DK164745B - STABILIZED, ENZYMOUS AND BUILDER-CONTAINING LIQUID DETERGENT MIXTURE AND ITS USE - Google Patents

Description

in

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BACKGROUND OF THE INVENTION The present invention relates to stable, buoyant, and enzyme-containing liquid detergent compositions suitable for washing clothes or for soaking. More particularly, the invention relates to aqueous, enzyme-containing liquid detergent mixtures containing one or more surfactants and which are characterized by being physically stable, homogeneous liquid mixtures.

The invention further relates to a method for washing clothes 10 using the present detergent composition.

In the composition of stable in serous enzyme-containing liquid detergent mixtures, much attention has been directed to the prior art. The desirability of incorporating enzymes into detergent mixtures is primarily due to the efficacy of proteolytic and amylolytic enzymes in decomposing proteinaceous and starchy materials found on contaminated textiles, thereby facilitating the removal of stains, such as sleeping spots, bloodstains, chocolates and 20 similar, during laundry. However, enzymatic materials suitable for laundry detergents, especially proteolytic enzymes, are relatively expensive. In fact, they are generally among the most expensive constituents of a typical commercial liquid detergent, although contained in relatively small quantities. Furthermore, enzymes are known to be unstable in aqueous agents. It is for this reason that an excess of enzymes are generally required in liquid detergents to compensate for the expected loss of enzyme activity during prolonged storage times. Accordingly, the prior art is loaded with proposals for stabilizing enzyme-containing liquid detergent mixtures, and in particular non-containing liquid detergent mixtures, using various materials incorporated into the mixture to act as enzyme stabilizers.

In the case of liquid detergents containing a builder, the problem of enzyme metabolism is particularly acute. This is primarily due to the fact that detergent builders have a destabilizing effect 2

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on enzymes, even in agents containing enzyme stabilizers, which are otherwise effective in non-buildup preparations. Furthermore, incorporation of a builder into a liquid detergent presents a further problem, namely the ability to form a stable single-phase mixture. The solubility of sodium tripolyphosphate is e.g. relatively limited in aqueous agents and especially in the presence of anionic and nonionic surfactants.

British Patent Laid-Open No. 2,079,305 discloses an aqueous, liquid and enzyme-containing liquid detergent which is stabilized by a mixture of a polyol and boric acid. As indicated in the Examples of the British disclosure, relatively large amounts of glycerol 15 are required to stabilize the enzymes in the agent. Nevertheless, as demonstrated by the following in the present disclosure, the enzyme stabilizing effect provided by a mixture of glycerol and borax in a liquid aqueous liquid detergent is relatively modest.

20 European Publication No. 125,505 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 substitute for a polyol, such as glycerol, in known enzyme stabilizing mixtures of glycerol and a boron compound. However, the dicarboxylic acid borax mixtures of this disclosure, like the prior art mixture of glycerol and borax, are unable to provide anything other than 30 a modest stabilizing effect in the present builder-containing liquid detergents. Therefore, there is a need to noticeably improve enzyme stability in aqueous, builder-containing detergents of the type defined herein to levels well above the present capability of the prior art.

The present invention relates to a stabilized enzyme-containing and buoyant liquid detergent blend comprising: 3

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(a) 5-20% by weight of one or more surfactant surfactant compounds selected from anionic, nonionic and amphoteric surfactant compounds, 5 (b) 5-30% by weight of one or more builder salts selected from alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitride 1 otri acetates and polyacetal carboxylates, (c) an effective amount of an enzyme or enzyme bond selected from alkaline protease enzymes and α-amylase enzymes, (d) an enzyme stabilizing system, and (e) the residual water and optionally a minor amount of excipients. and the detergent composition is characterized in that the enzyme stabilizing system, based on the weight of the detergent mixture, consists of (i) 1 - 10% glycerol, (ii) 1-8% of a boron compound selected from boric acid, boron oxide and alkali metal borates. and (iii) 0.5 - 8% of a carboxylic acid compound selected from saturated and unsaturated di- and / or tricarboxylic acids having 2 to 8 carbon atoms and water-soluble salts thereof.

In a preferred embodiment of the liquid detergent composition according to the invention, it comprises: (a) 5 - 15% of an a1k1 imeta1a 1alkylbenzenesulfonate wherein the alkyl group contains 12 to 15 carbon atoms, 30 (b) 2 - 5% of an a The 1-carbon-ethyl-1-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 8: 1, 35 (c) 5 - 30% sodium tripolyphosphate, 4

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(d) 1 - 10% sodium carbonate, the weight ratio of (c) to (d) being from 2: 1 to 6: 1, (e) an effective amount of the enzyme or enzyme mixture, (f) having the enzyme stabilizing system based on of the weight of the detergent mixture contains (i) 3-7% glycerol, (ii) 1-5% alkali metal borate and (iii) 0.5-4% of the carboxylic acid compound, and (g) the remainder water and optionally excipients.

The method according to the invention for washing clothes with the present detergent mixture is characterized by the characterizing part of claim 15 71 s.

The liquid detergent composition described is a commercially acceptable powerful detergent capable of satisfactorily cleaning laundry items containing both oily and particulate contaminants. The detergent composition of the invention can also be used to pre-treat heavily contaminated areas, such as collars and cuffs, on items to be washed.

The present invention is based on the invention of a three-component enzyme stabilizing system, as defined herein, which provides an enzyme stable serotonizing effect on the liquid detergent compositions of the invention that is far beyond what is obtainable with conventional enzyme stabilization isotope. 30 rer. The enzyme stabilizing effect thus obtained reflects a synergism among the three components. According to the invention, the enzyme stability obtained by the mixture of glycerol and borax or a mixture of borax and a dicarboxylic acid, as disclosed in the prior art, can be synergistically improved by using the three-component stabilization system defined herein. in the liquid detergent compositions in question with a view to significantly increasing the level 5

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of the enzyme stack 1 in addition to the stability provided by either the mixture of glycerol and borax or of the mixture of borax and dicarboxylic acid when 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 included in the detergent compositions of the invention is a mixture of glycerol, a boron compound selected from boric acid, boron oxide and an alkaline number of borate, and a carboxylic acid compound as defined herein. The weight of the stabilizing system in the present builder-containing liquid detergent mixtures is generally 3-25 wt%, preferably 3-15 wt%. The weight ratio of glycerol to borax in the stabilizing mixtures is generally from 1 to 3. The preferred amount of glycerol in the mixture is from 3 to 7%, the preferred amount of boron compound is from 1 to 5%, and the preferred amount of carboxyl compound is is from 0.5 to 4%, based on the weight of the mixture.

20

The carboxylic acid compounds which can be used in the enzyme stabilizing system included in the detergent composition of the invention include saturated as well as unsaturated di- and tr in carboxylic acids having 2 to 8 carbon atoms, including oxalic acid 25 (H00CC00H), malonic acid (H00CCH2C00H), maleic acid (H00CCH = CHC00H) and succinic acid (HOOCCH2CH2COOH). The carboxylic acids may contain hydroxy or amine substituents, as exemplified by malic acid (HOOCCHOHCH2COOH), tartaric acid (di hydroxyacetic acid), aspartic acid (amino acid) and citric acid. Preferred carboxylic acids according to the invention are succinic, maleic, malonic and malic. From a commercial standpoint, a particularly preferred carboxylic acid compound is citric acid and / or its salts because of their relatively low cost.

The alkaline proteolytic enzymes suitable for the present compositions comprise the various commercial liquid enzyme preparations which have been adapted for use 6

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in detergents. Powder-like enzyme preparations can also be used, although they are generally less suitable for incorporation into the liquid liquid detergents. Thus, suitable liquid enzyme preparations include "Alkalase®," Esperase "®, "Mexatase "® and" AZ-Protease ".

Suitable liquid α-amylase enzyme preparations include those sold under the trademarks "Thermamyl" ® and “Maxamyl” ®.

10 "Esperase" ® is particularly preferred for the present compositions because of its optimized activity at the higher pH values applicable to the builder-containing detergents.

The preferred surfactants for use in the present liquid mixtures are the synthetic anionic surfactant compounds and in particular a mixture of higher alkylbenzenesulfonate and alkyl polyethoxy sulfate. Although other water-soluble higher alkylbenzene sulfonates may also be present in the compositions of the present invention, such as potassium salts and, in some cases, the ammonium or alkanol-20 ammonium salts, when appropriate, it has been found that the sodium salt is highly preferred, which is also the case for alkyl polyethoxysulfate surfactant compound. Alkylbenzenesulfonate is one in which the higher alkyl group has 12 to 15 carbon atoms, preferably 13 carbon atoms. The alkyl polyethoxy sulfate, which may also be referred to as a sulfated polyethoxylated higher linear alcohol, or that. 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 12 to 15 carbon atoms, e.g. ca. 13 carbon atoms and containing 3 to 11 ethylene oxide groups, preferably 3 to 7, more preferably 3 to 5 and most preferably 3 ethylene oxide groups. The ratio of alkylbenzene sulfonate to polyethoxy sulfate in the surfactant mixture is preferably from 2: 1 to 8: 1 and most preferably from 3: 1 to 5: 1 by weight. At ratios above 5: 1, the physical stability of the product may be adversely affected.

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Under appropriate circumstances, other anionic surfactants such as fatty alcohol sulphates, paraffin sulphonates, olefin sulphonates, monoglyceride sulphates, sarcosinates and similarly functioning surfactants, preferably as a 1 potassium metal surfactants, e.g. sodium salts, are present, sometimes to partially replace the aforementioned synthetic organic surfactants, but if present, they are usually present in addition to such surfactants. The supplementary surfactants will usually be sulfated or sulfonated products (usually as the sodium salts) and will contain long chain (8 to 20 carbon atoms) linear alkyl groups or fatty alkyl groups. In addition to any additional anionic synthetic organic surfactants, nonionic and amphoteric materials may also be present, such as the "Neodoles" ®, which are condensation products of ethylene oxide and higher fatty alcohols, e.g. "Neodol" ® 23 - 6.5, which is a condensation product of a higher fatty alcohol of 12 to 13 carbon atoms with 6.5 moles of ethylene oxide. Examples of the various mentioned surfactants and classes of surfactants can be found in Surface Active Agents, Volume II, by Schwartz, Perry and Berch 2 ^ (Inter-science Publishers, 1958).

The buildup of the salt salt combination of the invention which has been found to satisfactorily improve the purity of the mixture of synthetic anionic organic surfactants and provide the desired pH in the liquid detergent mixture and in the wash water is a mixture of sodium tripolyphosphate and sodium carbonate. The builder salts are used in the present compositions in amounts of generally from 5 to 25% by weight. In the preferred builder salt combination, sodium tripolyphosphate is present in an amount of 5 - 20% by weight, preferably 10 to 16% by weight, and sodium carbonate is present in an amount of 1 - 10% by weight, preferably 3 to 7% by weight, with the weight ratio between tripolyphosphate and carbonate in the preferred builder mixtures is from 2: 1 to 6: 1, most preferably from 2: 1 to 4: 1. As used herein, the term alkali metal "carbonates" or "carbonate" should include the carbonates, bicarbonates and sesquicarbonates of such an alkali metal.

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For the best work-up, easier mixing and good end-use properties, it is preferred that the sodium tri-polyphosphate has a low content of phase I tripolyphosphate. The content of type I tripolyphosphate will thus normally be less than 30% of the used. tripolyphosphate. Although incompletely neutralized tripolyphosphate can be used in some cases, the phosphate used can usually be considered to be pentane sodium tripolyphosphate, Na 2 P 2 O 2 Q. In some cases, such as when potassium salts of 10 other materials are present, ion exchange in an aqueous medium may, of course, result in salts other than the sodium tri-polyphosphate present, but for the purposes of the present description, sodium tripolyphosphate is considered in the form of the tanodium salt as being the tripolyphosphate used as the material normally charged to the mixer to prepare the subject liquid detergent composition.

Other preferred coatings which may be used in place of sodium tripolyphosphate and sodium carbonate or in connection therewith include a polyacetate carboxylate as described herein and sodium nitriloacetate (NTA). Various mixtures of said water-soluble builder salts can of course be used. The tripolyphosphate-carbonate composition described has nevertheless proved to be the most preferred, although the other builders and mixtures thereof may also be used.

Other builders which may be used in addition to the amounts of the builders mentioned above include other phosphates such as tetrasodium pyrophosphate or tetrasodium pyrophosphate, sodium bicarbonate, sodium citrate, sodium gluconate, sodium silicate, and sodium sesquicarbonate. Among the water-insoluble builders which 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 disclosed in U.S. Patent Nos. 4,144,226 and 4,315,092. U.S. Patent No. 4,146,495 discloses cleaners containing polyacetal carboxylates as builders.

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g

The polyacetal carboxylates which can be used here as builders can be considered to be those described in U.S. Patent No. 4,144,226 and may be prepared by the process mentioned therein. Such a typical product will have the formula 5 R, - (CHO) - R-i j n i

C O OM

wherein M is selected from alkali metal, ammonium, alkyl groups having 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamines, both having 1 to 4 carbon atoms in their alkyl groups, n being on average at least 4; and R 1 and R 2 are any chemically stable groups which stabilize the polymer against rapid depolymerization in alkaline solution. The polyacetal carboxylate will preferably be one wherein M is alkali metal, e.g. sodium, n is from 50 to 200, R

CH, CH-0 MOOC

3 2,, HCO or H, C-CO-I 3 i

H, C MOOC

20 or a mixture thereof, R2 is also 2ch3

-CH

25! ch 3 and n are on average from 20 to 200, more preferably from 30 to 80. The calculated weight average of the molecular weights of the polymers will usually range from 2000 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 provided by the Monsanto Company and is known as Builder U.

w D

calculated average molecular weight of approx. 8,000 and an active polymer content of approx. 80%.

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Although the preferred polyacetal carboxylates have been described above, it will be understood that they may be wholly or partially replaced by other such polyacetal carboxylates or related organic builder salts described in the descriptions of the above-mentioned patents on such compounds, methods of preparation thereof and agents in which they are used. Also, the chain terminating pits described in the various patents, in particular U.S. Patent No. 4,144,226, may be used provided they have the desired stabilizing properties which allow the depolymerization of said builders into acidic media, facilitating biodegradation. thereof in wastewater streams but retains their stability in alkaline media such as washing solutions.

The only other necessary component of the liquid detergent compositions in question is water. Usually, the hardness content of such water will be less than approx. 300 ppm as CaCO 3, and preferably it will be less than 150 ppm. It may often be desirable to use deionized water, although tap water 20 having a hardness content of less than 50 or 100 ppm will frequently be equally satisfactory.

Various adjuvants may be present in the liquid detergent compositions such as fluorescent detergents, perfumes, 25g colorants. The fluorescent clearing agents include the well-known stilbene derivatives including the cotton and nylon clearing agents, such as those sold under the trademark "Tino-pal" (5BM Conc.). The perfumes used usually include essential oils, esters, aldehydes and / or alcohols, all of which are known in the art of perfume. The coloring agents 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 can antigen scavengers such as sodium carboxymethyl cellulose, dispersing agents such as sodium polyacrylate, bleaching agents, bactericides, fungicides, anti-foam agents such as silicones, anti-contaminants,

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π esters, preservatives such as formalin, foam stabilizers such as laurine myristine diethanolamide, and auxiliary solvents such as ethanol. Usually, the individual amounts of such excipients will be less than 3%, often less than c 1% and sometimes even less than 0.5%, with the exception of any fillers and solvents as well as additional detergents and builders, the amounts of which may sometimes be as high such as 10%. The total amount of excipients including unspecified synthetic detergents and builders will normally not exceed 20% of the product and suitably constitute less 10% thereof, more desirably less than 5% thereof. The adjuvants used will, of course, be selected so as not to interfere with the washing action of the liquid detergent and thus to avoid instability of the product upon standing. Excipients which cause the formation of accidental deposits on the laundry must also be avoided.

The liquid detergent in question is effective and easy to use. Compared to powerful laundry detergent powders, much smaller volumes of the liquids in question are used to achieve similar cleaning of contaminated laundry. For example, using a typical preferred detergent composition of the present invention is needed. only approx. 132 g or 1/2 cup of liquid for a pre-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 filling machines. Thus, the concentration of the liquid detergent mixture in the wash water is about the size of approx. 0.2%. The amount of the liquid detergent mixture in the wash water will usually be in the range of approx. 0.05 to approx.

0.3%, preferably from 0.15 to 0.25%. The amounts of the various constituents of the liquid mixture may vary accordingly. Similar results can be obtained by using larger amounts of a more dilute detergent mixture, but the larger amount required will require further packaging and will generally be less suitable for consumer use and may also result in product separation.

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The viscosity of the liquid detergent in question is usually in the range of 1000 to 10,000 cents in poise, preferably 2000 to 5000 centipoise, but products with other suitable viscosities can also be used. At said viscosities, the liquid detergent mixture can be poured and is stable, non-separating and uniform. The pH of the liquid detergent suspension in on, usually in the range of from 7 to 11.5, preferably from 8 to 10.5, is found to help maintain product stability and washability.

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

Example 1

Component Percent Sodium Tripolyphosphate 15.0 Sodium Carbonate 5.0 Sodium Linear Tridecylbenzenesulfonate 12.2 AE0S (1) 2.8 Carboxymethyl Cellulose (CMC) 0.15 Optical Clarifier 0.4 Perfume 0.3 Enzyme ("Esperase" ® 8.0L) (2) 1.0 glycerol 4.0 borax 3.0 triethanolamine 1.0 30 sodium citrate 2.0 water and auxiliary residue (1) Natr in umalkyl1 polyethoxy sulfate wherein the alkyl group has 12 to 15 carbon atoms and the polyethoxy moiety has 3 ethoxy groups .

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(2) "Esperase" ® has an activity of 8.0 KNPU / g.

The mixture shown above was prepared by the following procedure: 32.5 parts of deionized water at 4 ° C are added to a suitable mixer such as a vertical cylindrical tank equipped with a stirrer. With the stirrer set to medium stirring, a mixture of 5.0 parts of anhydrous calcined soda and 0.17 parts of sodium carboxymethyl cellulose is introduced into the water. The agitator speed is then increased to 10 maximum stirring, and 15.0 parts of pentane sodium tripolyphosphate is slowly added to the mixer over a period of 10-15 minutes to form a milky white suspension. The agitator speed is then reduced to a slow / medium high setting while adding 19.1 parts of a high 15 AI (about 50%) LTBS slurry. Then, the solution of (S) optical clarifier / color consisting of 0.4 parts of "Tinopal" LMS-X, 0.06 parts of blue dye and 2.0 parts of deionized water is added. Once a uniform blue colored solution is obtained, 0.3 parts of perfume is added to the mixture with stirring. This is followed by the slow addition of 4.0 parts of glycerol, 3.0 parts of borax and 1.0 part of triethanolamine (TEA improves long-term product stability) as a three component slurry. Stirring is continued until the mixture is uniform in appearance and then 2.0 parts sodium citrate and 4.0 parts water are slowly added. Stirring of the mixture is then reduced while a mixed AI detergent base material consisting of 5.7 parts of LTBS slurry (about 50% AI) and 4.7 parts of AEOS (about 60% AI) is added to the mixture. This is followed by the slow addition of 1.0 part proteolytic enzyme under continuous stirring until all materials are completely dispersed or dissolved.

Example 2 35 Enzyme-containing builder-containing liquid detergent mixtures A to G were formulated as listed below in Table 1. Percentages indicated weight%. The arrows must indicate the extent to which mixtures B through G are identical to mixture A.

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Table 1

Component A B C D E F G

pentane sodium tripolyphosphate 15% sodium carbonate (anhydrous) 5 linear linear tridecylbenzenesulfonate 12.2 AEOS (1 * 2.8 initial clarifier 0.4 ("Tinopal" LMS-X) 10 perfume 0.3 CMC 0.2 enzymes , glycerol - 4-4--4 borax - 3 3 - 3 3 15 carboxylic acid compound - - - 2 2 2 water and auxiliary residue (1) Sodium alkyl polyethoxy sulfate, wherein the alkyl group has 12 to 15 carbon atoms, and the polyethoxy moiety has 3 ethoxy groups (2) "Esperase" ® has an activity of 8.0 KNPU / g (kilogram Novo protease units / gram).

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Among others, A to G's enzyme actions were investigated after 7 days of storage at 43 ° C. The measured enzyme activity for each mixture after this storage time is given in Table 2 and Table 3 as a percentage of the initial value. The various carboxylic acids and salts used in the compositions of mixtures A, B, C, D, E and G are shown in Table 2 as well as the enzyme activities corresponding to each mixture.

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Table 2

Enzyme Stab1 in Tet

Percent of active enzyme

5 Mix after 7 days at 43 ° C

A (control) ND *

B (with g 1ycero1) ND

C (with borax) ND

10 D (with glycerol and borax) 45

Mixture E (with carboxylic acid compound 1se) wherein the carboxylic acid compound is: 15 (1) succinic acid ND * (2) malonic acid "(3) malic acid" (4) oxalic acid "20 (5) maleic acid" (6) tartaric acid " (7) aspartic acid "(8) citric acid" (9) sodium succinate (10) sodium tartrate "(11) sodium citrate (12) sodium glycolate" (13) sodium tetrahydroxysuccinate "30 * ND = not detectable (below 10% residual activity).

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Agent G (with g 1ycero1 / borax / carboxylic acid compound) in which Percent of active enzyme

the carboxylic acid compound is: after 7 days at 43 ° C

5 (1) sodium succinate 60 (2) succinic acid 94 (3) malonic acid 91 (4) malic acid 79 (5) oxalic acid 81 10 (6) maleic acid 88 (7) tartaric acid 63 (8) aspartic acid 84 (9) citric acid 62 (10) sodium tartrate 54 (11) sodium citrate 57 (12) sodium glycolate 50 (13) sodium tetrahydroxysuccinate 61

As shown in Table 2, mixture A, the control mixture, as well as mixtures B and C containing glycerol and borax as individual stabilizers, showed almost no enzyme activity after the 7 day storage time at 43 ° C. could not be measured accurately, they are designated "ND". Mixture D containing glycerol / borax in the absence of a carboxylic acid compound provided an improvement in enzyme stability over mixtures A, B and C, but more than 50% of the enzyme was deactivated. However, the various mixtures E containing a variety of carboxylic acid compounds, as indicated, showed absolutely no improvement in enzyme stability relative to mixtures A, B and C. However, the mixtures G, which are mixtures of the present invention, exhibit the unexpected and synergistic enhancement of enzyme stability achieved by using glycerol / borax in combination with a carboxylic acid compound see in the liquid liquid detergent in question. It should be noted that in each of the 13 mixtures corresponding to the mixture G tested, the enzyme activity was improved over the mixture D (containing glycerol and borax).

Claims (11)

A comparison of the enzyme activities obtained with mixtures D (glycerol / borax) and various mixtures F (borax / carboxylic acid compound) and G (composite of the invention) is shown below in Table 3. Table 3 Percent of active enzyme Detergent composition according to claim 1, characterized in that it comprises: 20 (a) 5 - 15¾ of an alkali metal alkylbenzenesulfonate, wherein the alkyl group contains 12 to 15 carbon atoms, (b) 2 - 5¾ 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 8: 1, (c) 5 - 30% sodium tripolyphosphate, 30 (d) 1 - 10¾ sodium carbonate, the weight ratio of (c) to (d) being from 2: 1 to 6: 1, (e) an effective amount of the enzyme or enzyme mixture, (f) having the enzyme stabilizing system based on the weight of the detergent mixture contains (i) 3-7% glycerol, (ii) 1-5% alkaline imetalborate and (-iii) 0.5-4% of the carboxylic acid compound, and (g) the remainder water and optionally excipients. 5 Detergent composition according to claim 2, characterized in that the alkali metal alkyl benzyl sulfonate is sodium-1 especially tridecylbenzenesulfonate and that the alkali metal in the alkali metal alkyl polyethoxy sulfate is sodium, all of the alkyl group having about 12 to 15 carbon atoms and the polyethoxy moiety having about 3 ethylene oxide groups. Detergent composition according to claim 3, characterized in that the ratio of tridecylbenzenesulfonate to polyethoxy sulfate is from 3: 1 to 5: 1. Detergent composition according to claim 2, characterized in that the boron compound is an alkali metal borate. Detergent composition according to claim 5, characterized in that the borate is borax. A method of washing clothes in which the stained and / or contaminated fabrics to be washed are contacted with a stabilized enzyme-containing and builder-containing liquid detergent mixture comprising: (a) 5-20% by weight of a or more surfactant surfactant compounds selected from anionic, nonionic and amphoteric surfactant compounds, (b) 5-30% by weight of one or more builder salts selected from alkali metal tripolyphosphates, alkali metal nitrilotri acetates and polyacetylcarboxylic acid, (c) an effective amount of an (d) an enzyme stabilizing system, and (e) the residual water and optionally perfume and other excipients, characterized in that the enzyme stabilizing system consists of ( i) 1 - 10% glycerol, (ii) 1-8% of a boron compound selected from boric acid, boron oxide and alkali metal borates, and (iii) 0.5 - 8% of a carboxylic acid compound see selected from t saturated or unsaturated di- and / or tricarboxylic acids having 1 to 8 10 carbon atoms and water-soluble salts thereof. Process according to claim 7, characterized in that the liquid detergent mixture comprises: 15 (a) 5 - 15% of an alkali metal alkylbenzenesulfonate, wherein the alkyl group contains 12 to 15 carbon atoms, (b) 2 - 5% of an alka 1 imeta 1 alkyl of 1 polyethoxy su barrel, wherein the alkyl group contains 10 to 18 carbon atoms and the polyethoxy moiety has 3 to 11 ethylene oxide groups, the weight ratio between (a) and (b) being from 2: 1 to 8: 1, (c) 5-20% sodium tripolyphosphate, (d) 1-10% sodium carbonate, the weight ratio of (c) to (d) being from 2: 1 to 6: 1, (e) an effective amount of said enzyme or said (f) wherein the enzyme stabilizing system, based on the weight of the detergent, contains (i) 3-7% glycerol, (ii) 1-5% of an alkali metal borate and (iii) 0.5-4% of said carboxylic acid orbi ndel se, and 35 (g) the remainder of water and any lesser amounts of excipients. DK 164745 B 21 Process according to claim 8, characterized in that the alkali metal alkylbenzene sulfonate is sodium linear tridecylbenzenesulfonate and that the alkali metal in said alpha-1k1imethoxy-polyethoxy sulfate is sodium, the alkyl group contains 12 to 15 carbon atoms and the polyethoxy moiety has about 3 ethylene oxide groups. Process according to claim 9, characterized in that the ratio of tridecylbenzenesulfonate to polyethoxy sulfate is from 3: 1 to 5: 1. 10 10 Mixing after 7 days at 43 ° C D (glycerol / borax) 45 F (borax / malonic acid) 13 G (glycerol / borax / malonic acid) 91 15 F (Borax / Aspartic Acid) 39 G (Glycerol / Borax / Aspartic Acid) 84 F (Borax / Citric Acid) ND * G (Glycerol / Borax / Citric Acid) 62 20. ND = not detectable (below 10% remaining activity). As shown in Table 3, the various mixtures G containing a three-component stabilizer system of the invention provided a synergistic improvement of enzyme stability relative to mixtures D and F prepared in accordance with the prior art. Claims. Stabilized enzyme-containing and builder-containing liquid detergent mixture comprising: (a) 5-20% by weight of one or more surfactant surfactant compounds selected from the anionic, nonionic and amphoteric ID compounds of the anion, (b) 5-30% by weight of a or more builder salts selected from alkali metal tripolyphosphates; and (e) the residual water and optionally a small amount of excipients, characterized in that the enzyme stabilizing system, based on the weight of the detergent mixture, consists of (i) 1 - 10¾ glycerol, (ii) 1-8¾ of a boron compound. selected from boric acid, boron oxide and alkali metal borates, and (iii) 0.5 - 8¾ of a carboxylic acid compound see selected from 15 saturated and unsaturated di- and / or tricarb oxyl acids having 2 to 8 carbon atoms and water-soluble salts thereof. Process according to claim 8, characterized in that the boron compound is borax. 15 20 25 30 35