AT394385B - STABILIZED, CLEAR, SINGLE-PHASE, BUILDER AND ENZYME-CONTAINING LIQUID DETERGENT - Google Patents

Description

AT 394 385 B

The invention relates to a stabilized, clear, single-phase, builder and enzyme-containing liquid detergent based on anionic surfactants in water, consisting of (a) 8 to 20% by weight of one or more anionic surfactants, (b) 5 to 25% by weight. %, in particular 10 to 20% by weight, of a water-soluble phosphate-free builder salt, (c) an effective amount of an enzyme or enzyme mixture from the group consisting of alkaline protease enzymes and α-amylase enzymes, (φ an enzyme stabilizing system and (e) 25 to 75% by weight of water.

The formulation of stabilized, enzyme-containing liquid detergents has been the goal of many efforts to date. It is desirable to incorporate enzymes in detergents primarily because of the effectiveness of proteolytic and amylolytic enzymes in breaking down protein and starch on soiled textiles, thereby facilitating the removal of stains such as dripping, blood, chocolate and the like during washing. However, enzymatic substances suitable for detergents, in particular proteolytic enzymes, are relatively expensive. In general, they are even the most expensive part of a typical commercial liquid detergent, even when present in a relatively small amount. It is also known that enzymes are unstable in aqueous mixtures. For this reason, an excess of enzymes is generally required in liquid detergents in order to compensate for the decrease in the enzyme action during extended storage times, which must be expected. The relevant literature is therefore full of proposals for stabilizing liquid detergents containing enzyme, in particular builder-free liquid mixtures by using various substances which are incorporated into the mixtures and serve as enzyme stabilizers.

In the case of liquid detergents that contain a builder, the problem of enzyme instability is particularly critical. This is primarily due to the fact that builders have a destabilizing effect on enzymes, even in mixtures which contain enzyme stabilizers which are otherwise effective in formulations which do not contain builders. In addition, the incorporation of a builder into a liquid detergent poses another difficulty, namely that of forming a stable single-phase solution, since the solubility, e.g. B. of sodium tripolyphosphate, is relatively limited in aqueous mixtures, especially in the presence of anionic and nonionic surfactants. For example, British Patent 2,079,305 proposes an aqueous liquid detergent containing builder and enzyme which is stabilized by a mixture of polyol and boric acid. However, the mixtures described in the examples are cloudy suspensions instead of stable, clear, single-phase solutions, which are easily subject to phase separation during longer storage times. As a result, enzyme stability and physical product stability continue to be problems to be solved by formulating an economically acceptable liquid detergent containing builder and enzyme.

The object of the invention is therefore to make a stabilized, clear, single-phase, builder and enzyme-containing liquid detergent based on anionic surfactants available in water.

To achieve the object, a liquid detergent of the type specified at the outset is proposed according to the invention, which is characterized in that component (d), based on the weight of the detergent, (i) 12 to 25% by weight of propylene glycol and (ii ) 1 to 5 wt .-% of a boron compound from the group consisting of boric acid, boron oxide and alkali borates and the detergent is practically free of crosslinked polyacrylate polymers.

For washing, the stained and / or soiled materials are brought into contact with an aqueous solution of the liquid detergent defined above. Unlike the known detergents containing builders and enzymes, the compositions of the invention are distinguished by the fact that they are clear, single-phase, homogeneous solutions which are physically stable over long storage times and over a wide temperature range. To avoid phase separation or product separation, the compositions according to the invention are essentially free of phosphate builder salt.

Unlike the enzyme and builder-containing liquid detergents based on anionic surfactants of the prior art, the anionic detergent substance in the detergents according to the invention is solubilized in the presence of a builder salt. In addition, the enzyme-containing detergents according to the invention are distinguished by the presence of an enzyme-stabilizing system which not only ensures the long-term stability of the enzyme in a wide temperature range, but also promotes the solubility of the anionic surfactant and of the phosphate-free builder in the aqueous detergent, thereby forming a physically stable single-phase solution for the specific range of the specified compositions is made possible.

As already mentioned, the enzyme stabilizing system of the invention is a mixture of propylene glycol and a boron compound from the group of boric acid, boron oxide and alkali borate capable of reaction with propylene glycol, the amount of propylene glycol preferably being 15 to 20% by weight and the amount of Boron compound is preferably 1 to 3%, based on the weight of the detergent

The alkaline proteolytic enzymes suitable for the detergents according to the invention include the -2-

AT 394 385 B various commercially available liquid enzyme preparations which have been adapted for use in detergents, enzyme preparations in powder form also being useful, although experience has shown that they are less expedient for incorporation into liquid detergents containing builders. Suitable liquid enzyme preparations are, for example, " Alcalase " and " Esperase " sold by Novo Industries, Copenhagen, Denmark and " Maxatase " and " AZ Protease " sold by Gist-Biocades, in Delft, The Netherlands. Esperase is particularly preferred for the detergents according to the invention because of its optimal effectiveness at the higher pH values of the detergents containing builders.

Suitable liquid α-amylase enzyme preparations are e.g. B., those of Novo Industries and Gist-Brocades under the respective trade names " Termamyl " or " Maxamyl " sold.

The anionic surfactant used in the detergent according to the invention can be one of the many known surfactants which have been described, for example, by Schwartz, Perry and Berch in Surface Active Agents, Volume 2, published in 1958 by Interscience Publishers, to which reference is made here.

The most preferred anionic surfactants are the higher (10 to 18 or 20 carbon atoms) alylbenzenesulfonate salts or sulfonates in which the alkyl group preferably has 10 to 15 carbon atoms, with a straight chain alkyl group having 12 to 13 carbon atoms being most preferred. Such an alkylbenzenesulfonate preferably has a high content of 3- (or higher) phenyl isomers and a correspondingly low content (generally well below 50%) of 2- (or lower) phenyl isomers; in other words, the benzene ring is preferably largely attached to the 3, 4, 5, 6 or 7 position of the alkyl group, and the content of isomers in which the benzene ring is attached to the 1 or 2 position is accordingly low . Typical alkylbenzenesulfonate surfactants are described in U.S. Patent 3,320,174. Of course, more highly branched alkylbenzenesulfonates can also be used, but are generally not preferred because of their lack of biodegradability.

Other anionic surfactants that can be used are the olefin sulfonate salts, which generally comprise long chain alkenyl sulfonates or long chain hydroxyalkanesulfonates (with the OH group on the carbon atom that is not directly linked to the carbon atom bearing the -SO ^ H group).

The olefin sulfonate surfactant usually consists of a mixture of such compounds in varying amounts, often together with long chain disulfonates or sulfate sulfonates. Such olefin sulfonates are described in patents such as in U.S. Patent 2,061,618, 3,409,637, 3,332,880, 3,420,875, 3,428,654, 3,506,580 and in British Patent 1,129,158. The number of carbon atoms in the olefin sulfonate is usually in the range of 10 to 25, more often 10 to 18 or 20, and is e.g. B. a mixture mainly composed of Cj2 > C] 4 and Cjg compounds with an average of about 14 carbon atoms, or a mixture of C ^, and Cjg compounds with an average of about 16 carbon atoms.

Another class of valuable anionic surfactants is that of the higher paraffin sulfonates. These can be primary paraffin sulfonates, which can be obtained by reacting long-chain α-olefins with bisulfites, e.g. B. bisulfite, or paraffin sulfonates in which the sulfonate groups are distributed along the paraffin chain, such as in the products obtained by reacting a long-chain paraffin with sulfur dioxide and oxygen under ultraviolet light and then neutralizing with sodium hydroxide or another suitable base (as described in US Pat. No. 2,503,280,2507,088.3 260,741.3 372,188 and in German Pat. No. 735,096). The paraffin sulfonates preferably contain 13 to 17 carbon atoms and are normally the monosulfonate, but optionally it can be the di-, tri- or higher sulfonates. Mostly the di- and polysulfonates are applied in a mixture with a corresponding monosulfonate, e.g. B. as a mixture of mono- and disulfonates containing up to about 30% of the disulfonate. The hydrocarbon substituent thereof is preferably linear, although branched-chain paraffin sulfonates can optionally be used, although they are inferior in terms of biodegradability.

Other suitable anionic surfactants are sulfated ethoxylated higher fatty alcohols of the formula RCXCj ^ O ^ SOßM, wherein R is a fatty alkyl having 10 to 18 or 20 carbon atoms, m = 2 to 6 or 8 (a value of about 1/5 to 1/2 the number of carbon atoms in R is preferred) and M is a solubilizing salt-forming cation, such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino, or a higher alkylbenzenesulfonate in which the higher alkyl radical has 10 to 15 carbon atoms.

Ethylene oxide is the preferred lower alkylene oxide of the anionic alkoxylate surfactant, the proportion thereof in the polyethoxylated higher alkanol sulfonate is preferably 2 to 5 moles of ethylene oxide groups per mole of anionic surfactant, with 3 moles being particularly preferred, especially if the higher alkanol has 11 or 12 to 15 carbon atoms owns. In order to maintain the desired hydrophilic-lipophilic balance when the amount of carbon atoms in the alkyl chain is in the lower part of the 10 to 18 carbon atom range, the ethylene oxide content of the surfactant can be reduced to about 2 moles per mole, whereas if that higher alkanol has 16 to 18 carbon atoms corresponding to the higher part of the range, the number of ethylene oxide groups can be increased to 4 or 5 and in some cases even 8 or 9. Accordingly, a different cation can also be chosen to achieve the best solubility. This can be any suitable solubilizing metal or residue, but is usually -3-

AT 394 385 B

Alkali metal, e.g. As sodium or ammonium. When lower alkylamine or alkanolamine groups are used, the alkyls and alkanols generally contain 1 to 4 carbon atoms, and the amines and alkanolamines can be mono-, di-, and tri-substituted, such as in monoethanolamine, diisopropanolamine, and trimethylamine.

The poly-lower alkoxy-higher alkanol sulfates can be used to achieve an optimal cleaning effect in combination with other preferred anionic surfactants, such as. B. the higher alkylbenzenesulfonates can be used in the liquid detergents containing builders according to the invention. A preferred poly-ethoxylated alcohol sulfate surfactant is sold by Shell Chemical Company under the trade name Neodol 25-3S.

Examples of the higher alcohol polyethene oxysulfates that can be used in the liquid detergents of the invention are mixed C 1-15 normal or primary alkyl triethenoxy sulfate, sodium salt;

Myristyl triethenoxy sulfate, potassium salt; n-decyl diethenoxy sulfate, diethanolamine salt; Lauryl diethenoxy sulfate, ammonium salt; Palmityltetraethene oxysulfate, sodium salt; mixed C 14.15 normal primary alkyl mixed tri- and tetra-ethenoxysulfate, sodium salt; Stearylpentaethene oxysulfate, trimethylamine salt; and mixed C10-I8 normal primary alkyl triethenoxy sulfate, potassium salt.

Other valuable anionic surfactants include the higher acyl sarcosinates, e.g. B. Sodium N-lauroyl sarcosinate; higher fatty alcohol sulfates such as sodium lauryl sulfate and sodium tallow alcohol sulfate; sulfated oils; Sulfates of mono- or diglycerides of higher fatty acids, e.g. B. stearin monoglyceride monosulfate; of these, the higher alcohol sulfates have proven to be inferior to the polyethoxylated sulfates in terms of their cleaning effect; aromatic poly (lower alkenoxy) ether sulfates, such as the sulfates of the condensation products of ethylene oxide and nonylphenol (which usually have 1 to 20 oxyethylene groups per molecule, preferably 2 to 12; polyethoxy-higher alcohol sulfates and alkylphenol polyethoxysulfates with a lower alkoxy (with 1 up to 4 carbon atoms, e.g. methoxy) substituents on a carbon atom close to the carbon atom bearing the sulfate group, e.g. the monomethyl ether monosulfate of a long chain vicinal glycol, e.g. a mixture of vicinal alkanediols with 16 to 20 carbon atoms in a straight chain; Acyl esters of isethionic acid, e.g. oleyl isethionates; acyl-N-methyltaurides, e.g. potassium N-methyllauroyl or oleyl taurides; higher alkylphenyl polyethoxysulfonates; higher alkylphenyl disulfonates, e.g. pentadecylphenyl disulfonate; and higher fatty acid soaps, e.g. mixed Coconut oil and tallow soaps in a 1: 4 ratio.

Among the types of anionic surfactants mentioned above, the sulfates and sulfonates are generally preferred, but the corresponding organic phosphates and phosphonates can also be used if there are no objections to their phosphorus content. In general, the water-soluble anionic surfactants (including soaps) are salts of alkali metal ions such as potassium, lithium and especially sodium, although salts of ammonium and substituted ammonium cations such as those described above, e.g. B. triethanolamine, triisopropylamine, can also be used.

If necessary, a nonionic surfactant can be used in smaller amounts to supplement the anionic surfactant in the builder-containing liquid detergents according to the invention. When used in such a combination with an anionic surfactant, the amount of nonionic surfactant is generally less than about 10%, and preferably less than about 5%, based on the weight of the total mixture.

The nonionic surfactants are usually poly-lower alkoxylated lipophiles in which the desired hydrophilic-lipophilic balance is obtained by adding a hydrophilic poly-lower alkoxy group to a lipophilic portion. In the compositions of the invention, the nonionic surfactant used is preferably a poly-lower alkoxylated higher alkanol in which the alkanol has 10 to 18 carbon atoms and in which the number of moles of lower alkylene oxide (with 2 or 3 carbon atoms) is 3 to 12. Of these materials, those in which the higher alkanol is a higher fatty alcohol having 11 or 12 to 15 carbon atoms and which contain 5 to 8 or 5 to 9 lower alkoxy groups per mole are preferably used. Preferably the lower alkoxy is ethoxy, but in some cases it is desirably mixed with propoxy, the latter, if present, generally being the minor (less than 50%) component. Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, e.g. B. Neodol 25-7 and Neodol 23-6.5, manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols with an average of about 12 to 15 carbon atoms and with about 7 moles of ethylene oxide, and the latter is a corresponding mixture in which the number of carbon atoms of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups per Mol is about 6.5 on average. The higher alcohols are primary alcohols. Other examples of such surfactants include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are Union Carbide Corporation linear secondary alcohol ethoxylates. The former is a mixed ethoxylation product of a 11 to 15 carbon atom linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but is reacted with 9 moles of ethylene oxide. -4-

AT 394 385 B

Higher molecular weight nonionic substances, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohol containing 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being approximately 11, are also valuable for the detergents according to the invention. These products are also manufactured by Shell Chemical Company. Other valuable nonionic compounds include Plurafac B-26 (BASF Chemical Company), which is the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides.

In the preferred poly-lower alkoxylated higher alkanoia, the best balance between the hydrophilic and lipophilic portions is obtained when the number of lower alkoxy groups is about 40 to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60% thereof. The nonionic surfactant preferably consists of at least 50% of the preferred ethoxylated alkanoia. Higher molecular weight alkanols and various other, normally solid, nonionic surfactants and detergent substances can contribute to the gel formation of the liquid detergent and are consequently usually omitted or limited in the detergents according to the invention, although small amounts of the same can be used because of their cleaning properties etc. In both the preferred and less preferred nonionic surfactants, the alkyl groups present are preferably linear, although a small amount of little branching can be tolerated, such as e.g. B. on a carbon atom adjacent to the terminal carbon atom of the straight chain or two carbon atoms away from it and away from the ethoxy chain, provided that such an alkyl branch is no longer than three carbon atoms. Typically, the amount of carbon atoms in such a branched configuration is small and rarely exceeds 20% of the total carbon atom content of the alkyl. Similarly, middle or secondary association with the ethylene oxide in the chain can occur, although linear alkyls that are terminally linked to the ethylene oxide chains are most preferred and are considered to be the optimal combination for cleaning power, biodegradability and non-gelling properties . In such a case it is usually only a small part of these alkyls, generally less than 20%, but can be larger, as in the case of the tergitols mentioned above. Furthermore, propylene oxide, when present in the lower alkylene oxide chain, will usually make up less than 20% of the same, and preferably less than 10% thereof.

The phosphate-free builder salts are generally used in the detergents according to the invention in amounts of from 5 to 25% by weight and preferably from 10 to 20% by weight. Special examples of water-soluble, inorganic builders which do not contain phosphorus are water-soluble inorganic carbonate, bicarbonate and silicate salts. According to the alkali metal, such as. As sodium and potassium carbonates, bicarbonates and silicates, particularly valuable.

Water soluble organic builders such as alkali, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfates can also be used. Specific examples of polyacetate and polycarboxylate builders are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzene polycarbonate (e.g. penta- and tetra-) acids, carboxymethoxy succinic acid and citric acid.

The percentage of water, the main solvent in the detergents according to the invention, is generally 25 to 75%, preferably 40 to 60%, based on the weight of the detergent.

The optical brighteners or whitening agents used in the liquid detergents of the invention are important components of modern detergents which give the washed laundry and the washed textiles a luminous appearance, so that the laundry is not only clean but also appears clean, although it is possible for one In order to use a single brightener in the liquid detergents of the invention for a specific purpose, it is generally desirable to use brightener blends which have good brightening effects on cotton, nylon, polyester and blends of such materials and which are also bleach resistant. A good description of such optical brighteners can be found in the article by A. E. Siegrist " The Requirements of Present Day Detergent Fluorescent Whitening Agents " in J. Am. Oil Chemists Soc., January 1978 (Volume 55). This article and U.S. Patent 3,812,041, both of which are incorporated herein by reference, contain detailed descriptions of a wide variety of suitable optical brighteners. Brighteners which can be used for the detergents according to the invention are, for example: Calcofluor 5BM (American cyanamide): Calcofluor White ALF (American cyanamide); SOF A-2001 (Ciba); CDW (Hilton-Davis); Phorwite RKH, Phorwite BBH and Phorwite BHC (Verona); CSL, powder, acidic (American cyanamide); FB 766 (Verona); Blancophor PD (GAF); IINPA (Geigy); Tinopal RBS 200 (Geigy).

Auxiliaries may be present in the liquid detergents to ensure additional properties, both functional and aesthetic. Such valuable adjuvants are dirt-bearing or anti-anti-reprecipitants, such as polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose; Thickeners, e.g. B. gums, alginates, agar agar, foam improvers, e.g. B. Laurin myristine diethanolamide; Foam sealer, e.g. B. silicones; Bactericides, e.g. B. tribromosalicylanilide, hexachlorophen; Dyes; Pigments (water dispersible); Protective substances; Ultraviolet absorber; Fabric softeners, opacifying agents, e.g. B. polystyrene suspensions; and fragrances. Of course, these materials are classified according to the desired properties of the finished product, their compatibility with the other components and their -5-

AT 394 385 B selected solubility in the liquid detergent.

The liquid detergents according to the invention are effective and easy to use. Compared to powdery coarse detergents for washing laundry, much smaller volumes of the detergents according to the invention are used to achieve comparable cleaning of the soiled laundry. For example, using a typical preferred formulation of the invention, only about 132 g or 1/2 cup of liquid is required for a full tub in an automatic top-loading washing machine in which the volume of water is 55 to 75 liters and for the side or front-filling machines, the required amount is even less. The concentration of the liquid detergent in the wash water is of the order of about 0.2%. In general, the liquid detergent is present in the wash solution in an amount of about 0.05 to 0.3%, preferably 0.15 to 0.25%. The proportions of the various constituents of the liquid detergent can vary accordingly. Equivalent results can be obtained by using larger amounts of a more dilute formulation, however, the larger amount required requires additional packaging and is generally less convenient for use.

Example 1:

Enzyme and liquid detergents A-E were formulated as shown in Table 1. The percentages given are percentages by weight.

Table IAB £ DE sodium dodecylbenzene sulfonate 7% 7% 7% 7% 7% ethoxylated Ci2 " ^ 15 'alcohol sulfate (3 mol EO / mol alcohol) ^) 7 7 7 7 7 brightener 0.2 0.2 0.2 0.2 0.2 sodium nitrilotriacetate 15 15 15 15 15 PBB® 1 1 1 1 1 fragrance 0.3 0.3 0.3 0.3 0.3 protease enzyme ^) 1 1 1 1 1 propylene glycol ... 20 20 20 20 borax ... ... 1 2 3 water INvol

Percent active enzyme after (a) 4 days at 43.3 ° C ............ 98% (b) 6 days at 43.3 ° C 0 15 61 86 88 (1) Neodol 25 -3S from Shell Oil Company (2) Polar brilliant blue, 1% active dye solution (3) " Esperase " the Novo Industries from 5% enzyme, 75% propylene glycol and the rest water with an activity of 8.0 KNPU / g (Kilo Novo protease unit / g). -6-

AT394 385 B

The enzyme activities of detergents A-E were tested after 6 days of storage at 43.3 ° C., the percentage activity being given in relation to the initial value given in Table I. The activity after 4 days was only determined for sample E. Mixtures A and B were the only compositions that did not contain an enzyme stabilization system according to the invention, they showed complete (detergent A) or almost complete (detergent B) loss of enzyme activity after 6 days. Detergents C, D and E reflect the remarkable improvement in enzyme stability due to the incorporation of propylene glycol and borax into the detergent mixture.

Mixtures B to E were all clear, single-phase, homogeneous solutions that retained their physical stability and clarity after 6 months of storage at both room temperature and 43.3 ° C. Mixture A, which was not composed according to the invention, was physically unstable due to the absence of propylene glycol, which in addition to being an enzyme stabilizing effect (in conjunction with the boron compound mentioned above) the solubility of the anionic surfactants and the NTA builder in the aqueous Mixture promotes.

Example 2

Liquid detergent mixtures F and G containing enzyme and builder were formulated, which were similar to mixtures A to E, except that sodium citrate was used as builder salt instead of sodium NTA. The compositions are shown in the following Table Π

Tables L £ sodium dodecylbenzene sulfonate 7% 7% ethoxylated C ^ -Cis alcohol sulfate (3 moles EO / mole alcohol) 7 7 brightener 0.2 0.2 sodium citrate 12 12 pbbW 1 1 fragrance 0.3 0.3 Proteaseenzym® 1 1 propylene glycol 20 20 borax ... 2 water percent active enzyme after 4 days at 43.3 ° C 20 95 (1) polar brilliant blue, 1% active dye solution. (2) "Esperase" from Novo Industries, containing 5% enzyme, 75% propylene glycol and the balance water, with an activity of 8.0 KNPU / g. (Kilo Novo protease units / g)

Composition G according to the invention showed an enzyme activity of 95% after 4 days, whereas composition F, which did not contain any boron compound, lost more than 3/4 of its original enzyme activity.

Both compositions were clear single-phase solutions that remained stable after 6 months of storage at both room temperature and 43.3 ° C. -7-

AT 394 385 B

Example 3

Liquid detergent compositions Η, I and J containing enzyme and builder were formulated which were substantially similar to compositions F and G in Example 2, except that they contained a mixture of protease and α-amylase enzymes instead of a single protease enzyme. The compositions are shown in Table III.

Table ΙΠ EII sodium dodecylbenzenesulfonate 7% 7% 7% ethoxylated C alcohol sulfate (3 moles EO / mole alcohol) 7 7 7 brightener 0.2 0.2 0.2 sodium citrate 12 12 12 PBßW 1 1 1 fragrance 0.3 0 .3 0.3 protease enzyme ^ 1 1 1 a-amylase enzyme 0.4 0.4 0.4 propylene glycol 20 20 20 borax - 1 3 water percent active enzyme after 4 days at 433 ° C. a-amylase enzyme 50% 67% 87 % Protease enzyme 30 73 94 (1) polar brilliant blue, 1% active dye solution (2) " esperase " from Novo Industries, containing 5% enzyme, 75% propylene glycol and the rest water, with an activity of 8.0 KNPU / g. (Kilo Novo protease units / g). (3) " Termamyl " from Novo Industries, containing 5% enzyme, 18% NaCl and the remainder water with an activity of 120,000 Novo-amylase units per gram.

Compositions I and J according to the invention showed a significantly more stable enzyme activity after 4 days for both the protease and for the amylase enzymes, compared to composition H which did not contain any boron compound and consequently 1/2 of its initial amylolytic activity and about 1 / 3 lost its initial proteolytic activity during the 4 day storage period.

All three compositions were clear single-phase solutions that remained physically stable after 6 months of storage. -8th-

Claims (7)

AT394 385 B PATENT CLAIMS 1. Stabilized, clear, single-phase, builder and enzyme-containing liquid detergent based on anionic surfactants in water, consisting of (a) 8 to 20% by weight of one or more anionic surfactants, (b) 5 to 25 % By weight, in particular 10 to 20% by weight, of a water-soluble phosphate-free builder salt, (c) an effective amount of an enzyme or enzyme mixture from the group consisting of alkaline protease enzymes and α-amylase enzymes, (d) an enzyme stabilizing system and (e) 25 to 75% by weight of water, characterized in that component (d), based on the weight of the detergent, (i) 12 to 25% by weight of propylene glycol and (ii) 1 to 5% by weight. -% of a boron compound from the group consisting of boric acid, boron oxide and alkali borate and the detergent is practically free of crosslinked polyacrylate polymers. 2. Detergent according to claim 1, characterized in that the builder salt is sodium citrate. 3. Detergent according to claim 1, characterized in that the builder salt is sodium nitrilotriacetate. 4. Detergent according to claim 1, characterized in that it contains essentially no phosphate builder salt. 5. Detergent according to claim 1, characterized in that it contains 15 to 20 wt .-% propylene glycol and 1 to 3 wt .-% of the boron compound. 6. Detergent according to claim 1, characterized in that the boron compound is borax. 7. Detergent according to claim 1, characterized in that the anionic surfactant is a mixture of a Cjg-Cjg-alkylbenzenesulfonate and a polyethoxylated Cjq-Cjg alcohol sulfate. -9-