellulases are known, for example, from German laid-open documents DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832. EP 269 077, EP 270 974, EP 273 125 and EP 339 550 known. Suitable commercial products are, for example, Celluzyme® and Carezyme® from Novo Nordisk or KAC® from Kao. In addition to Carezyme®, the preferred cellulases also include those from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase, which 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.

In addition to the enzymes mentioned, the agents according to the invention can, if desired, include further enzymes, in particular from the group consisting of lipases, cutinases, isopeptidases, xylanases, hemicellulases, pullulanases, neopullulanases, mannanases, mycodextranans, polygalacturanase, keratanases, chondroitinases, pectinases, laccatases and oxidases / or contain peroxidases.

The saccharide-based surfactants include, on the one hand, alkyl glycosides of the general formula RO (G) _x , in which R is 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 is the symbol which stands 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 and can also take fractional numbers, is an analytically determinable number between 1 and 10; x is preferably 1.2 to 1.4. The saccharide-based surfactants also include polyhydroxy fatty acid amides of the formula I,

R ¹

R-CO-N- [Z]

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula II

R0O-R ²

R-CO-N- [Z] II

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1 -C 6 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical , [Z] is preferably obtained by reductive amination of a sugar, for example 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 Reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst can be converted into the desired polyhydroxy fatty acid amides.

The content of preferred liquid detergents in such surfactants based on saccharide is 0.5 to 25% by weight. preferably 1 to 10 wt .-% and in particular 1.5 to 5 wt .-%, each based on the total agent.

Another essential component of the invention of the enzyme-containing, higher-viscosity liquid detergent is a polymeric thickener. These organic high-molecular substances, which are also called swelling agents, soak up liquids, swell them up and finally convert into viscous real or colloidal solutions, come from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers and their mixtures.

From nature-derived polymers which can be used as thickening agents according to the invention using, ^"for example, agar-agar, carrageen, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, carob bean flour, starch, dextrins, gelatin and casein.

Modified natural products come primarily from the group of modified starches and celluloses. carboxymethyl cellulose and other cellulose ethers are exemplary here. Hydroxyethyl and propyl cellulose and core meal ether called.

A large group of thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds. Vinyl polymers, polycarboxylic acids, polyethers. Polyimines, polyamides and polyurethanes. Such fully synthetic polymeric thickeners are preferably present in agents according to the invention in amounts from 0.2% by weight to 4% by weight, in particular from 0.4% by weight to 3% by weight and particularly preferably from 0.5% by weight. -% to 2 wt .-% contain. In a preferred embodiment of the invention, mixtures of optionally modified natural polymer and fully synthetic polymer are used as polymeric thickeners. Thickeners from the substance classes mentioned are commercially available and are sold, for example, under the trade names Acusol -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer. 30% strength in water, Rohm & Haas). Dapral ^® -GT-282-S (alkyl polyglycol ether, Akzo), Deuteron polymer 11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schoener GmbH), Deuteron ^® -XN (non-ionic polysaccharide, Schoener GmbH), Dicrylan ^® thickener-O (ethylene oxide adduct, 50% in water isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride copolymer, Monsanto). Thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox ^& -AM (anionic acrylic acid-acrylic acid ester copolymer dispersion, 25% in water, Stockhausen), SER-AD -FX-1100 (hydrophobic urethane polymer. Servo Delden), Shellflo ^® -S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell).

Preferred aqueous liquid detergents contain 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.4 to 1.5% by weight, of a polysaccharide as thickening agent. A preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons. Xanthan is formed from a chain with ß-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan. Xanthan can be described by the following formula:

Basic unit of xanthan

Preferred aqueous liquid detergents each contain from 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.4 to 1.5% by weight, of xanthan as the thickener.

The first component of the enzyme stabilization system in the agents according to the invention is alkali metal formate and / or a boron compound, which are preferably used in amounts of 0.5 to 7% by weight, the alkali metal formates being selected from lithium formate, sodium formate, potassium formate and mixtures thereof can be. Examples of boron compounds which can be used in the context of the present invention are boric acid, boron oxide, alkali borates such as ammonium, sodium and potassium ortho, meta and pyroborates, borax in its various hydration stages and polyborates such as alkali metal pentaborates. Organic boron compounds such as esters of boric acid can also be used. Preferred liquid detergents contain 0.5% by weight to 5% by weight, preferably 0.75% by weight to 3% by weight and in particular 1% by weight to 2% by weight of sodium formate, boric acid and / or sodium tetraborate. As a second component of the enzyme stabilization system, the liquid detergents according to the invention contain polyhydric alcohol, such as glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol and or hexylene glycol. The use of glycerol and / or propylene glycol is particularly preferred, the latter preferably 1.2 -Propylenegylokol is, but also 1,3-Propypenglykol as well as mixtures of both can be used. This second component is preferably present in amounts of 0.5% by weight to 15% by weight in agents according to the invention.

In addition to the saccharide-based surfactant essential to the invention, the liquid detergents according to the invention can contain further surfactant, it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants, the proportion of the nonionic surfactants, including the saccharide-based surfactants essential to the invention, should be greater than the proportion of anionic surfactants. The total surfactant content of the liquid detergents according to the invention is preferably in the range from 15% by weight to 80% by weight, in particular from 20% by weight to 60% by weight.

The additional nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are 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. _] Alcohols with 3 EO, 4 EO or 7 EO, C ₉ .n alcohol with 7 EO, Cι ₃ .ι ₅ - alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _{_12-1} 4 alcohol containing 3 EO and Cι _ι ₈ alcohol containing 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 this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

Another class of nonionic surfactants used with preference are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as are described, for example, in Japanese Patent Application JP 58/217598 or which are preferably described in of the international patent application WO 90/13533.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-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.

Anionic surfactants that can be used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C. ₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁ ₈ monoolefins with 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 derived from C ₁ -C ₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization be won. Likewise, the esters of α-sulfo fatty acids (ester sulfonates). For example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid. Caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the -C ₈ -C fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the -C ₀ -C o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. For reasons of washing technology, the C ₂ -C ₆ alkyl sulfates and C ₂ -Ci ₅ alkyl sulfates and C ₄ -C ₅ alkyl sulfates are preferred. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. _l - Alcohols, such as 2-methyl-branched C _π alcohols with an average of 3.5 moles of ethylene oxide (EO) or Cι .ι ₈ fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -ι fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). 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.

Soaps are particularly suitable as further anionic surfactants. Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

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 triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The content of preferred liquid detergents in anionic surfactants is 5 to 35% by weight, preferably 8 to 30% by weight and in particular 10 to 25% by weight, in each case based on the total composition.

The viscosity of the agents according to the invention can be measured using customary standard methods (for example Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 500 to 5000 mPas. Preferred agents have viscosities of 1000 to 4000 mPas, values between 2000 and 3500 mPas being particularly preferred. In addition to the constituents mentioned so far, the agents according to the invention may contain further ingredients which further improve the technical and / or aesthetic properties of the liquid detergent. In the context of the present invention, preferred agents additionally contain one or more substances from the group of builders, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors. Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides. Antioxidants. Corrosion inhibitors. Antistatic agents. Ironing aids, phobing and impregnating agents, swelling and anti-slip agents as well as UV absorbers.

The builders that can be contained in the liquid detergents according to the invention include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Suitable crystalline, layered sodium silicates have the general formula NaMSi O _{2x +} ι ^' y H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Such crystalline layered silicates are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na Si O ₅ -yH 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.

Amorphous sodium silicates with a modulus Na O: SiO from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delayed in dissolution, can also be used and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. Within the scope of this invention the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles are added

Electron diffraction experiments provide washed-out or even sharp diffraction maxima. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The optionally used fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X) , which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and which has the formula nNa ₂ O ^■ (ln) K ₂ O ^■ Al ₂ O ₃ ^■ (2 - 2.5) SiO ₂ ^• (3.5 - 5.5) H ₂ O can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₈ -C ₈ fatty alcohols with 2 to 5 ethylene oxide groups, Cι -Cι fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method, for example using Coulter Counter) and preferably contain 18 to 22 wt .-%. in particular 20 to 22% by weight of bound water.

Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as those carboxylic acids which carry more than one acid function. For example, these are citric acid. Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid. Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. In particular, citric acid and succinic acid. To name glutaric acid, adipic acid, gluconic acid and any mixtures of these. Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. The molar masses given for polymeric polycarboxylates are, for the purposes of the present specification, weight-average molar masses M _{w of} the particular acid form, which can in principle be determined by means of gel permeation chromatography (GPC), a UV detector being used. The measurement is carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard, those measured against polystyrene sulfonic acids Molar masses are usually significantly higher. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol. To improve the solubility in water, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid known from European patent EP 0 727 448 B1. Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to German patent application DE 43 00 772 AI, are monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to German patent DE 42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred organic builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE 195 40 086 A1 that they have a bleach-stabilizing effect in addition to cobuilder properties. Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0 280 223. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid. Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 owns. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used. A preferred dextrin is described in European patent application EP 0 703 292 AI. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0 232 202, EP 0 427 349, EP 0 472 042 and EP 0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110 , WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C of the saccharide ring can be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable builder materials. Ethylene diamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts. Also preferred in this connection are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 become. Further useful organic builders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 Contain carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such builders are described, for example, in international patent application WO 95/20029. Organic builder substances are preferably present in the agents according to the invention in amounts of 1% by weight to 8% by weight.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl in the agents according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.

Non-aqueous solvents that can be used in the agents according to the invention come, for example, from the group of monohydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene ether glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures thereof Solvent. Non-aqueous solvents can be used in the liquid detergents according to the invention in amounts between 0.5 and 10% by weight, but preferably below 5% by weight and in particular below 3% by weight.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 2% by weight of the total formulation. In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and are not sensitive to the other ingredients of the compositions and to light, and have no pronounced substantivity towards textile fibers. so as not to stain them.

Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.

Suitable anti-redeposition agents. which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and on Polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances absorb on the fiber and bring about a brightening and fake bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and pure with the yellow tone of the grayed or yellowed laundry White results. Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole , Benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles. The optical Brighteners are usually used in amounts between 0.05 and 0.3% by weight, based on the finished agent.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of 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. Soluble starch preparations and starch products other than those mentioned above can also be used. e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the composition

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the fiber direction, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlyl sulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely with the agents according to the invention. In order to prevent undesirable changes in the agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates. Phosphites and phosphonates.

An increased wearing comfort of washed textiles can result from the additional use of antistatic agents, which can additionally be added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are described, for example, in patent applications FR 1 156 513, GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate ironing, silicone derivatives, for example, can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 mPas, it being possible for the silicones to be used in amounts between 0.2 and 5% by weight, based on the total agent. Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.

In order to avoid the decomposition of certain detergent ingredients catalyzed by heavy metals, substances can be used which complex heavy metals. Suitable heavy metal complexing agents are, for example, the alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates. A preferred class of complexing agents are the phosphonates, which are used in preferred liquid detergents in amounts of 0.01 to 1.5% by weight, preferably 0.02 to 1% by weight and in particular 0.03 to 0.5% by weight. -% are included. These preferred compounds include in particular organophosphonates such as, for example, 1-hydroxyethane-l, l-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-l, 2.4 tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts. Particularly preferred liquid detergents contain l-hydroxyethane-l, l-diphosphonic acid in the form of their ammonium or alkali metal salts.

The agents according to the invention can be prepared by simply mixing the constituents in stirred kettles, water, any non-aqueous solvents and surfactants which may be present being expediently introduced and the further constituents being added in portions. A separate heating during production is not necessary, if it is desired, the temperature of the mixture should not exceed 80 ° C. Examples

The liquid detergents E1 to E4 according to the invention, the composition of which is given in Table 1, were prepared by mixing the individual constituents.

Table 1: Liquid detergent [% by weight]

Keltrol ^® T: xanthan gum, polysaccharide (Kelco)

Turpina 4 NL: hydroxyethane-1,1-diphosphonic acid, tetra-Na salt Protease I: BLAP® 260 Protease II: Savinase® 16.0 L (Novo Nordisk) Amylase: Termamyl® L 300 (Novo Nordisk) Cellulase: Carezyme® 4500 L. (Novo Nordisk)

The liquid detergents had viscosities in the range from 2400 mPas to 3200 mPas. To test their storage stability, they were stored for 16 weeks in different climatic conditions and their appearance was assessed visually. They showed good stability both in the summer climate (25 - 40 ° C) and in the autumn climate (10 - 30 ° C) or in the winter climate (0 - 10 ° C). The enzymatic activity did not decrease significantly.

Claims

claims

1. Enzyme-containing, aqueous, higher-viscosity liquid detergent, containing surfactant and 0.1 wt .-% to 5 wt .-% of polymeric thickener and other usual ingredients of detergents and cleaning agents, characterized in that it contains surfactant based on saccharide, at least one enzyme from the group comprising cellulase. Amylase and protease and an enzyme stabilizer system from the components a) boron compound and / or sodium formate and b) polyhydric alcohol.

2. Composition according to claim 1, characterized in that it contains an optionally genetically modified protase from Bacillus lentus and / or Savinase®.

3. Composition according to claim 2, characterized in that it additionally contains amylase.

4. Composition according to claim 2 or 3, characterized in that it additionally contains cellulase.

5. Composition according to one of claims 1 to 4, characterized in that the surfactant based on saccharide is selected from the alkyl glycosides and the polyhydroxy fatty acid amides and mixtures thereof.

6. Composition according to one of claims 1 to 5, characterized in that the content of surfactants based on saccharide 0.5 to 25 wt .-%, preferably 1 to 10 wt .-% and in particular 1.5 to 5 wt. -%, in each case based on the total average.

7. Composition according to one of claims 1 to 6, characterized in that the polymeric thickener is a mixture of optionally modified natural polymer and fully synthetic polymer.

8. Composition according to one of claims 1 to 7, characterized in that it is 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and in particular 0.4 to 1.5 wt .-%, contains a polysaccharide as a thickener.

9. Agent according to one of claims 1 to 8, characterized in that it, based in each case on the total agent 0.2 wt .-% to 4 wt .-%, preferably 0.3 wt .-% to 3 wt .-% and in particular contains 0.4% to 1.5% by weight of xanthan.

10. Composition according to one of claims 1 to 9, characterized in that it contains 0.2 wt .-% to 4 wt .-%, in particular 0.4 wt .-% to 3 wt .-% of fully synthetic polymeric thickener.

1 1. Agent according to one of claims 1 to 10, characterized in that it has a viscosity of 500 mPas to 5000 mPas, preferably from 1000 mPas to 4000 mPas and in particular from 2000 mPas to 3500 mPas.