DK165331B - LIQUID, SUBSTANCING DETERGENT AND WASHING PROCEDURE - Google Patents

Description

in

DK 165331 B

The present invention relates to stable, builder-containing, acid-containing, liquid detergents suitable for laundry or soaking formulations. More particularly, the invention relates to aqueous, enzyme-containing, liquid detergents containing one or more detergent builders and characterized by being physically stable, homogeneous, liquid agents.

The formulation of stabilized, enzyme-containing liquid detergents has been the subject of much attention in the prior art. The desire to incorporate enzymes into detergents is primarily due to the efficacy of proteolytic and amylolytic enzymes to degrade proteinaceous and starch-like materials found on soiled clothing or fabric, thereby facilitating the removal of stains, such as dots, bloodstains, chocolates, and the like. , during washing. However, enzymatic materials suitable for detergents, especially proteolytic enzymes, are relatively expensive. In fact, they are generally among the most expensive ingredients in a typical 20 commercial liquid detergent, although present in relatively smaller quantities. In addition, enzymes are known to be unstable in aqueous agents. It is for this reason that generally, an excess of enzymes are required in liquid detergent formulations to compensate for the expected loss of enzyme activity during long storage periods. The prior art therefore encompasses many proposals for stabilizing enzyme-containing liquid detergents and especially non-liquid-containing detergents using various materials incorporated into the agent to act as enzyme stabilizers.

The problem of enzyme instability is particularly acute in the case of liquid detergents containing a builder. This is primarily because detergent builders have a destabilizing effect on enzymes, even in agents containing enzyme stabilizers which are otherwise effective in non-buffered formulations. In addition, incorporating a builder

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2 in a liquid detergent is a further problem, namely the ability to form a single phase stable agent, the solubility of e.g. sodium tripolyphosphate is relatively limited in aqueous agents and especially in the presence of anionic or nonionic detergents.

6B Patent Application No. 2,079,305, published January 20, 1982, discloses an aqueous, builder-containing, enzyme-containing liquid detergent which is stabilized by a mixture of a polyol and boric acid. As mentioned in the examples in the GB application, relatively large amounts of glycerol are required to stabilize the enzymes in the agent. However, the enzyme-stabilizing effect provided by a mixture of glycerol and borax in a builder-containing aqueous liquid detergent is relatively modest, as shown hereinafter in the present description.

European Patent Application Publication No. 0126505 discloses an aqueous, enzyme-containing liquid detergent 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 enzyme stabilizing mixtures of glycerol and a boron compound. However, such dicarboxylic acids / borax mixtures, like the aforementioned mixtures of glycerol and borax, are also unable to provide anything other than a modest stabilizing effect in the present builder liquid detergents.

The present invention discloses a stabilized, fabric softening, builder-containing, enzyme-containing, liquid detergent comprising: (a) from 5 to 20% by weight of one or more surfactant detergent compounds selected from anionic, nonionic, and amorphous tergent compounds ;

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3 (b) from 5 to 30% by weight of one or more builder salts selected from alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxylates; 5 (c) from 5 to 20% by weight of a swelling concrete grinder; (d) an effective amount of an enzyme or enzyme mixture selected from alkaline protease enzymes and α-amylase enzymes; (E) an enzyme stabilizing system, and (f) the residue comprising water and optionally perfume and other excipients, which detergent is characterized in that the enzyme stabilizing system consists of the weight of the detergent, (i) from 1 to 10¾ glycerol. , (ii) from 1 to 8% of a boron compound selected from boric acid, boron oxide and alkali metal borates and (iii) from 0.5 to 8% of a carboxylic acid compound selected from saturated di- or tricarboxylic acids having 2 to 8 carbon atoms and water soluble salts thereof.

In a preferred embodiment of the invention, the liquid detergent comprises: (a) from 5 to 15% of an alkali metal alkyl benzene sulfonate, wherein the alkyl group contains 12 to 15 carbon atoms; (b) from 0.5 to 5% of an alkali metal alkyl polyethoxy sulfate, wherein the alkyl group contains 10 to 18 carbon atoms and the polyethoxy moiety has 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from 2: 1 to 6: 1; (c) from 5 to 20% sodium tripolyphosphate; (D) from 1 to 10% sodium carbonate, sodium bicarbonate or mixtures thereof, the weight ratio of (c) to (d) being from 2: 1 to 6: 1;

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4 (e) from 10 to 15% sodium abentonite; (f) an effective amount of the aforementioned enzyme or enzyme mixture; (G) an enzyme stabilizing system which, based on the weight of the detergent, contains (i) from 1 to 5% glycerol, (ii) from 1 to 5% of an alkali metal borate and (iii) from 0.5 to 4% of said detergent carboxylic acid compound, and 10 (h) the remainder comprising water and optionally perfume and other excipients.

In accordance with the process of the invention, washing of stained and / or soiled materials is carried out by contacting such materials with an aqueous solution of the above-defined liquid detergents.

The liquid detergent described is a commercially acceptable, powerful laundry detergent capable of satisfactorily cleaning laundry pieces containing both oily and particulate soils. In addition, the agents described can be used to pre-treat highly soiled areas of laundry pieces, such as collars and cuffs.

The present invention is based on the discovery of an enzyme-stabilizing three-component system as defined herein, which provides an enzyme-stabilizing effect on the liquid detergents of the invention that is much greater than the effect obtainable with conventional enzyme stabilizers. The enzyme stabilizing effect thus obtained reflects a synergy between the three components. In accordance with the invention, the enzyme stability provided by a mixture of glycerol and borax or a mixture of borax and a dicarboxylic acid, as described in the prior art, can be synergistically improved by using the stabilizing three-component system. as defined herein, in the aforementioned liquid agents such that the level of enzyme stability is significantly raised above the level provided by either the mixture of glycerol and borax or the mixture of borax and dicarboxylic acid, used independently of each other as enzyme stabilizers. For commercial purposes, a desirable enzyme stability generally corresponds to ca. a half-life of one week at a temperature of 43 ° C.

The enzyme stabilizing system of the invention is a mixture of glycerol, a boron compound selected from 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 builder-containing liquid detergents is generally from about 15% to about 15%. 3 to approx. 25%, preferably from. ca. 6 to approx. 15% by weight.

The weight ratio of glycerol to borax in the stabilizing mixtures is generally from ca. 0.5 to 3. The preferred amount of glycerol in the agent is from about 1 to approx. The preferred amount of boron compound is from about 5%. 1 to approx. The preferred amount of carboxylic acid compound is from about 5%. 0.5 to approx. 4%, based on the weight of the detergent.

The carboxylic acid compounds useful in the enzyme stabilizing system of the invention comprise saturated di-25 and tricarboxylic acids having 2 to 8 carbon atoms including oxalic acid (H00CC00H), malonic acid (HOOCCH2COOH), maleic acid (H00CCH: CHC00H) and succinic acid (H00C . The carboxylic acids may contain hydroxy or amino substituents as illustrated by malic acid (H00CCHOHCH2C00H), tartaric acid (dihydroxyacetic acid), aspartic acid (amino acid) and citric acid. Preferred carboxylic acids of the invention are aspartic acid, tartaric acid, malonic acid and malic acid. From a commercial point of view, a particularly preferred carboxylic acid compound is citric acid and / or its salts because of their relatively low price.

The alkaline proteolytic enzymes useful in the present compositions comprise the various commercial fluids.

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6 enzyme preparations which have been adapted for use in detergents. Enzyme formulations in powder form are also useful, although they are generally less suitable for incorporation into the liquid-containing detergents. Thus, suitable liquid enzyme preparations include Alcalase® and Esperase® sold by Novo Industri A / S, Copenhagen, Denmark and Maxatase® and "AZ-Protease" sold by Gist-Brocades, Delft, The Netherlands.

10 Among the appropriate liquid α-amylase enzyme preparations are preparations sold by Novo Industri A / S and Gist-Brocades under the trademark Termamyl® and the brand Maxamyl® respectively.

Esperase® is particularly preferred for the detergents 15 because of its optimized effect at the higher pH values corresponding to the detergent-containing detergents.

The preferred detergents for use in the present liquids are the synthetic anionic detergent compounds 20 and, in particular, a mixture of higher alkylbenzenesulfonate and alkylpolyethoxy sulfate. While other water-soluble higher alkylbenzene sulfonates may also be present in the present formulations, such as potassium salts and in some cases the ammonium or alkanolammonium salts, when appropriate, it has been found that the sodium salt is highly preferred, as is the case with for the alkyl polyethoxysulfate detergent component. Alkylbenzenesulfonate is a compound in which the higher alkyl group has 12 to 15 carbon atoms, preferably 13 carbon atoms. The alkyl polyethyoxy sulfate, which can also be referred to as a sulfated, polyethoxylated, higher linear alcohol or as the sulfated condensation product of a higher fatty alcohol and ethylene oxide or polyethoxylene glycol, is a compound wherein the alkyl group has 10 to 18 carbon atoms, preferably 12 to 15 , eg. ca. 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 to about 3 carbon atoms. 3 ethylene oxide groups. The weight ratio of alkylbenzene sulfonate to polyethoxy sulfate in the detergent mixture is preferably from about 2: 1 to 6: 1 and most preferably from approx. 2: 1 to 4: 1. The physical stability of the product may be adversely affected at ratios above 5: 1.

5. Under appropriate circumstances, other anionic detergents such as fatty alcohol sulfates, paraffin sulfonates, olefin sulfonates, monoglyceride sulfates, sarcosinates and detergents which act in a similar manner, preferably as the alkali metal salts, e.g. sodium salts, are present, sometimes as partial substitutes for the aforementioned synthetic organic detergents, but usually when present, in addition to such detergents. Usually, the supplemental detergents will be sulfated or sulfonated products (usually as the sodium salts) 15 and will contain long chain (8 to 20 carbon atoms) linear or fatty alkyl groups. In addition to any additional anionic, synthetic, organic detergents, non-ionic and amphoteric materials may also be present as "Neodol" sold by Shell Chemical Company, and as condensation products of 20 ethylene oxide and higher fatty alcohols, for example "Neodol "23-6.5, which is a condensation product of a higher fatty alcohol of about 12 to 13 carbon atoms of about 6.5 moles of ethylene oxide. Examples of the various detergents and detergent classes mentioned can be found in the text Surface Active Agents, Volume II, by 25 Schwartz, Perry, and Berch (Interscience Publishers, 1958), the disclosures of which are incorporated herein by reference.

The builder salt combination of the invention, which has been found to satisfactorily improve the washability of the mixture of synthetic, anionic, organic detergents and produce the desired pH in the liquid detergent and in the wash water, is a mixture of sodium tripolyphosphate and sodium carbonate. The builder salts are generally used in the present compositions in amounts of from ca. 5 to approx. 25% by weight. In the preferred builder-salt combination, sodium tripolyphosphate is present in amounts ranging from ca. 5 to approx. 20%, preferably 10 to 16%, and sodium carbonate are present from ca. 1 to approx. 10% by weight, preferably from 3

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8 to 7% / with the weight ratio of tripolyphosphate to carbonate in the preferred buffer mixtures being from about 2: 1 to 6: 1 and most preferably from approx. 2: 1 to 4: 1. As used herein, the term "alkali metal carbonates" or "carbonate" should include the carbonates, bicarbonates and sesquicarbonates of such alkali metals.

For best processing, easier mixing and good ready-to-use properties, it is preferred that the sodium tripolyphosphate has a low content of phase I tripolyphosphate. Thus, the content of tripolyphosphate of type I will normally be less than 30% of that. tripolyphosphate used. Although in some cases incompletely neutralized tripolyphosphate can be used, the phosphate 15 used can usually be considered as pentane sodium tripolyphosphate, Na5P3010 · In some cases, when potassium salts of other materials are present, ion exchange in an aqueous medium can obviously result in others. salts than the sodium tripolyphosphate present, but for the purposes of this invention, it is believed that the sodium tripolyphosphate, such as the pentane sodium salt, which is the material normally poured onto the mixer to produce the liquid detergent, is the tripolyphosphate used.

Other preferred builder salts which may be used in place of sodium tripolyphosphate and sodium carbonate or in addition include a polyacetal carboxylate as described herein and sodium nitrilotriacetate (NTA). Of course, various mixtures of said water-soluble builder salts can be used. However, the tripolyphosphate / carbonate mixture described above has been found to be most preferred, although the other builders and mixtures thereof are also effective. Other builders which may be used as supplements in addition to the proportions of the builders mentioned above include other phosphates such as tetrasodium pyrophosphate or tetras potassium pyrophosphate, sodium bicarbonate, sodium citrate, sodium gluconate, sodium silicate, and sodium sexticarbonate. Among the water-insoluble builders which can be used, the zeolites, such as Zeolite A, are usually in the form of its crystal hydrate, although amorphous zeolites may also be useful.

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

The polyacetal carboxylates useful in the present invention as builders can be considered as those described in U.S. Patent No. 4,144,226 and may be prepared by the process mentioned therein. A typical such product will have the formula 15

Ri - (CH °) n - «2 COOM

wherein M is selected from alkali metal, ammonium, alkyl groups 20 having 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups, both having 1 to 4 carbon atoms in the alkyl groups thereof, n being on average at least 4, and R1 and R2 being any chemically stable group which stabilizes the polymer against rapid depolymerization in alkaline solution. Preferably, the polyacetal carboxylate will be one where M is alkali metal, e.g. sodium, n is from 50 to 200, Rj is

CH3CH20 M00C

HCO- or H3C-CO-

30 H3C M00C

or a mixture thereof, R 2 is OCH 2 CH 3

35 -CH

CH3

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10 and n average are from 20 to 100, more preferably from 30 to 80. The calculated weight average molecular weights of the polymers will usually be in the range of 2,000 to 20,000, preferably from 3,500 to 10,000 and more preferably from 5,000 to 9,000. , eg. ca. 8000.

A particularly preferred sodium polyacetal carboxylate is supplied by the Monsanto Company and is known as Builder U. It has a calculated average molecular weight of approx. 8,000 and an active polymer content of approx. 80%.

Although the preferred polyacetal carboxylates have been described above, it is to be understood that they may be wholly or partially replaced by other such polyacetal carboxylates or related organic builder salts disclosed in the aforementioned patents for such compounds, processes for their preparation and agents wherein is used. The chain terminating groups described in the various patents, in particular U.S. Patent No. 4,144,226, may also be used provided that the 20 have the desired stabilizing properties which allow said builders to be unpolymerized in acidic media, facilitate biodegradation. thereof in wastewater, but maintain their stability in alkaline media such as washing solutions.

The bentonite used herein is a colloidal clay (aluminum silicate) containing montmorillonite. Swelling bentonites are generally characterized as sodium bentonites, ie. bentonite in which the dominant cation is sodium. Of the sodium bentonite species, those from Wyoming (generally referred to as Western or Wyoming bentonite) are particularly preferred.

Bentonite's swelling capacity is generally associated with its substance softening properties. In water, swelling capacity of sodium abentonite ranges from 3 to 20 ml / g, preferably 7 to 35 ml / g, and its viscosity at a concentration of 6% in water is usually in the range of 3 to 30 centipoise, preferably 8 to 30 centipoise. .

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11

Preferred swelling bentonites are sold under the trademark "HI-JEL" ® by Georgia Kaolin Co. These materials are the same as the bentonites previously sold under the trademarks "MINERAL COLLOID" ® and "THIXO-JEL" ®. They are selectively mined 5 and enriched bentonites and those which are considered most suitable are available as "HI-JEL" Nos. 1, 2 and 3, etc., corresponding to "THIXO-JEL" Nos. 1, 2, 3 and 4. Such materials have a maximum free moisture content (prior to addition to the liquid medium) from 4 % to 8% and with a density of approx.

2.6. The bentonite is preferably one which will pass through a 200 mesh screen in the US. and most preferably, at least 90% of the particles will pass through a screen # 325, so that the equivalent diameter of the bentonite can be considered to be less than 74 microns and more preferably less than ca. 44 microns.

15

Typical chemical analyzes of some bentonites useful in the preparation of the present liquid detergents show that they contain from 64.8 to 73.0% SiO 2, 14 to 18% Al 2 O 3, 1.6 to 2.7% MgO, 1.3 to 3.1% CaO, 2.3 to 3.4% Fe2O3, 0.8 to 2.8% Na2O, and 0.4 to 7.0% K2O.

Although western bentonites are preferred, it is also possible to use other bentonites, such as those bentonites, which may be produced by treating Italian or similar 25 bentonites containing relatively small amounts of exchangeable monovalent metals (sodium and potassium) with alkaline materials such as sodium carbonate to increase the cation exchange capacities of such products. It is believed that the Na 2 O content of the bentonite should be at least approx. 0.5%, preferably at least 1% and more preferably at least 2%, so that the clay will be satisfactorily swollen with good softening properties and dispersion properties in aqueous suspension. Preferred swelling bentonites among the types described above are sold under the trademarks "Laviosa" and "Winkelmann", e.g. "Laviosa" AGB and "Winkelmann" G-13.

Other bentonites which are particularly useful for the liquid detergents in question due to their white or very light color include the American Colloid Company's Polarite KB 325, a California bentonite and Georgia Kaolin's GK 129, a Mexican bentonite.

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The viscosity of the present liquid detergents is usually in the range of from about. 1,000 to approx. 10,000 centipoise, preferably from 2,000 to 7,000 centipoise, but products with other appropriate viscosities may also be useful. At the viscosities mentioned, the liquid detergent is pourable, stable, non-separable and uniform. The pH of the liquid detergent suspension, which is usually in the range of 7 to 11.5, preferably from 8 to 10.5, seems to help maintain the stability and pourability of the product.

The following examples illustrate the invention. Unless otherwise stated, all parts are parts by weight and temperatures in ° C.

20 25 30 35

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13

Example 1

Component Percent

Pentanium Tripolyphosphate 11.0 Bentonite (Georgia Kaol in 129) 12.0

Sodium carbonate 2.0

Sodium sesquicarbonate 2.0

Sodium 1i near-tridecylbenzene sulfate 8.0 AEOS (1) 3.0 Carboxymethyl cellulose (CMC) 0.2

Optical Clarifier 0.3

Perfume 0.4

Enzyme (Esperase 8.0L) (2) i, o

Glycerol 3.0 Borax 2.5

Citric Acid 2.0

Water and excipients residue (1) Sodium alkyl polyethoxy sulfate wherein the alkyl group has 12 to 20 carbon atoms and the polyethoxy moiety has 3 ethoxy groups.

(2) Esperase® sold by Novo Industri A / S with an activity of 8.0 KNPU / g.

The agent listed above was prepared by the following procedure: 30.0 parts of deionized water at 4 ° C is added to an appropriate mixer such as a vertical cylindrical container equipped with a stirrer. With the stirrer set for medium stirring, a mixture 30 consisting of 2.0 parts of anhydrous, calcined soda, 2.0 parts of sodium sesquicarbonate and 0.2 parts of sodium carboxymethyl cellulose is incorporated into the water. The agitator speed is then increased to maximum stirring, and a mixture of 11.0 parts of pentane sodium tri-polyphosphate and 12.0 parts of bentonite is slowly added to the mixer over a period of 10 to 15 minutes to form an off-white suspension. The stirring speed is then reduced to a slow / medium setting, while 8.64 14

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portions of a high Ai LTBS slurry (about 55%) are added. Then add the optical brightener / color solution consisting of 0.3 parts of Tinopal LNS-X (CIBA-GEIGY), 0.99 parts of dye and 4.02 parts of deionized water. When a uniform bluish-green-colored solution is obtained, 0.4 parts of perfume are added to the mixture with stirring. This is followed by the slow addition of 3.0 parts of glycerol and 2.5 parts of borax in the form of a two-component slurry. Stirring is continued until the mixture has a uniform appearance, and then 2.0 parts of citric acid and 9.0 parts of water are slowly added. Stirring of the mixture is then reduced, while 10.95 parts of a mixed AI detergent base consisting of a LTBS slurry (about 30% AI) and AEOS (about 27.5% AI) are added to the mixture. This addition is followed by a slow addition of 1.0 parts of proteolytic enzyme with continued stirring until all materials are completely dispersed or dissolved.

Example 2 Enzyme-containing liquid detergents A to G were formulated as listed below in Table 1. The percentages indicate weight%. The arrows must indicate the extent to which means B to G are identical to detergent A.

25 30 35

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15

Table 1

Component A B C D £ 5 £ Pentan sodium tripolyphosphate 11.0

Bentoni t (Georgia-Kaolin 129) 12.0

Sodium carbonate 2.0 Sodium sesquicarbonate 2.0

Sodium 1-linear tridecylbenzenesulfonate 8.0 AEOSd) 3.0

Optical Clarifier 15 (Tinopal® LMS-X) 0.3

Perfume 0.4 CMC 0.2

Enzyme (2) 1.0 Yrs ▼ v ir *

Glycerol - 3.0 ”3.0 - - 3.0 Borax - - 2.5 2.5 - 2.5 2.5

Carboxylic Acid Compound - 2.0 2.0 2.0

Water and auxiliary residues (1) Sodium alkyl polyethoxy sulfate, wherein the alkyl group has 12 25 to 15 carbon atoms and the polyethoxy moiety has 3 ethoxy groups.

(2) Esperase® sold by Novo Industri A / S with an equity of 8.0 KNPU / g (Kilo Novo Protease Units / g).

The enzyme activities of agents A to F were investigated after 7 days of storage at 43 ° C. The measured enzyme activity of each agent after this storage period is given in Table 2 as a percentage of the initial value. The various carboxylic acids and salts used in the general formulations of agents A, B, C, D, E and G are shown in Table 2 as well as the enzyme activities corresponding to each agent.

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16

Table 2

ENZYME STABILITY

Detergent Percent of active enzyme

5 after 7 days at 43 ° C

A (control) i.d. * B (with glycerol) i.d.

C (with borax) i.d.

D (with glycerol and borax) 50 10

Detergent E (with carboxylic acid compound) wherein the carboxylic acid compound is a (1) succinic acid i.d.

(2) Malonic Acid i.d.

(3) Malic acid i.d.

(4) Tartaric acid i.d.

(5) Aspartic acid i.d.

(6) Citric Acid i.d.

(7) Sodium tartrate i.d.

(8) Sodium citrate i.d.

* i.d. = not detectable (below 10% residual activity) Detergent G (with glycerol / borax / Percent active enzyme carboxylic acid compound) wherein after 7 days at 43 ° C the boxboxylic acid compound is: _ (1) succinic acid 70 30 (2) Malonic acid 70 (3 ) Malic acid 78 (4) Tartaric acid 73 (5) Aspartic acid 90 (6) Citric acid 74 35 (7) Sodium tartrate 66 (8) Sodium citrate 52 17

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As shown in Table 2, detergent A, the control detergent, as well as detergents B and C containing individual stabilizers of glycerol and borax, respectively, showed almost no enzyme activity after the 7-day storage period S at 43 ° C. Although enzyme activities below 10% could not be accurately measured, they are designated "id". Detergent D containing glycerol / borax in the absence of a carboxylic acid compound gave improvement in enzyme stability compared to detergent A, but about 50% of the enzyme was However, various agents 10 E containing a variety of carboxylic acid compounds as indicated showed no improvement in enzyme stability at all compared to detergent A. However, detergents G formulated in accordance with the invention show the unexpected and synergistic improvement in enzyme stability, 15 obtained by using glycerol / borax in combination with a carboxylic acid compound in the liquid detergents in question. It can be found that almost every one of the agents corresponding to detergent G showed a significant improvement in enzyme activity over detergent. agent D (containing glycerol and borax).

Table 3 below provides a comparison of the enzyme activities obtained with detergent D (glycerol / borax) and various detergents F (borax / carboxylic acid compound) and 25 G (formulated in accordance with the invention).

30 35

Claims (10)

A stabilized, fabric softening, enzyme-containing, builder-containing, liquid detergent comprising: (a) from 5 to 20% by weight of one or more surfactant detergent compounds selected from anionic, nonionic and amorphous detergent compounds; (B) from 5 to 30% by weight of one or more builder salts selected from alkali metal tripolyphosphates, alkali metal carbonates, alkali metal trilotriacetates and polyacetal carboxylates; (C) from 5 to 20% by weight of a swelling bentonite clay; (d) an effective amount of an enzyme or enzyme mixture selected from alkaline protease enzymes and α-amylase enzymes; (E) an enzyme stabilizing system and (f) the remainder comprising water and optionally perfume and other adjuvants, characterized in that the enzyme stabilizing system consists of, on the watch of the detergent, (i) from 1 to 10% glycerol, (ii) from 1 to 8% of a boron compound selected from boric acid, boron oxide and alkali metal borates and (iii) from 0.5 to 8% of a carboxylic acid compound selected from saturated di- and tricarboxylic acids having 2 to 8 carbon atoms and water-10 soluble salts thereof. Liquid detergent according to claim 1, characterized in that it comprises: (a) from 5 to 15% of an alkali metal alkyl benzenesulfonate, wherein the alkyl group contains 12 to 15 carbon atoms; (b) from 0.5 to 5% of an alkali metal alkyl polyethoxy sulfate wherein the alkyl group contains 10 to 18 carbon atoms and the polyethoxy moiety has 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from 2: 1 to 6: 1; (c) from 5 to 20% sodium tripolyphosphate; (D) from 1 to 10% sodium carbonate, sodium bicarbonate or mixtures thereof, the weight ratio of (c) to (d) being from 2: 1 to 6: 1; (e) from 10 to 15% of a sodium bentonite; (F) an effective amount of said enzyme or enzyme blend; (g) the enzyme stabilizing system, based on the weight of the detergent, contains (i) from 1 to 5% glycerol (ii) from 1 to 5% of an alkaline metal metal borate and (iii) from 0.5 to 4% of said detergent and (h) the residue comprising water and optionally less essential excipients. Liquid detergent according to claim 2, characterized in that the alkali metal acylbenzenesulfonate is the sodium 1-nitride decylbenzenesulfonate and the alkali metal alkyl polyethoxy sulfate is one wherein the alkali metal is sodium, the alkyl group contains 12 to 15 carbon atoms and the polyethoxy moiety has about 3 ethylene oxide groups. 10 Liquid detergent according to claim 3, characterized in that the ratio of tridecylbenzenesulfonate to polyethoxy sulfate is from 2: 1 to 4: 1. A method of washing comprising contacting stained and / or soiled fabrics to be washed with a stabilized, enzyme-containing builder-containing liquid detergent comprising: 20 (a) from 5 to 20% by weight of one or more surfactants of the tergent compounds selected from anionic, non-ionic and amorphous detergent compounds; (b) from 5 to 30% by weight of one or more builder salts selected from alkali metal tripolyphosphates, alkali metal carbonates, alkali metal trilotriacetates and polyacetal carboxylates; (c) from 5 to 20% by weight of a swelling bentonite clay; (D) an effective amount of an enzyme or enzyme mixture selected from alkaline protease enzymes and α-amylase enzymes; (e) an enzyme stabilizing system and (f) the residue comprising water and optionally perfume and other auxiliary pesticides, characterized in that the enzyme stabilizing system consists of, based on the weight of the detergent, (i) DK 165331 B from 1 to 10% glycerol , (ii) from 1 to 8% of a boron compound selected from boric acid, boron oxide and alkali metal borates, and (iii) from 0.6 to 8% of a carboxylic acid compound selected from saturated di- and tricarboxylic acids having 2 to 8 carbon atoms and van -5 soluble salts thereof. 5 Detergent after 7 days at 43 ° C D (Glycerol / borax) 50 'F (Borax / malonic acid) 45 G (Glycerol / borax / malonic acid) 70 F (Borax / aspartic acid) 72 10 G (Glycerol / Borax / Aspartic Acid) 90 F (Borax / Citric Acid) 42 G (Glycerol / Borax / Citric Acid) 74 As shown in Table 3, the various detergents provide 15 G containing a three-component starch in the system of the invention in accordance with the invention. , a synergistic improvement in enzyme stability over detergent D and detergent F formulated in accordance with the prior art. 20 Patent claims. Process according to claim 5, characterized in that the liquid detergent comprises: 10 (a) from 5 to 15% of an alkali metal cool benzenesulphonate, wherein the alkyl group contains 12 to 15 carbon atoms; (b) from 0.5 to 5% of an alkali metal alkyl polyethoxy sulfate wherein the alkyl group contains 10 to 18 carbon atoms and the polyethoxy moiety has 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from 2: 1 to 6 : 1; (c) from 5 to 20% sodium tripolyphosphate; (D) from 1 to 10% sodium carbonate, sodium bicarbonate or mixtures thereof, the weight ratio of (c) to (d) being from 2: 1 to 6: 1; (e) from 10 to 15% of a sodium bentonite; (F) an effective amount of said enzyme or enzyme mixture; (g) the enzyme stabilizing system which, based on the weight of the detergent, contains (i) from 1 to 5% glycerol (ii) from 1 to 5% of an alkali metal borate and (iii) from 0.5 to 4% of said detergent and (h) the residue comprising water and optionally less essential excipients. Process according to claim 6, characterized in that the alkali metal alkylbenzene sulfonate t is sodium 1-linear trihydride, and the 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 polyethoxide moiety. 3 ethylene oxide groups. 5 Process according to claim 7, characterized in that the ratio of tridecylbenzenesulfonate to polyethoxy sulfate is from 2: 1 to 4: 1. Process according to claim 6, characterized in that the liquid detergent contains from 8 to 16% sodium tripolyphosphate and from 2 to 6% sodium carbonate, sodium bicarbonate or mixtures thereof. Process according to claim 6, characterized in that the carboxylic acid compound is aspartic acid or a water-soluble salt thereof. 20 25 30 35