LU85392A1 - SINGLE PHASE LIQUID ANIONIC DETERGENT COMPOSITION CONTAINING DETERGENT ADJUVANT AND CONTAINING STABILIZED ENZYMES AND WASHING METHOD USING THE SAME - Google Patents

Description

"1"!

The present invention relates to stable liquid detergent compositions containing one or more enzymes and a detergency builder, suitable for leaching or pre-soaking formulations. More particularly, the invention relates to aqueous liquid detergent compositions containing enzymes, which contain a non-phosphate detergency builder and which are characterized as being homogeneous, single-phase, clear and physically stable liquid compositions.

The formulation of liquid detergent compositions: containing stabilized enzymes has constituted in the prior art a particular center of interest. The desire to incorporate enzymes into detergent compositions is mainly due to the effectiveness of the proteolytic and amylolytic enzymes in breaking down protein and starchy materials found on soiled fabrics, so as to facilitate the removal of stains, for example sauce stains, blood stains, chocolate stains, etc., during the laundering operation. However, enzyme materials suitable for bleaching compositions, particularly proteolytic enzymes, are relatively expensive. Indeed, they generally constitute the most expensive ingredient of a commercial liquid detergent composition, even when they are present in relatively minor amounts. In addition, it is known that enzymes are unstable in aqueous compositions. This is the reason why liquid detergent formulations generally require an excess of enzyme in order to compensate for the expected loss of enzyme activity during extended periods of storage. Consequently, the prior art abounds with proposals aimed at stabilizing the liquid detergent compositions containing enzymes, and in particular the liquid compositions without detergency builder by the use of various substances which are incorporated in the $ 2 t * compositions and serving as enzyme stabilizers.

In the case of liquid detergent compositions containing a detergency builder, the problem of enzyme instability is particularly acute. First of all, this is due to the fact that detergency builders have a destabilizing effect on enzymes, even in compositions containing enzyme stabilizers which are otherwise effective in formulations without detergency builders. In addition, the incorporation of a detergency builder into a liquid detergent composition poses another problem, namely the ability to form a stable single-phase solution, the solubility of sodium tripolyphosphate, for example, being relatively limited in aqueous compositions, and in particular in the presence of anionic and nonionic detergents. Thus, for example, British Patent Application No. 1,079,305 of January 20, 1982 describes an aqueous liquid detergent composition, with detergency builder, containing enzymes, which is stabilized by a mixture of a polyol and acid boric. The compositions described in the examples, however, instead of being stable, clear, single-phase solutions, are cloudy suspensions which are likely to exhibit separation after prolonged periods of storage.

Therefore, the problems of enzyme stability and physical product stability are still problems to be overcome in the formulation of a commercially acceptable liquid detergent composition with detergency builder, containing enzymes. 30 cial.

The present invention provides an aqueous liquid stabilized detergent composition with clear, single-phase detergency builder containing enzymes, comprising: (a) about 8-20% by weight of one or more i 3 t * * (b) about 5 to 25% by weight of a non-phosphated, water-soluble detergency builder salt; (c) an effective amount of an enzyme or mixture of enzymes selected from the group consisting of proteases and alkaline alpha-amylases; (d) an enzyme stabilization system containing, on the basis of the detergent composition, (i) approximately 12 to 25% of propylene glycol and (ii) approximately 1 to 5% of a boron compound chosen from the group comprising boric acid, boric oxide and alkali metal borates; and (e) about 25 to 75% by weight of water.

According to the process of the invention, the leaching of stained and / or soiled materials is carried out by bringing these materials into contact with an aqueous solution of the liquid detergent composition defined above. Unlike the adjuvant detergent compositions containing enzymes known in the prior art, the compositions of the present invention are solutions whose characteristic is to be transparent, homogeneous, single-phase, and physically stable for extended periods of storage and over a wide range of temperatures. In order to avoid separation of the product, the compositions of the invention are preferably substantially free of detergent builder salt of the phos p h a te type.

Unlike liquid anionic detergent compositions with detergency builder containing enzymes of the prior art, the anionic surfactant contained in the compositions of the invention is solubilized in the presence of a detergency builder salt. In addition, the enzyme compositions of the invention are characterized by the presence of an enzyme stabilization system which, in addition to providing long term stability to the enzyme over a wide range of temperatures, serves to

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f 4 T * * detergency builder without phosphate of the aqueous composition, allowing the formation of a single-phase solution, physically stable in the particular range of compositions indicated.

The enzyme stabilization system according to the invention is a mixture of propylene glycol and a boron compound chosen from boric acid, boron oxide and an alkali metal borate capable of reacting with propylene glycol. The amount of propylene glycol is from about 12 to 25%, preferably about 15 to 20%, by weight, and the amount of the boron compound can vary between about 1 and 5%, preferably between about 1 and 3%, by weight of the composition.

Alkaline proteolytic enzymes suitable for the compositions of the invention include various commercial liquid enzymatic preparations for use in detergent compositions, powdered enzyme preparations also being useful to use, although generally they are less convenient to incorporate into liquid detergent compositions with detergency builder. Thus, suitable liquid enzyme preparations include "Alcalase" and "Esperase" sold by Novo Industries, Copenhagen, Denmark, and "Maxatase" and "AZ-25 Protease" sold by Gist-Brocades, Delft, Netherlands.

"Esperase" is particularly preferred for the composition of the invention because of its optimized activity at higher pH corresponding to the detergent compositions with detergency builder.

Among the suitable α-amylase liquid enzymatic preparations, mention may be made of those sold by Novo Industries and Gist-Brocades under the trade names "Termamyl" and "Maxamyl", respectively.

The synthetic anionic detergent used in the practice of the invention can be any of a wide variety of such well-known compounds "* 5 and described in detail in Surface Active Agents, Vol. II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, descriptions relating to this detergent being cited for reference in this memo.

The anionic detergent compounds which are particularly preferred are the (alkyl in * - j q_ -jg or ^ q) benzenesulfonates in which the alkyl group preferably contains 10 to 15 carbon atoms, preferably al-10 a straight chain alkyl radical of 12 or 13 carbon atoms. Preferably, such an alkylbenzenesulfonate has a high content of isomers whose phenyl group is fixed in position 3 or higher and a corresponding low content (generally much less than 50%) of isomers whose phenyl group is fixed in position 2 or lower; in other words, the benzene nucleus is preferably largely attached at the 3, 4, 5, 6 or 7 position of the alkyl group and the content of isomers in which the benzene nucleus is attached at the 1 or 2 position is weak in correspondence. Examples of surfactants of the alkyl benzene sulfonate type are described in US Pat. No. 3,320,174. Naturally, more highly branched alkyl benzene sulfonates can also be used, but in general, no prê-25 fère-pas, due to their lack of biodegradability.

Other useful anionic detergents are olefin sulfonates. In general, these contain long chain alkenyl sulfonates or long chain hydroxyalkane sulfonates (the OH group being on the carbon atom which is not directly attached to the atom carbon bearing the group -SO ^ H). The detergent olefin sulphonate usually includes a mixture of these types of compounds in varying amounts, often with long chain disulfonates or sulfate sulfonates. These olefin sulfonates are described in patents such as U.S. Patents 2,061,618, 3,409,637; .

r “6 No. 3,332,880; No. 3,420,875; No. 3,428-654; No. 3,506,580; and British Patent No. 129,158. The number of carbon atoms in the olefin sulfonate is generally comprised between 10 and 25, most commonly between 10 and 18 5 or 20, for example a mixture mainly of C ^, and C- | g, having an average of about 14 carbon atoms, or a mixture mainly of C · ^, C-jg and C-jg having an average of about 16 carbon atoms.

Another class of useful anionic detergents is that of (higher paraffin) sulfonates. These can be primary paraffin sulfonates obtained by reacting long chain alpha-olefins or bisulfites, for example sodium bisulfite, or paraffin sulfonates whose sulfonate groups are distributed along the chain paraffinic, for example products obtained by reacting a long chain paraffin with sulfur dioxide and oxygen under ultraviolet light, then neutralizing with sodium hydroxide or other suitable base (as in US Pat. Nos. 2,503,280; No. 507,088; -3,260,741; 3,372,188; and German patent 735,096). Paraffin sulfonates preferably contain 13 to 17 carbon atoms and are normally the mono-sulfonate, but if desired, it may be di- or trisulfonates, or higher sulfonates. For example, the di- and polysulfonates are used in admixture with a corresponding monosulfonate, for example, as a mixture of mono- and di-sulfonates containing up to about 30% of the disulfonate. Its hydrocarbon substituent t 30 is preferably linear, but if desired, branched chain paraffin sulfonates can be used, although they are less advantageous from the point of view of biodegradability.

Other suitable anionic detergents are the sulfated ethoxylated higher fatty alcohols of formula R0 (C ^ H ^ Oj ^ SOgM, where R is a fatty alkyl group of 10 to 18 7 or 20 carbon atoms, m is between 2 and 6 or 8 (and preferably has a value of about 1/5 to 1/2 the number of carbon atoms of R) and M is a cation forming a solubilization salt such as a metal cation al- 5 hug, ammonium, lower alkylamino or lower alkanolamino, or a (higher alkyl) benzene-su! Fonate in which the alkyl group contains 10 to 15 carbon atoms.

Ethylene oxide is the preferred lower alkylene oxide for the anionic alkoxy late type detergent, and its proportion in polyethoxylated (higher alkanol) sulphate is preferably 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, three moles constituting the preferred amount, particularly when the higher alkanol has 11 or 12 to 15 carbon atoms. In order to maintain the desired hydrophi 1 e-1 ipophi 1 e ratio, when the carbon atom content of the alkyl chain is in the lower range of 10 to 18 carbon atoms, the oxide content detergent ethylene can be reduced to about two moles per mole, while when the higher alkanol has 16 to 18 carbon atoms and is in the upper part of the range, the number of ethylene oxide groups can be increased to 4 or 5 and, in some cases, up to 8 or 9. Similarly, the salt-forming cation can be modified to obtain the best solubility. It can be any suitable metal or solubilization radical, but it is most often an alkali metal, for example sodium, or ammonium. If lower alkyl or alkanolamine groups are used, the alkyl and alkanol groups generally have 1 to 4 carbon atoms, and the amines and alkanolamines may be mono-, di- and trisubstituted, for example the monoethano-35 lamin, diisopropanolami ne and trimethylamine ne.

Poly (lower alkoxy) (higher alkanol) sul- 1 · 8 fates can be used in combination with other preferred anionic detergents such as (upper alkyl) benzenesulfonates to impart optimal detergent power to liquid detergent compositions 5 with detergency builder according to the invention. A preferred polyethoxylated alcohol coolant type detergent is available from Shell Chemical Company and is marketed under the designation "Neodol 25-3S".

Examples of polyethenoxy sulphates (higher alcohol) which can be used in the liquid detergent compositions of the invention include the following: (normal or primary mixed or primary C 1 -C 4 alkyl-sodium triphenoxy sulphate; myristyl - potassium triethenoxy sulphate; diethanola-15 mine n-decyl diethenoxysulfate; ammonium 1auryl-diethenoxy sulphate; sodium palmityl-tetraethenoxy sulphate; (normal or primary mixed alkyl in (tri- and tetra-ethenoxy mixed) sodium sulphate; stearyl-pentaethenoxy-tri-methylamine sulphate; and (normal or primary C10-18 mixed alkyl) potassium triethenoxy-sulphate.

Other useful anionic detergents include (higher acyl) sarcosinates, for example sodium N-lau-royl-sarcosinate; (higher fatty alcohol) sulfates such as sodium auryl sulfate and sodium tallow (al-25 cool) sulfate; sulfated oils; ________sulfates of mono- or diglycerides of higher fatty acids, for example stearic monoglyceride monosulfate; although among these, it has been found that the (higher alcohol) sodium sulfates were lower than the polyethoxylated sulfates in terms of detergent power; aromatic poly (lower alkenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and nonylphenol (generally having 1 to 20 oxyethylene groups per molecule, preferably 2 to 12); polyethoxy (higher alcohols) sulfates and alkylphenol-polyethoxy sulfates having an alcohol substituent.

1 I

%% 9 xy lower (1 to 4 carbon atoms, for example methoxy) on a carbon atom similar to that carrying the sulfate group, for example the monomethyl-monoether-v monosulfate of a long chain vicinal glycol, for example a mixture of vicinal alkane-diols of 16 to 20 straight chain carbon atoms; acyl esters of isethionic acid, for example o-leyl isethionates; acyl-N-methyl-taurides, for example the N-methyl-1auroyl - or potassium ol eyl-taurides; (higher al-10 kyle) phenyl-polyethoxy-sulfonates; the (higher alkyl) phenyl-sulphouates, for example pentadé-cyl-phenyl-disuifonate; and soaps of higher fatty acids, for example mixed soaps of coconut oil and tallow in a ratio of 1: 4.

15

Among the above-mentioned types of anionic detergents, sulfates and sulfonates are generally preferred, but the corresponding organic phosphates and phosphonates can also be used when their phosphorus content is not harmful. In general, water-soluble anionic synthetic organic detergents (including soaps) are alkali metal cation salts, for example potassium, lithium, and in particular sodium, although the salts of ammonium cations and substituted ammonium cations, for example those previously described, for example tri-ethanol friend, triisopropylamine, can also be used.

Optionally, non-ionic detergent may be used in minor amounts to enhance the anionic detergent compound of the present liquid detergent compositions with detergency builder. When used in this combination with an anionic detergent, the amount of nonionic detergent is generally less than about 10%, and preferably less than about 5% by weight, based on the total composition. I

10

Nonionic detergents are generally polyalkoxylated lipophilic compounds in which the desired hydrophilic to lipophilic ratio is obtained by the addition of a hydrophilic poly (lower alkoxy) group to a lipophilic unit. In the case of the compositions according to the invention, the nonionic detergent used is preferably a poly (lower alkoxy) higher alkanol in which the alkanol group contains 10 to 18 carbon atoms and in which the number of moles of oxide of lower alkylene (2 or 3 carbon atoms) is between 3 "and 12. Among these materials, it is preferred to use those in which the higher alkanol is a higher fatty alcohol of 11 or 12 to 15 carbon atoms and which contain 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy is the ethoxy group, but in some cases it can be mixed with a propoxy group, the latter, if present, generally being a minor constituent (less than 50%). Examples of such compounds are those in which the alkanol group contains 12 to 15 carbon atoms and which contain approximately 7 ethylene oxide groups per mole, for example Neodol 25-7 and Neodol 23-6.5, these products being manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms, with about 7 moles of ethylene dioxide, and the latter is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups per mole is on average about 6.5. Higher alcohols are primary alkanols. Other examples of these detergents include Tergitol® 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The former is a mixed ethoxylation product of a linear secondary alkanol of 11 to 15 carbon atoms with seven moles of ethylene oxy-11, and the latter is a similar product but containing nine moles of reacted ethylene oxide.

Also of interest in the compositions 5 of the present invention are the higher molecular weight nonionic compounds, for example Neodol 45-11, which are analogous condensation products of ethylene oxide and higher fatty alcohols, higher fatty alcohol i having 14 or 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. These products are also manufactured by Shell Chemical Company.

* Other useful nonionic detergents are represented by Plurafac B-26 (BASF Chemical Company), the product of the reaction of a higher linear alcohol and a mixture of ethylene and propylene oxides.

In higher poly (lower alkoxy) alkanols, the best ratio of hydrophilic and li-pophilic units is obtained when the number of lower alkoxy groups is about 40% to 100% of the number of carbon atoms and the higher alcohol, preferably 40 to 60% of this number. The nonionic detergent preferably consists of at least 50% of the preferred ethoxylated alkanols. The higher molecular weight alkanols and various other normally solid and surfactant nonionic detergent compounds can contribute to the gelling of the liquid detergent composition and therefore are normally avoided or used only in limited amounts in the compositions of the invention, although minor proportions can be used * due to their cleaning properties, etc. As regards the preferred and less preferred nonionic detergents, the alkyl groups present are preferably linear, although a certain degree of branching can be accepted, for example on the atom following the terminal carbon atom of the straight chain or two carbon atoms from this terminal atom and far from the ethoxylated chain provided that this branched alkyl group has a chain length of 1 * 12 not more than three carbon atoms. Normally, the proportion of carbon atoms in such a branched configuration is minor, and rarely exceeds 20% of the total content of carbon atoms in the alkyl group. Similarly, although the linear alkyl groups which are terminally linked to the ethylene oxide chains are highly preferable and are considered to provide the optimum combination of detergency, biodegradability and non-gelling characteristics, there may be a median or secondary bond to the ethylene oxide of the chain. In this case, this usually relates to only a small proportion of these alkyl groups, generally less than 20%, but in the case, for example, of the Tergitoi s mentioned above, this proportion may be higher. Also, when the lower alkylene oxide chain contains propylene oxide, the latter generally constitutes less than 20%, and preferably less than 10% of said chain.

The phosphate-free detergency builder salts are used in the compositions of the present invention in proportions of between about 5 and 25%, and preferably about 10 to 20% by weight. Examples. particular mags of water-soluble phosphorus-free hydrosoluble mineral additives include carbonates, bicarbonates and water-soluble mineral silicates. Particular preference is given here to carbonates, bicarbonates and silicates of alkali metals, for example sodium and potassium.

The water-soluble organic builders are also useful and include polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates of alkali metals, ammonium and substituted ammonium. Particular examples of polyacetates and polycarboxylates used as detergency builders include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene-diaminetetraacetic acid, nitrilo-triacetic acid, benzene-polycarboxylic acids (that is to say penta- and tetra-), carboxymethoxysuc-cinic acid and citric acid.

The proportions of water, the main solvent for the compositions of the present invention, are generally about 25 to 75%, preferably 40% to 60% based on the weight of the liquid composition.

The optical brighteners used in liquid detergent compositions are important constituents of current detergent compositions which impart a shiny appearance to laundry and washed materials, so that the laundry is not only clean, but gives also an impression of cleanliness.

Although it is possible to use a single optical brightener for a particular purpose in the liquid detergent compositions of the invention, it is generally desirable to use mixtures of brighteners which exert satisfactory brightening effects on cotton, "Nylons", polyesters and blends of these materials and which are also stable towards the bleaching agent. A suitable description of these types of brightening agents can be found in the article "The Requirements of Present Day Detergent Fluorescent Whitening 25 Agents" by AE Siegrist, J. Am. 01 Chemists Soc., January 1978 (volume 55) . This article and the U.S. Patent.

3,812,041 of May 21, 1974 which are cited by reference contain detailed descriptions of a wide variety of suitable optical brighteners.

Among the brightening agents useful in the liquid detergent compositions of the present invention, there may be mentioned: Calcofluor 5BM (American Cyanamid); Calco-fluor White ALF (American Cyanamid); S0FA-2001 (Ciba); CDW (Hilton-Davis); Phorwite RKH, Phorwite BBH and Phor-35 wite BHC (Verona); CSL, powder, acid (American Cyanamid);

FB 766 (Verona); Blancophor PD (GAF); UNPA (Geigy); Ti-nopal RBS 200 (Geigy). AT

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Liquid detergent compositions can contain adjuvants intended to impart additional functional or aesthetic properties. Useful adjuvants include suspending, or anti-repositioning agents, for example polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose; thickeners, for example gums, alginates, agar; foam reinforcing agents, for example dietauri-friendly myauric; Foam destroyers, e.g. silicones; bacteria, for example tribromosalicylanil ide, hexachlorophene; dyes; pigments (dispersible in water); preservatives; ultraviolet light absorbers; fabric softeners; Opacifiers, for example polystyrene suspensions; and perfumes. Naturally, these materials will be chosen on the basis of the properties desired for the finished product, their compatibility with the other constituents, and their solubility in the liquid composition.

The liquid compositions of the invention are effective and easy to use. Compared to detergent powders for washing coarse laundry, much smaller volumes of the liquids of the invention are used to achieve comparable cleaning of soiled laundry. For example, using a typical preferred formulation of the present invention, only about 132 g or half a cup of liquid is required for a full tub of an automatic top-loading washing machine in which the volume water is 55 to 75 liters; and even less for front loading machines. Thus, the concentration of the liquid detergent composition in the washing water is of the order of about 0.2%. In general, the proportion of liquid composition in the washing solution is between approximately 0.05 and 0.3%, preferably between 0.15 and 0.25%.

1/15

The proportions of the various constituents of the liquid composition can vary correspondingly.

Equivalent results can be obtained by using higher proportions of a more dilute formulation, but the greater amount required will require additional packaging and will generally be less convenient for the user.

EXAMPLE 1

Liquid detergent compositions A-E with adjuvant h 10 and containing enzymes are formulated as described in Table I. The percentages indicated are percentages by weight.

Table 1

A B C D E

15 _____

Sodium dodecylbenzene sulfonate 7% 7¾ '7 2 7% 7%

Al cool-sulfate in 5 etho-xylë (3 moles of 0E * / mole of alcohol) ^) 7 7 7 7 7 20 Brightening agent 0.2 0.2 0.2 0.2 0.2 0.2

Sodium nitrilotriacetate 15 15 · 15 15 15 PBB (2) L 11111

Perfume 0.3 0.3 0.3 0.3 0.3

Protease enzyme ^) 11111 25 Propyl ene-glycol —- 20 '20 20 20

Borax - - 1 2 3 Ηλ, Ο ........... the rest —..........

Percentage of enzyme activity after 30 (a) 4 days at 43 ° C ...... -..... 98% (b) 6 days at 43 ° C 0 15 61 86 88 (1) Neodol 25-3S sold by Shell 0i1 Company.

(2) "Polar Brilliant Blue" - 1% solution of active dye.

16 (3) "Esperase" sold by Novo Industries containing 5% enzyme, 75% propylene glycol, the remainder consisting of 1 ^ 0 having an activity of 8.0 KNPU / g (kilo * units of Novo Protease / g) ^ (*) OE (ethylene oxide)

The enzymatic activities of the AE compositions are tested after 6 days of storage at 43 ° C., the percentage of activity relative to the initial value being indicated in Table I. The activity after 10 4 days is measured only for composition E. Compositions A and B are the only compositions which do not contain an enzyme stabilizing system according to the invention, and they show a total (composition A) or almost total loss (composition B) of the enzymatic activity after 6 days. Compositions C, D and E reflect the marked improvement in the stability of the enzymes attributed to the incorporation of propylene glycol and borax in the detergent composition.

The compositions B to E are all homogeneous, clear, single-phase solutions which retain their physical stability and their clarity after 6 months of storage at room temperature and at 43 ° C. Composition A which is not in accordance with the invention is physically unstable due to the absence of propylene-gly-25-col which, in addition to its role of stabilizing the enzymes (together with the abovementioned boron compound ), promotes the solubility of anionic detergents and NTA (nitri-1otriacetate) adjuvant in the aqueous composition.

EXAMPLE 2 The liquid detergent compositions F and G with detergency builder and containing enzymes are formulated in a manner essentially analogous to compositions A-E with the difference that sodium citrate is used as detergency builder salt instead of sodium NTA. The compositions are presented below in Table II.

17.

ί

; Table II

F G

Sodium dodecyl benzene sulfonate 7% 7% * Al cool-sul fate in ethoxylate 5 (3 moles of EO / mole of alcohol) 7 7

Brightening agent 0.2 0.2

Sodium citrate 12 12 PBB ^ 1 1

Fragrance 0.3 0.3 1 (21 10 Protease enzyme '‘1 1

Propylene glycol 20 20

Borax - 2 H ^ O ------ the rest ----- 15 Percent of enzymatic activity after 4 days at 43 ° C. 20 95 (1) "Polar Brilliant Blue" - one 1% solution of active dye.

(2) "Esperase" sold by fJovo Industries containing 5% of enzyme, 75% of propylene glycol, the rest being 1 ^ 0 having an activity of 8.0 KNPU / g (kilo-units of Novo Protease / g).

Composition B according to the invention manifests an enzymatic activity after four days of 95%, compared ~ 1M to composition F which does not contain a boron compound and consequently loses more than three-quarters of its initial enzymatic activity.

Both compositions are clear solutions. „30 single phase cells which remain physically stable after six months of storage at room temperature and 43 ° C.

EXAMPLE 3

Liquid detergent compositions H, I and J with adjuvant and containing an enzyme are formulated in a manner essentially analogous to compositions F and G of Example 2 except that they contain a mixture of protease and alpha -amylase instead of only the protease. The compositions are presented below in Table 111.

Table III

H J,

Sodium dodecylbenzene sulfonate 7% 7% 1%

Al cool-su! f ate in ·] 5 ethoxylated * 10 (3 moles of EO / mole of alcohol) 777

Brightening agent 0.2 0.2 0.2 d Sodium citrate 12 12 12! PBB ^) 1 1 1 I Perfume 0.3 0.3 0.3 (21 1 the Protease enzyme '' 111 (31; Enzyme α-amylase '' 0.4 0.4 0.4

Propylene glycol 20 20 20

Borax - 1 3 H ^ O ------ the rest ------ 20 d Percent of enzymatic activity

d after 4 days at 43 ° C

j Enzyme "ct-amylase 50% 67% 87%

Enzyme Protease .30 73 94 (1) "Polar Brilliant Blue" - a 1% solution of neck orTüvtTactif (2) "Esperase" sold by Novo Industries containing 5% enzyme, 75% propylene glycol, the rest consisting of H ^ O having an activity of 8.0 KNPU / g (kilo- - - units of Novo Protease / g).

(3) "Termamyl" sold by Novo Industries containing 5% of enzyme, 18% of NaCl, the remainder consisting of H 2 O having an activity of 120,000 units of Novo amylase per gram.

19

The compositions I and J according to the invention show a clearly more stable enzymatic activity after four days in the case of the protease and of the amylase compared to the composition H which does not contain boron, and by therefore, loses about half of its initial amylolytic activity and about a third of its initial proteolytic activity during the four-day period.

The three compositions are single-phase limpi-10 solutions which remain physically stable after six months of storage.

i

Claims (15)

20 1. A stabilized, aqueous composition, with adjuvant, clear, single-phase, liquid and containing one or more enzymes, characterized in that it comprises: 5 (a) approximately 8 to 20% by weight of one or more anionic surfactant detergent compounds; (b) about 5 to 25% by weight of a non-phosphated, water-soluble detergency builder salt; (c) an effective amount of an enzyme or mixture of enzymes selected from the group consisting of alkaline proteases and alpha-amylases; (d) an enzyme stabilization system containing, based on the weight of the detergent composition, (i) about 12 to 25% propylene glycol and (ii) about 15 1 to 5% of a selected boron compound in the group comprising boric acid, boric oxide and alkali metal borates; and (e) about 25 to 75% by weight of water. 2. Detergent composition according to claim 20 1, characterized in that the detergency builder salt is sodium citrate. 3. Detergent composition according to claim 1, characterized in that said detergency builder salt is sodium nitrilotriacetate. 25 4 - Detergent composition according to claim 1, characterized in that it is substantially free of detergency builder of the phosphate type. 5. A detergent composition according to claim 1, characterized in that it contains about 15 to 20% by weight of propylene glycol and about 1 to 3% by weight of said boron compound. 6. Detergent composition according to claim 1, characterized in that said boron compound is borax. 35 7 - Detergent composition according to claim i "V! 1, characterized in that said adjuvant detergency salt I is present in a proportion of approximately 10 to 20% by weight. 8. Detergent composition according to claim | - 1, characterized in that the anionic detergent is a mixture of a (C 1 -C 6 alkyl) benzene sulfonate and an al-cool-su! fate in C- | 0_C · ^ polyethoxylated. 9. Washing method, characterized in that it brings the stained and / or soiled fabrics to be washed into contact with a liquid detergent composition with a single phase, clear, with adjuvant, and containing one or more enzymes, comprising (a) about 8 to 20% by weight of one or more surfactant anionic detergent compounds; (b) about 5 to 25% by weight of a phosphate-free and water-soluble detergency builder salt; (C) an effective amount of an enzyme or mixture of enzymes selected from the group consisting of alkaline proteases and alpha-amylases; (d) an enzyme stabilization system containing, on the basis of the weight of the detergent composition, (i) approximately 12 to 25% of propylene-20-glycol and (ii) approximately 1 to 5% of a compound of boron selected from the group consisting of boric acid, boric oxide and alkali metal borates; and (e) about 25 to 75% by weight of water. 10. The method of claim 9, character-ized in that the adjuvant detergency salt is sodium citrate. 11. Method according to claim 9, characterized in that the adjuvant detergency salt is sodium le.nitrilo-triacetate. 30 12 - Process according to claim 9, character ized in that the detergent composition is substantially free of detergency builder salt of the phosphate type. 13. Method according to claim 9, characterized in that the detergent composition contains about 35 to 20% by weight of propylene glycol and about 1 to 3% 22 »V 14. Method according to claim 9, characterized in that said detergent composition contains approximately 10 to 20% of an adjuvant detergency salt of the type - non-phosphate. 15. The method of claim 9, character ized in that the detergent composition contains a mixture of (C ^ QC ^ g) benzene sulfonate and a polyethoxylated C- | 0-C- | 8 alcohol-sulfate . P