SE467827B - STABILIZED ENZYMINE-CONTAINING EFFECTIVE LIQUID DETERGENT COMPOSITION AND ITS USE IN WASHING TEXTILES - Google Patents

Description

20 25 30 467 827 acute. This is mainly due to the fact that detergent builders have a destabilizing effect on enzymes, even in compositions containing enzyme stabilizers, which are otherwise effective in non-fortified preparations. Furthermore, the incorporation of an enhancer into a liquid detergent composition adds an additional problem, namely the ability to form a stable composition in one phase. For example, the solubility of sodium tripolyphosphate is relatively limited in aqueous compositions and especially in the presence of anionic and nonionic detergents.

In GB patent application no. U.S. Patent No. 2,079,305, issued January 20, 1982 discloses an aqueous fortified enzyme-containing liquid detergent composition which is stabilized by a mixture of a polyol and boric acid. As noted in the examples in the said British patent application, relatively large amounts of glycerol are required to stabilize the enzymes in the composition. Nevertheless, as will be demonstrated later in the present specification, the enzyme stabilizing effect provided by a mixture of glycerin and borax in an enhanced aqueous liquid detergent composition is relatively modest.

In the European patent application no. 0126505 discloses an aqueous enzyme-containing liquid detergent composition containing an enzyme-stabilizing mixture consisting of certain dicarboxylic acids and borax. The dicarboxylic acids are recommended as a replacement for a polyol such as glycerol in known stabilizing mixtures consisting of glycerol and a boron compound.

However, the dicarboxylic acid-borax mixtures of this publication as well as the aforementioned prior art mixture of glycerin and borax do not provide anything other than a modest stabilizing effect in the present enhanced liquid detergent compositions. Thus, there is a need to markedly improve enzyme stability in aqueous fortified liquid detergent compositions of the type defined herein to levels which far exceed what can be achieved with the prior art.

The present invention provides a stabilized enhanced enzyme-containing liquid detergent composition comprising: a) b) c) d) e) ca. 5 - 20% by weight of one or more surfactant detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds, approx. 5 to 30% by weight of one or more builder salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxylates, an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline protease enzymes and alpha-enzymes enzyme stabilizing system containing, based on the weight of the detergent composition, of (i) approx. 1 - 10% glycerin, (ii) ca. 1-8% of a boron compound selected from the group consisting of boric acid, boron oxide and alkali metal borates, and (iii) approx. 0.5 to 8% of a carboxylic acid compound selected from the group consisting of mono-, di- and / or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof, and the balance being water and any perfume and other additives.

According to a preferred embodiment of the invention, the liquid detergent composition a) Ib) comprises approx. 5 - 15% of an alkali metal alkylbenzene sulfonate, where the alkyl group contains 12 - 15 carbon atoms, approx. 2 - 5% of an alkali metal alkyl polyethoxy sulphate where the alkyl group contains 10 to 18 carbon atoms and the polyethoxide moiety 3 - 11 ethylene oxide groups, and wherein the weight ratio a) to b) is approx. 2: 1 - 8: 1, 10 15 ào 25 30 467 827 c) ca. 5 - 20% sodium tripolyphosphate, d) approx. 1 - 10% sodium carbonate, the weight ratio c) to d) being approx. 2: 1 - 6: 1, e) an effective amount of the aforementioned enzyme or enzyme mixture, f) an enzyme stabilizing system containing, based on the weight of the detergent composition, of (i) approx. 3 - 7% glycerin, (ii) ca. 1 - 5% of an alkali metal borate and (iii) approx. 0.5 - 4% of said carboxylic acid compound, and g) the balance constituting water and possibly perfume and other additives.

In accordance with the process of the invention, washing of stained and / or soiled materials is carried out by bringing these materials into contact with an aqueous solution of liquid detergent compositions defined above.

The described liquid detergent is a commercially acceptable high performance laundry detergent which can satisfactorily clean laundry articles containing both oily and particulate dirt. In addition, the described compositions can be used for pre-treatment of heavily soiled areas, such as collars and cuffs, on garments to be washed.

The present invention is based on the discovery of a three component enzyme stabilizing system as defined herein, which provides an enzyme stabilizing effect to the liquid detergent compositions of the invention which far exceeds what can be achieved with conventional enzyme stabilizers.

The enzyme stabilizing effect thus obtained reflects a synergism of the three components. In accordance with the present invention, the enzyme stability provided by a mixture of glycerin and borax or a mixture of borax and a dicarboxylic acid as described in the prior art can be synergistically improved by the use of the three-component stabilizing system as defined in used herein in the present liquid compositions to significantly increase the degree of enzyme stability beyond that achieved by either the mixture of glycerin and borax or the mixture of borax and dicarboxylic acid, when used independently as enzyme stabilizers. For commercial purposes, a desired enzyme stability generally corresponds to an approximate half-life of one week at a temperature of approx. 43 ° C (110 ° F).

The enzyme stabilizing system of the invention is a mixture of glycerin, a boron compound selected from the gray group consisting of boric acid, boron oxide and an alkali metal borate and a carboxylic acid compound as defined herein. The weight of the stabilizing system in the present reinforced liquid detergent compositions is generally about 3 - 25% by weight, preferably approx. 6 - 15% by weight. The weight ratio of glycerin to borax in the stabilizing mixtures is generally approx. 1 to 3. The preferred amount of glycerin in the composition is approx. 3 - 7%, the preferred amount of boron compound is approx. 1-5% and the preferred amount of carboxylic acid compound is about 0.5 - 4%, based on the weight of the composition.

The carboxylic acid compounds which can be used in the enzyme stabilizing system according to the invention comprise saturated as well as unsaturated mono-, di- and polycarboxylic acids having 1 to 8 carbon atoms, among which are oxalic acid (HOOCCOOH), malonic acid (HOOCCHZCOOH), maleic acid (HOOCCH: CHCOOH ) and succinic acid (HOOCCHZCHZCOOH). The carboxylic acids may contain hydroxy or amino substituents such as malic acid (HOOCCHOHCH 2 COOH), tartaric acid (dihydroxy succinic acid), aspegetic acid (amino succinic acid) and citric acid. Preferred carboxylic acids according to the invention are succinic acid, maleic acid, malonic acid and malic acid. From a commercial point of view, a particularly preferred carboxylic acid is citric acid and / or its salts due to their relatively low cost. The alkaline proteolytic enzymes suitable for the present compositions include various commercial liquid enzyme formulations adapted for use in detergent compositions. Enzyme formulations in powder form are also useful, although in general this is less convenient when incorporated into liquid fortified detergent compositions. Thus, suitable liquid enzyme formulations include "Alcalase" and "Esperase", sold by Novo Industries, Copenhagen, Denmark and "Maxatase" and "AZ-Protease", sold by Gist-Brocades, Delft, The Netherlands.

Suitable GC amylase liquid enzyme formulations include those sold by Novo Industries and Gist-Brocades under the trademarks "Termamyl" and "Maxamyl" respectively.

"Esperase" is particularly preferred for the present compositions due to its optimized activity at the higher pH values corresponding to the enhanced detergent compositions.

The preferred detergents for use in the present liquid compositions are the synthetic anionic detergent compounds and in particular a mixture of higher alkyl benzene sulfonate and alkyl polyethoxy sulfate. While other water-soluble higher alkyl benzene sulfonates may also be present in the present compositions, such as potassium salts and in some cases the ammonium or alkanolammonium salts, where appropriate, it has been found that the sodium salt is highly preferred, as is also the case with respect to the alkyl polyethoxy sulfate detergent component. The alkylbenzene sulfonate is one in which the higher alkyl has 12 to 15 carbon atoms and preferably 13 carbon atoms. The alkyl polyethoxy sulfate, which may also be called sulfated polyethoxylated higher linear alcohol or the sulfated condensation product of a higher fatty alcohol and ethylene oxide or polyethoxylene glycol, is one in which the alkyl group has 10 to 18 carbon atoms, preferably 10 to 15 carbon atoms, to example approx. 13 carbon atoms, and comprising 3 to 11 ethylene oxide groups, preferably 3 to 7, more preferably 3 to 5 and most preferably 3 or about 3 ethylene oxide groups. The ratio of alkylbenzenesulfonate to polyethoxy sulfate in the detergent mixture is preferably about 2: 1 - 8: 1 and most preferably approx. 3: 1 - 5: 1, expressed as weight. In conditions above 5: 1, the physical stability of the product can be adversely affected.

Under appropriate circumstances, other anionic detergents such as fatty alcohol sulfates, paraffin sulfonates, olefin sulfonates, monoglyceride sulfates, sarcosinates and similarly acting detergents, preferably in the form of alkali metal, for example sodium, salts, may sometimes be present in part as a substitute. for the aforementioned synthetic organic detergents but in general, if present, except for these detergents. Normally the supplementary detergents are sulphated or sulphonated products (usually in the form of the sodium salts) and contain long-chain (8 - 20 carbon atoms) linear or fatty alkyl groups. In addition to any additional anionic synthetic organic detergents, nonionic and amphoteric materials may also be present, such as the Neodols, which are sold by Shell Chemical Company, which are condensation products of ethylene oxide and higher fatty alcohols, e.g. Neodol product of a higher fatty alcohol with approx. 12 - 13 carbon atoms with 23-6.5, which is a condensation- approx. 6.5 moles of ethylene oxide. Illustrations of the various detergents and classes of detergents mentioned can be found in the text Surface Active Agents, Volume II, by Schwartt, Perry and Berch (Interscience Publishers, 1958), and the description thereof is incorporated herein by reference.

The builder salt combination of the invention, which has been found to satisfactorily improve the cleaning ability of the mixture of synthetic anionic organic detergents and gives the desired pH in the liquid detergent and in the washing water, is a mixture of sodium tripolyphosphate and sodium tripolyphosphate . The amplifier salts are used in the present compositions in amounts which generally amount to approx. 5 - 25% by weight. For the preferred builder salt combination, sodium tripolyphosphate is present in amounts of about 5 - 20%, preferably 10 - 16%, and sodium carbonate is present in an amount of approx. 1 to 10% by weight, preferably 3 to 7%, the weight ratio of tripolyphosphate to carbonate in the preferred builder salt mixtures amounting to approx. 2: 1 - 6: 1 and most preferably approx. 2: 1 - 4: 1. As used herein, the term alkali metal "carbonates" or "carbonate" refers to the carbonates, bicarbonates and sesquicarbonates of said alkali metal.

For best preparation, easier mixing and good end-use properties, it is preferred that the sodium tripolyphosphate has a low content of phase I - type tripolyphosphate. Thus, normally the phase I type tripolyphosphate content is less than 30% of the tripolyphosphate used. Although in some cases incompletely neutralized tripolyphosphate can be used, the phosphate used can normally be considered to be pentasodium tripolyphosphate, Na5P3O10. Of course, in some cases, such as when potassium salts of other materials are present, ion exchange in an aqueous medium may result in the presence of salts other than sodium tripolyphosphate, but for the purpose of the present description it is considered that sodium tripolyphosphate, in the form of the pentasodium salt, the material normally charged to the mixer for the preparation of the present liquid detergent, is the tripolyphosphate used.

Other preferred builder salts that can be used in place of sodium tripolyphosphate and sodium carbonate or added thereto include a polyacetal carboxylate described herein and sodium nitrilotriacetate (NTA). Of course, different mixtures of the mentioned water-soluble builder salts can be used. Nevertheless, the described polyphosphate-carbonate mixture has been found to be most preferred, although other builders and mixtures thereof also work. Other builders which can be used as a supplement in addition to the amounts of the above-mentioned builders include other phosphates such as tetrasodium pyrophosphate or tetra potassium pyrophosphate, sodium bicarbonate, sodium citrate, sodium glyconate, sodium silicate and sodium sesquicate. Among the water-insoluble builders that can be used, the zeolites, such as Zeolite A, are usually in the form of its crystalline hydrate, although amorphous zeolites can also be used.

Polyacetal carboxylates are generally described in U.S. Pat. 4,144,226 and 4,315,092. U.S. Pat. U.S. Patent No. 4,146,495 discloses detergent compositions containing polyacetal carboxylates as builders.

The polyacetal carboxylates which are useful herein as builders can be considered to be those described in U.S. Pat. 4,144,226 and can be prepared by the method described therein.

A typical such product has the formula R 1 - (FHo) n - R ccom 2 wherein M is selected from the group consisting of alkali metal, ammonium, alkyl groups having 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups, both having 1 to 4 carbon atoms in the alkyl portion thereof , n averages at least 4 and R1 and R2 are any chemically stable groups which stabilize the polymer against rapid depolymerization in alkaline solution. Preferably the polyacetal carboxylate is one wherein M is alkali metal, for example sodium, n is 50 - 200, R 1 is CH 3 CH 2 O MOOC HCO or H 3 C-CO-II H 3 C MOOC or a mixture thereof, R 2 is OCH 2 CH 3 -CH CH 3 and you average is 20 - 100, more preferably 30 - 80.

The calculated weight average molecular weights for the polymers are normally in the range 2,000 - 20,000, preferably 3,500 - 10,000 and more preferably 5,000 - 9,000, for example approx. 8,000.

A particularly preferred sodium polyacetal carboxylate is supplied by the Monsanto Company and is known as Builder U. Det-. ta has an estimated average molecular weight of approx. 8,000 and an active polymer content of approx. 80%. Although the preferred polyacetal carboxylates are described above, it is to be understood that they may be substituted in whole or in part with other such polyacetal carboxylates or related organic builder salts as described in the above patents relating to such compounds, processes for their preparation and compositions in which they are exploited.

Furthermore, the chain terminating groups described in the various patents, in particular U.S. Pat. 4,144,226 are utilized, provided that they have the desired stabilizing properties which enable the said amplifiers to be depolymerized in acidic media, facilitating their biodegradation in waste water streams, but maintains their stability in alkaline media, such as washing solutions.

The only other required component of the present liquid detergents is water. Normally, the hardness content of such water is less than approx. 300 ppm, as CaCO 3, and preferably it is less than 150 ppm. It is often desirable to use deionized water, even though city water with a hardness content of less than 50 or 100 ppm can often be just as satisfactory.

Various additives may be present in the liquid detergents, such as fluorescent brighteners, perfumes and dyes. The fluorescent brighteners include the well-known stilbene derivatives, including the cotton and nylon brighteners, such as those sold under the Tinopal brand (5BM Conc.). The perfumes used generally include essential oils, esters, aldehydes and / or alcohols, all of which are known in the perfumery art. The dyes may include dyes and water-dispersible pigments of various types, including ultramarine blue. Inorganic filler salts such as sodium sulfate and sodium chloride may be present, as well as anti-redeposition agents such as sodium carboxymethylcellulose, dispersants such as sodium polyacrylate, bleaching agents, bactericides, fungicides, antifoams such as silicones, antifoulants such as copolyurstinylstimulants - as ethanol. Normally the individual proportions of these additives amount to less than 3%, often less than 1% and sometimes even less than 0.5%, with the exception of any fillers and solvents as well as additional detergents and builders for which the proportions can sometimes be as high as 10%.

The total proportion of additives including unspecified synthetic detergents and enhancers is normally not more than 20% of the product and is desirably less than 10% thereof, more desirably less than 5% thereof. Of course, the additives used must be selected so that they do not interfere with the washing action of the liquid detergent and to avoid instability of the product during storage. Furthermore, the additives that cause the formation of unwanted deposits on the laundry must be avoided.

The present liquid compositions are effective and easy to use. Compared to high-performance laundry detergent powder, significantly smaller volumes of the present liquids are used to obtain the corresponding cleaning of soiled laundry.

When using a typical preferred formulation according to the present invention, only 132 grams or half a cup of liquid is required for a filled washing drum in a top-loading automatic washing machine in which the water volume is 57 to 68 liters, and even less is required for front-loading Machines. Thus, the concentration of the liquid detergent composition in the wash water is in the order of approx. 0.2%.

Usually the proportion of liquid composition in the washing solution is in the range of approx. 0.05 - 0.3%, preferably 0.15 - 0.25%.

The proportions of the various constituents of the liquid composition may vary accordingly. Equivalent results can be obtained using larger proportions of a more dilute preparation, but the larger quantity required requires additional packaging space and is generally less convenient for consumer use and also results in product separation.

The viscosity of the present liquid detergent is normally in the range of approx. 1,000 - 10,000 cps, preferably 2,000 - 5,000 cps, but products with other suitable viscosities may also be useful. At the mentioned viscosities, the liquid detergent is pourable, stable, non-separating and uniform. The pH of the liquid detergent suspension, which is usually in the range of 7 - 11.5, preferably 8 - 10.5, appears to help maintain product stability and pourability. The following examples illustrate but do not limit the invention. Unless otherwise indicated, all parts express parts by weight and all temperatures are given in OC.

Example 1 Component Percent Pentanodium tripolyphosphate 15.0 Sodium carbonate 5.0 Sodium linear tridecyl benzenesulfonate 12.2 AEosm 2.8 Carboxymethylcellulose (CMC) 0.15 Optical brightener 0.4 Perfume 0.3 Enzyme (Esparase 8.0L) (2 ) 1.0 Glycerin 4.0 Borax 3.0 Triethanolamine 1.0 Sodium citrate 2.0 Water and additives balance (1) Sodium alkyl polyethoxy sulphate where the alkylene has 12 to 15 carbon atoms and the polyethoxy moiety contains 3 ethoxy groups. (2) "Esperase" sold by Novo Industries with an activity of 8,0 KNPU / gram.

The composition shown above was prepared by the following procedure: 32.5 parts of deionized water at 4.4 ° C (4003) are added to a suitable mixing apparatus such as a vertical cylindrical tank equipped with a stirrer. With the stirrer adjusted for medium stirring, a mixture consisting of 5.0 parts of anhydrous soda and 0.17 parts of sodium carboxymethylcellulose is introduced into the water. The stirrer speed is then increased to maximum agitation and 15.0 parts of pentasodium tripolyphosphate are slowly added to the mixer over a period of 10-15 minutes to form a milky white suspension. The stirring speed is then lowered to a slow / medium setting while 19.1 parts of a high AI (approx. 50%) LTBS slurry is added. Then the optical brightener / color solution consisting of 0.4 parts of Tinopal LMS-X 0 (CIBA-GEIGY), 0.06 parts of blue color and 2.0 parts of deionized water As soon as a uniform blue solution is obtained, 0.3 parts of perfume are added to the mixture with stirring.

This is accompanied by a slow addition of 4.0 parts glycerin, 3.0 parts borax and 1.0 parts triethanolamine (TEA improves - the long-term product stability) in the form of a three-component slurry. Stirring is continued until the mixture is uniform in appearance and then slowly add 2.0 parts of sodium citrate and 4.0 parts of water. Stirring of the mixture is then reduced while adding a mixed AI detergent base consisting of 5.7 parts of LTBS slurry (about 50% AI) and 4.7 parts of AEOS (about 60% AI) to the mixture. This is followed by the slow addition of 1.0 part of proteolytic enzyme with continuous stirring until all materials are completely dispersed or dissolved.

Example 2 Enzyme-containing fortified liquid detergent compositions A to G were formulated as shown in Table 1 below. The percentages given refer to weight percent. The arrows indicate the extent to which compositions B to G are identical to composition A. ¿10 15 20 25 30 467 827 15 Table 1 Component Pentanodium tripolyphosphate 15% Sodium carbonate (anhydrous) 5 Sodium linear tridecyl- I »| w In [U m lm lm benzenesulfonate 12.2 Asos (1) 2.8 Optical brightness enhancer (Tinopal LMS-X) 0.4 Perfume 0.3 CMC 0.2 EIIZYIHQ) 1 vvv vf v V Glycerin - 4 - 4 '- - 4 Borax - _ - 3 3 - 3 Carboxylic acid compound - - - - 2 2 2 Water and additives Balance (1) Sodium alkyl polyethoxy sulphate where the alkyl group has 12 to 15 carbon atoms and the polyethoxy moiety has 3 ethoxy groups. (2) "Esperase" sold by Novo Industries with an activity of 8,0 KNPU / gram (Kilo Novo protease units / gram).

The enzymatic activities of compositions A to G were tested after 7 days of storage at 43.3 ° C (10 ° F). The measured enzymatic activity for each composition after this storage period is indicated in Table 2 and Table 3 as a percentage of the original value. The various carboxylic acids and salts used in the formulas for compositions A, B, C, D, E and G are shown in Table 2 as well as the enzymatic activities corresponding to each composition. 10 l5_ 20 25 - 467 827 16 Table 2 Enzyme stability Composition Percent active enzyme O after 7 days at 43.3 CA (control) B (with glycerin) C (with borax) D (with glycerin and borax) Composition E (with carboxylic acid) compound) wherein the carboxylic acid compound is: (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) ) (16) (17) * ND Succinic acid Malonic acid Malic acid Oxalic acid Maleic acid Tartaric acid Aspartic acid Citric acid Glycine Alanine Sodium succinate Sodium format Sodium acetate Sodium tartrate Sodium citrate Sodium glycolate Sodium tetrahydroxysuccinate = not detectable Composition G (with glycerin / borax / carboxylic acid compound) wherein the carboxylic acid compound is: Percent active enzyme after 7 days at 43.3 ° C (1) Sodium succinate 60 (2) Succinic acid b 94 (3) Malonic acid 91 (4) Malic acid 79 (4) 5) Oxalic acid 81 (6) Maleic acid 88 (7) Tartaric acid 63 (8) Aspartic acid 84 (9) Citric acid 62 (10) Glycine 80 (11) Alanine 79 (12) Sodium form 57 (13) Sodium acetate 50 (14) Sodium tartrate 54 (15) Sodium citrate 57 (16) Sodium glycolate 50 (17) Sodium tetrahydroxy succinate 61 As shown in Table 2, composition A showed the control composition, as well as compositions B and C which contained glycerin and borax, respectively, as individual stabilizers, virtually no enzyme activity after the 7-day storage period at 43.3 ° C. Since enzymatic activities below 10% could not be accurately measured, they are termed "ND". Composition D containing glycerin / borax in the absence of a carboxylic acid compound gave an improvement in enzyme stability relative to compositions A, B and C but more than 50% of the enzyme was deactivated. The various compositions E containing a number of different carboxylic acid compounds as indicated manifested absolutely no improvement in enzyme stability relative to compositions A, B and C. However, compositions G composed in accordance with the invention demonstrate the unexpected and synergistic improvement in enzyme stability. M7 927 18 achieved with the use of glycerin / borax in combination with a carboxylic acid compound in the present liquid detergent compositions. It should be noted that in each of the 17 compositions corresponding to composition G tested, the enzyme activity was improved relative to composition D (containing glycerin and borax).

A comparison of the enzymatic activities obtained with the compositions D (glycerin / borax) and different compositions F (borax / carboxylic acid compound) and G (composed in accordance with the invention) is shown below in Table 3.

Table 3 Enzyme stability Percent active enzyme O after 7 days at 43.3 C Composition D (Glycerin / borax) 45 F (Borax / malonic acid) 13 G (Glycerin / borax / malonic acid) 91 F (Borax / aspartic acid) 39 G (Glycerin / borax / aspartic acid) 84 F (Borax / citric acid) ND * G (Glycerin / borax / citric acid) 62 * ND = undetectable (below 10% residual activity) As shown in Table 3, the various compositions G containing a three-component stabilizer system in accordance with according to the invention a synergistic improvement in enzyme-y, stability compared to compositions D and F formulated according to the prior art.

Claims (1)

1. detergent composition, a) b) c) d) e) 20 net signed) 467 827 19 Patent claims Stabilized enzyme-containing enhanced liquid characteristic of 5 - 20% by weight of one or more surfactant detergent - compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds, 5 to 30% by weight of one or more builder salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetylene enactive carboxylates an enzyme mixture selected from the group consisting of alkaline protease enzymes and alpha-amylase enzymes, an enzyme stabilizing system containing, based on the weight of the detergent composition of (i) 1-10% glycerin, (ii) 1-8% of a boron compound selected from the group consisting of boric acid, boron oxide and alkali metal borates and (iii) 0.5 - 8% of a carboxylic acid compound selected from the group consisting of mono, di- and / or polycarb oxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof, and the balance constituting water and possibly other additives. Liquid detergent composition according to claim 1, characterized in that it comprises: 5 - 15% of an alkali metal alkyl benzene sulfonate where the alkyl group contains 12 - 15 carbon atoms, b) 2 - 5% of an alkali metal alkyl polyethoxy sulphate where the alkyl group contains 10 - 18 carbon atoms and the polyethoxy group 3 - 11 ethylene oxide groups, the weight ratio a) to b) being 2: 1 - 8: 1, c) 5 - 30%, preferably 5 - 20% sodium tripolyphosphate, d) 1 - 10% sodium carbonate, the weight ratio c) to d) being 2: 1 - 6: 1, e) an effective amount of said enzyme or enzyme mixture, f) the enzyme stabilizing system containing, based on the weight of the detergent composition, (i) 3 - 7 % glycerin, (ii) 1 - 5% of an alkali metal borate and (iii) 0.5 - 4% of said carboxylic acid compound, and g) the balance comprising water and any minor additives. Liquid detergent composition according to claim 2, characterized in that said alkali metal alkyl benzene sulfonate is sodium linear tridecyl benzenesulfonate and that said alkali metal alkyl polyethoxy sulfate is one wherein the alkali metal is sodium, the alkyl group contains 12 - 15 'a ethoxene group and a poly group. A liquid detergent composition according to claim 3, wherein the ratio of tridecylbenzene sulfonate to polyethoxy sulfate is 3: 1 - 5: 1. V01. IN? Liquid detergent composition according to claim 2, known as metal borate. in that said boron compound is an alkali 6. A liquid detergent composition according to claim 5, characterized in that said borate is borax. Liquid detergent composition according to claim 2, characterized in that it contains 10 - 16% sodium tripolyphosphate and 3 - 7% sodium carbonate. Liquid detergent composition according to claim 2, characterized in that said carboxylic acid compound is succinic acid or a: water-soluble salt thereof. Liquid detergent composition according to claim 2, characterized in that said carboxylic acid compound is maleic acid or a water-soluble salt thereof. 10. A liquid detergent composition according to claim 2, characterized in that said carboxylic acid compound is citric acid or a water-soluble salt thereof. ll. Liquid detergent composition according to claim 2, characterized in that said carboxylic acid compound is malonic acid or a water-soluble salt thereof. Liquid detergent composition according to claim 2, characterized in that said carboxylic acid compound is malic acid or a water-soluble salt thereof. A method of washing, according to which stained and / or soiled textiles to be washed are brought into contact with a stabilized enzyme-containing enhanced liquid detergent-characterized gene composition, in that the composition comprises: a) 5 to 20% by weight of a or more surfactant detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds, b) c) d) e) 14. 22 5 - 30% by weight of one or more builder salts selected from from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxylates, an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline protease enzymes and alpha-amylase enzymes, an enzyme stabilizing system containing, based on 10% glycerin, (ii) 1-8% of a boron compound selected from the group consisting of boric acid, boron oxide and alkali metal borates, and h (iii) 0.5 - 8% of a carboxylic acid compound selected from the group consisting of mono- or di- and / or polycarboxylic acids having 1 to 8 carbon atoms and water-soluble salts thereof, and in the balance constituting water and possibly perfume and other additives. The method of claim 13, wherein said liquid detergent composition comprises: a) b) c) d) 5 - 15% of an alkali metal alkyl benzene sulfonate wherein the alkyl group contains 12 to 15 carbon atoms, 2 - 5% of an alkali metal alkyl polyethoxy sulfate wherein the alkyl group contains 10 - 18 carbon atoms and the polyethoxy group 3 - 11 ethylene oxide groups, the weight ratio a) to b) being about 2: 1 - 8: 1, 5 - 30%, preferably 5 - 20% sodium tripolyphosphate, 1 - 10% sodium carbonate, wherein the weight ratio c) to d) amounts to 2: 1 - 6: 1, 'e 1) an effective amount of said enzyme or enzyme mixture, f) the enzyme stabilizing system containing, based on the detergent composition weight, (i) 3 - 7% glycerin, (ii) 1 - 5% of an alkali metal borate and (iii) 0.5 - 4% of said carboxylic acid compound, and g) the balance constituting water and any minor additives. The method of claim 14, wherein said alkali metal alkylbenzenesulfonate is sodium having a linear tridecylbenzenesulfonate and said alkali metal alkyl polyethoxy sulfate is one wherein the alkali metal is sodium, the alkyl group contains about 12 to 15 carbon atoms and the ethyl ethoxy group. A method according to claim 15, wherein the ratio of tridecylbenzenesulfonate to polyethoxy sulfate is 3: 1 - 5: 1. A method according to claim 14, wherein said boron compound is borax. 18. A method according to claim 14, characterized in that the liquid detergent composition contains 10 - 16% sodium tripolyphosphonate and 3 - 7% sodium carbonate. A method according to claim 14, wherein the carboxylic acid compound is succinic acid or a characteristic of a water-soluble salt thereof. 20. A method according to claim 14, characterized in that the carboxylic acid compound is citric acid or a water-soluble salt thereof. 467 827 24 21. A method according to claim 14, characterized in that the carboxylic acid compound is maleic acid or a water-soluble salt thereof. 22. A method according to claim 14, characterized in that the carboxylic acid compound is malonic acid or a water-soluble salt thereof. 9) * V1