NL8601926A - STABILIZED, COMPOSITE, ENZYME-CONTAINING LIQUID DETERGENT. - Google Patents

Description

*, i VO 8301

Stabilized, formulated, enzyme-containing liquid detergent.

The invention relates to stable, composite, enzyme-containing liquid detergents, which are suitable for washing or pre-soaking. More particularly, the invention relates to aqueous enzyme-containing liquid detergents containing one or more detergent builders and characterized in that they are physically stable, homogeneous liquid agents.

The mixing of stabilized enzyme-containing liquid detergents has been extensively described in the prior art. The desirability of incorporating enzymes into detergents is primarily due to the effectiveness of proteolytic and amylolytic enzymes in proteinaceous and starchy materials found on soiled laundry, thereby removing stains such as gravy stains, blood stains, chocolate stains , and the like during washing is facilitated.

Enzymatic materials suitable for detergents, especially proteolytic enzymes, are, however, relatively expensive.

They are generally the most expensive components in a typical commercial liquid detergent, even though they are present in relatively small amounts. In addition, the enzymes in aqueous compositions are known to be unstable.

For these reasons, an excess of enzymes is generally required in liquid detergents to offset the expected loss of enzyme activity over long periods of storage. Thus, there are extensive proposals in the prior art to stabilize enzyme-containing liquid detergents, especially non-formulated liquid detergents, using various materials incorporated into the detergent to act as enzyme stabilizers .

With liquid detergents containing a builder, the problem of enzyme instability is particularly acute. This is mainly due to the fact that builders have a destabilizing effect on enzymes, even in compositions that have enzyme stabilizers that are effective in non-composite agents. In addition, the inclusion of a builder in a liquid detergent raises an additional problem, namely, the formation of a stable, single-phase formulation; for example, the solubility of sodium tripolyphosphate in aqueous compositions is relatively limited, especially in the presence of anionic and nonionic detergents.

British patent application 2,079,305 discloses an aqueous formulated enzyme-containing liquid detergent stabilized by a mixture of a polyol and boric acid. As can be seen from the examples of the British patent application, relatively large amounts of glycerol are required to stabilize the enzymes in the composition. Still, as demonstrated below, the enzyme-stabilizing effect provided by a mixture of glycerol and borax in a composite aqueous liquid detergent is relatively modest.

European patent application publication number 0126505 discloses an aqueous enzyme-containing liquid detergent containing an enzyme-stabilizing mixture consisting of certain dicarboxylic acids and borax. The dicarboxylic acids are recommended as. a replacement for a polyol, such as glycerol in known enzyme stabilizing mixtures, consisting of glycerol and a boron compound. The dicarboxylic acid borax mixtures of. this publication, like the aforementioned known mixture of glycerol and borax, are incapable of giving only a modest stabilizing effect in the current formulated liquid detergents. Thus, there is a need for significantly improved enzyme stability in aqueous formulated liquid detergents as defined below to levels far above the present known capabilities.

The present invention provides a stabilized formulated enzyme-containing liquid laundry detergent comprising: (a) about 5-20 wt% of one or more surfactant detergents selected from the group consisting of anionic, nonionic and amphoteric detergents; (B) about 5-30% by weight of one or more builder salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxylates; (c) an effective amount of an enzyme or enzyme mixture selected from the group consisting of alkaline protease enzymes and β1-amylase enzymes; (d) an enzyme-stabilizing system based on the '* -¾ ft «3 * .¾ -" ·

- V. V »V

Λ * -3- weight of the detergent composition contains (i) about 1-10% glycerol; (ii) about 1-8% of a boron compound selected from the group consisting of boric acid, boron oxide and alkali metal borates and (iii) about 0.5-8% of a carboxylic acid compound selected from the group consisting of 5 mono-, di - and / or polycarboxylic acids with 1-8 carbon atoms and water-soluble salts thereof, and (e) with residual water and optionally perfume and other additives.

In a preferred embodiment of the invention, the liquid detergent comprises: (a) about 5-15% of an alkyl metal alkyl benzene sulfonate, wherein the alkyl group contains 12-15 carbon atoms; (b) about 2-5% of an alkali metal alkyl polyethoxysulfate, wherein the alkyl group contains 10-18 carbon atoms and the polyethoxy consists of 3-11 ethylene oxide groups, the weight ratio of (a) to (b) about 2: 1 to about 8: 1; (c) about 5-20% sodium tripolyphosphate; (d) about 1-10% sodium carbonate, the weight ratio of (c) to (d) being about 2: 1 to about 6: 1; (E) an effective amount of the aforementioned enzyme as an enzyme mixture; (f) an enzyme stabilizing system based on the weight of the detergent composition (i) about 3-7% glycerol, (ii) about 1-5% of an alkali metal borate and (iii) about 0.5-4% of said carboxylic acid compound, and (g) with water as the residue and optionally perfume and other additives.

By detergent herein is meant the composition, mixture or formulation of the ingredients and additives, thus the finished product.

According to the method of this invention, the cleaning of stained and / or soiled laundry is performed by contacting such materials with an aqueous solution of the above defined liquid detergents.

The liquid detergent described is a commercially available detergent for very soiled laundry, capable of satisfactorily cleaning laundry containing 30% oily and finely divided impurities.

In addition, the described compositions can be used for the pre-treatment of very heavily soiled areas, such as collars 5 and cuffs, of textile materials to be washed.

The present invention is based on the discovery of a three-component enzyme stabilization system as defined herein that imparts to the liquid detergent compositions of the invention an enzyme stabilizing effect much greater than that achievable with conventional enzyme stabilizers. The enzyme stabilizing effect thus achieved reflects a synergistic effect between the three components.

According to the invention, the enzyme stability provided by a mixture of glycerol and borax or a mixture of borax and a dicarboxylic acid, as described in the prior art, can be synergistically improved using the three-component stabilization system defined herein in the present liquid detergents, thereby significantly increasing the level of enzyme stability above that afforded by either a mixture of glycerol and borax or a mixture of borax and dicarboxylic acid when used independently as enzyme stabilizers.

For commercial purposes, the desired enzyme stability generally corresponds to a half-life of 1 week at a temperature of 43 ° C.

The enzyme stabilization system of the invention is a mixture of glycerol, a boron compound selected from boric acid, boron oxide and an alkali metal borate and a carboxylic acid compound as defined herein. The weight of the stabilization system in the present formulated liquid detergents is generally about 3-25%, preferably about 6-15% by weight. The weight ratio of glycerol to borax in the stabilization mixture is generally about 1 in 3.

The preferred amount of glycerol in the composition is about 3-7%, with the preferred amount of the boron compound being 1-5% and the preferred amount of the carboxylic acid compound being 0.5-4% based on the weight of the composition.

83013 2? é% -5-

The carboxylic acid compounds useful in the enzyme stabilization system of the invention include saturated, as well as unsaturated, mono-, di-, and polycarboxylic acids of 1-8 carbon atoms, which include, inter alia: oxalic acid (HOOCCOOH), malonic acid (HOOCCY ^ CQOH), maleic acid 5 (HOOCCH: CHCOOH) and succinic acid (HOOCCH.CH_COOH}. The carboxylic acids may contain 2 2 hydroxy or amino substituents, such as malic acid (HOOCCHOHCH 2 COOH), tartaric acid (dihydroxy succinic acid), aspartic acid (amino tartaric acid) and citric acid. Preferred carboxylic acids of the invention are succinic acid, maleic acid, malonic acid and malic acid.

From a commercial point of view, a particularly preferred carboxylic acid compound is citric acid and / or its salts, because of its relatively low price.

The alkaline proteolytic enzymes useful for the present compositions include the various commercial liquid enzyme preparations adapted for use in detergents. Powdered enzyme preparations are also useful, although as a general rule, less suitable for incorporation into the formulated liquid detergents. Thus, suitable liquid enzyme preparations include "Alcalase" and "Esperase" sold by Novo Industries, Copenhagen, Denmark and "Maxatase" and "Az-Protease" sold by Gist-Brocades, Delft, The Netherlands.

Suitable α-amylase liquid enzyme preparations are those sold by Novo Industries and Gist-Brocades under the tradenames Termamyl and Maxamyl.

Esparase is particularly preferred for the present compositions because of its optimized activity at the high pH values corresponding to the formulated detergents.

The preferred detergent compositions for use in the liquid detergent compositions herein are the synthetic anionic detergent compounds, especially mixtures of higher alkyl benzene sulfonates and alkyl polyethoxy sulfate. Although other water-soluble higher alkyl benzene sulfonates may also be present in the present mixtures, such as potassium salts and in some cases the ammonium or alkanol ammonium salts, where appropriate, it has been found that the sodium salt is highly preferred, which is also the case with respect to the alkyl polethethoxy sulfate detergent component. The alkyl benzene sulfonate contains an 8 6 0 19 2 2 1-6 higher alkyl group having 12-15 carbon atoms, preferably 13 carbon atoms. The alkyl polyethoxy sulfate, which may also be referred to as a sulfated, polyethoxylated higher straight alcohol or the sulfated condensation product of a higher fatty alcohol and ethylene oxide or polyethoxylene glycol, is a compound wherein the alkyl group contains 10-18 carbon atoms, preferably 12- Contains 15 carbon atoms, such as, for example, 13 carbon atoms and which contains 3-11 ethylene oxide groups, preferably 3-7, most preferably 3-5, and especially 3 or about 3, ethylene oxide groups. The ratio of alkyl benzene sulfonate to polyethoxy sulfate in the detergent mixture is preferably about 2: 1 to 8: 1, and most preferably about 3: 1 to 5: 1 by weight. At ratios above 5: 1, the physical stability of the product is adversely affected. Under certain conditions, other anionic detergents, such as fatty alcohol sulfates, paraffin sulfonates, olefin sulfonates, monoglyceride sulfates, sarcosinates and similarly acting detergents, preferably as alkali metal, e.g., sodium salts, may be present, sometimes partially replacing the aforementioned synthetic, organic detergents, but usually, if present, added to such detergents. Normally, the detergent additives added will be sulfated or sulfonated products (usually the sodium salts) and contain long (8-20 carbon atoms) straight or fatty alkyl groups.

In addition to any added anionic, synthetic, organic detergents, nonionic and amphoteric materials may also be present, such as the Neodolen sold by Shell Chemical Co., which are condensation products of ethylene oxide and higher fatty alcohols, eg Neodol 23-6.5 which is a condensation product of a higher fatty alcohol of about 12-13 carbon atoms with about 6.5 moles of ethylene oxide.

Illustrations of the various detergent agents and groups of these agents are found in the text Surface Active Agents, Vol. II, by Schwartz, Perry and Berch (Interscience Publishers, 1958), which descriptions are incorporated herein by reference.

The builder salt combination of this invention, which has been found to be satisfactory for improving the detergent capacity of the synthetic anionic organic detergent mixture and the desired pH

S3G 1 5 2? •% -7- in the liquid detergent 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 generally about 5-25% by weight. For the preferred builder salt combination 5, sodium tripolyphosphate is present in amounts of about 5-20%, preferably 10-16%, and sodium carbonate is present in about 1-10% by weight, preferably 3-7% by weight, the weight ratio of tripolyphosphate to carbonate in the preferred builder mixtures is about 2: 1 to 6 µl and most preferably about 2: 1 to 4: 1.

As used herein, the term alkali metal "carbonates" or "carbonate" refers to the carbonates, bicarbonates and sesquicarbonates of such alkali metals.

For the best processing, easier mixing and good end-use properties, it is preferred that the sodium tripolyphosphate 15 has a low phase I type tripolyphosphate content. Thus, the content of phase I type tripolyphosphate will normally be less than 30% of the tripolyphosphate used. Although in some cases an incompletely neutralized tripolyphosphate is useful, normally the phosphate used will be considered as pentasodium tripolyphosphate, Na ^ P ^ O ^. Naturally, in some cases, such as when potassium salts or other materials are present, ion exchange in an aqueous medium can lead to salts other than the sodium tripolyphosphate, but for the purposes of this application it is believed that sodium tripolyphosphate, as the pentasodium salt , the material normally loaded into the present liquid detergent mixer is the tripolyphosphate used.

Other preferred builder salts that may be used in place of sodium tripolyphosphate and sodium carbonate or added thereto include a polyacetal carboxylate as described herein and sodium nitrotriacetate (NTA). Of course, various mixtures of the listed water-soluble builder salts can be used. However, the described tripolyphosphate carbonate mixture appears to be most preferred, although the other builders and mixtures thereof are also active.

Other builders, which can be used as additives in addition to the amounts of the aforementioned builders, include other phosphates, such as tetrasodium pyrophosphate or tetrapotassium pyrophosphate, sodium bicarbonate, sodium citrate, sodium gluconate, sodium silicate and sodium sesquicarbonate. Among the water-insoluble builders that are useful are the zeolites, such as zeolite A, usually in the form of its crystalline hydrate, although amorphous zeolites are also useful. Polyacetal carboxylates are commonly described in U.S. Patents 4,144,226 and 4,315,092. U.S. Pat. No. 4,146,495 describes detergent compositions containing polyacetal carboxylates as builders.

The polyacetal carboxylates useful herein as builders can be those described in U.S. Patent 4,144,226 and can be prepared by the method recited therein. A typical product of this has the formula R. - (CHO) - R.

1, n 2

COOM

Wherein M is selected from alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms, tetraalkylammonium groups, and alkanolamine groups, both of 1 to 4 carbon atoms in the alkyl moiety thereof, n averaging at least 4 and 20 and r 2 optionally chemical stable groups which stabilize the poly more against rapid depolymerization in an alkaline solution. Preferably, the polyacetal carboxylate will be a compound wherein M is alkali metal, e.g. sodium, n is 50-200, R ^

CH CH O MOOC

O Z,, 25 HCO- or H C-CO-

1 ^ I

H3C MOOC

or a mixture thereof, R ^

OCH CH

I * ·

-CH

30 is CH 3 and n is on average 20-100, preferably 30-80.

The calculated weight-average molecular weight of the polymers will normally be in the range of 2,000-20,000, preferably 3,500-10,000, and most preferably 5,000-9,000, e.g. 550132? -9- are about 8,000. Particularly preferred sodium polyacetal carboxylate is supplied by Monsanto Co. and is known as 3uilder ü. It has a calculated average molecular weight of about 8,000 and an active polymer content of about 80%. While the preferred polyacetal carboxylates have been described above, it is understood that they may be wholly or partly replaced by other such polyacetal carboxylates or related organic builder salts described in the aforementioned patents on such compounds, methods of their preparation and compositions in which they have been used. Also, the chain-terminating groups as disclosed in the various patents, in particular U.S. Patent 4,144,226, can be used, provided they have the desired stabilizing properties, thereby depolymerizing the listed builders in acidic media and biodegradation 15 thereof in waste streams is facilitated, but retain their stability in alkaline media, such as wash solutions.

The only other required component of the liquid detergent compositions herein is water. Normally, the hardness content of the water is less than about 300 ppm as CaCO3, and it will preferably be less than 150 ppm. It may often be desirable to use deionized water, although city water with a hardness of less than 50 or 100 ppm is usually also satisfactory.

Various additives can be included in the liquid detergents, such as fluorescent whiteners, perfumes and dyes. The fluorescent whiteners include the well-known stilbene derivatives, including the cotton and nylon whiteners, such as those sold under the trademark Tinopal (5 BM Conc.). The perfumes which are useful usually include essential oils, esters, aldehydes and / or alcohols, all of which are known in the perfume art. The colorants can include dyes and water-dispersible pigments of various types, such as ultramarine blue.

Inorganic filler salts, such as sodium sulfate and sodium chloride, may be present, as can anti-graying agents, such as sodium carboxymethyl cellulose; dispersants, such as sodium poly-acrylate, bleaching agents, bactericides; fungicides, anti-foaming agents such as silicone, anti-soiling agents such as copolyesters, preservatives such as formalin, foam stabilizers such as lauric myristic diethanolamide, and co-solvents such as ethanol.

Normally, the individual amount of such auxiliaries will be less than 3%, often less than 1% or sometimes even less than 0.5%, 5 except for any fillers and solvents and additional detergents and builders, the amounts of which may be up to 10 % may increase.

The total proportion of the auxiliaries, including unnamed synthetic detergents and builders, will normally not exceed 20% of the product and desirably it is less than 10% and even more advantageously less than 5%. Naturally, the auxiliaries used will be chosen such that they do not interfere with the washing action of the liquid detergent and cause no instability of the product upon standing. Also, aids that lead to objectionable deposits on the laundry should be avoided.

The present liquid agents are efficient and easy to use. Compared to detergent powders for very dirty laundry, much smaller volumes of the present liquids can be used to achieve comparable cleaning of dirty laundry.

For example, using a typical preferred composition of the invention, only about 132 g or half a cup of liquid is required for a full washing drum in a top loading machine washer, wherein the water volume is 57-68 liters; and even less is necessary for front loaders. Thus, the concentration of the liquid detergent in the wash water is of the order of about 0.2%. Usually, the amount of the liquid agent in the wash solution will range from about 0.05 to 0.3%, and is preferably 0.15 to 0.25%. The amounts of the various constituents of the liquid agent can vary accordingly. Equivalent results can be obtained by using larger amounts of a more dilute composition, but the greater amount required requires additional packaging and is generally less convenient for consumer use and can also lead to product separation.

The viscosity of the present liquid detergent is normally in the range of from about 1,000 to 10,000 centipoise, for example, from 2,000 to 5,000 centipoise liquor, but products of other suitable viscosities can also be used. At the stated viscosities, the liquid agent is pourable, stable, non-shearing and uniform.

The pH of the liquid detergent slurry usually ranges from 7 to 11.5, and is preferably from 8 to 10.5, which contributes to maintaining product stability and pourability.

The following examples illustrate the invention without limiting it. Unless otherwise indicated, all parts are by weight and the temperature in degrees Celsius.

10 Example I ___________

Component Percentage pentasodium tripolyphosphate 15.0 sodium carbonate 5.0 sodium straight tridecylbenzene sulfonate 12.2 15 AE0SilJ 2.8 carboxymethyl cellulose (CMC) 0.15 optical brightener 0.4 perfume 0.3 (2) enzyme (Esperase 8.0 L) 1.0 20 glycerine 4.0 borax 3.0 triethanolamine 1.0 sodium citrate 2.0 water and auxiliary residues 25 (1) sodium alkyl polyethoxy sulfate, in which the alkyl contains 12-15 carbon atoms and the polyethoxy consists of 3 ethoxy groups.

(2) "Esperase" sold by Novo Industries has an activity of 8.0 KNPU / g.

The composition as indicated above was prepared by the following procedure: 32.5 parts of deionized water at 4.4 ° C are added to a suitable mixer, such as a vertical cylindrical tank equipped with a stirrer. After the stirrer is set to moderate stirring, a mixture consisting of 5.0 parts of anhydrous soda and 0.7 parts of sodium carboxymethyl cellulose is taken up in the water. The stirring speed is then increased to maximum stirring and 15.0 parts of penta- 8 o 2, 2-12 sodium tripolyphosphate are slowly added to the agitator over a period of 10-15 minutes to form a milky white suspension. The stirring speed is then lowered to a slow / moderate setting, while 19.1 parts of a high Al (about 50%) 5 LTBS suspension is added. Then the optical brightener / color solution consisting of 0.4 parts Tinopal LMS-X (Ciba-Geigy), 0.06 parts blue dye and 2.0 parts deionized water is added. Once a uniform blue-colored solution is obtained, 0.3 part perfume is added to the mixture with stirring. This is followed by the slow addition of 4.0 parts glycerol, 3.0 parts borax and 1.0 parts triethanolamine (with TEA improves long-term product stability) as a 3-component suspension. Stirring is continued until the mixture is uniform in appearance, after which 2.0 parts of sodium citrate and 4.0 parts of water are slowly added. The stirring of the mixture is then reduced while adding a mixed AI detergent base, consisting of 5.7 parts LTBS suspension (about 50% AI) and 4.7 parts AEOS (about 60% AI) to the mixture. added. This is followed by slow addition of 1.0 dl of the proteolytic enzyme with continuous stirring until all materials are completely dispersed or dissolved.

Example II

Enzyme-containing formulated liquid detergents A-G were mixed as indicated in Table A below. The percentages indicate the weight percentage. The arrows indicate to what extent compositions B-G are identical to composition A.

8601926 -13-

TABLE A

Component A BC D E F G

pentasodium tripolyphosphate 15% sodium carbonate (anhydrous) 5 5 sodium straight tridecylbenzene sulfonate 12.2 AEOS (1) 2.8 optical brightener (Tinopal LMS-X) 0.4 perfume 0.3 CMC 0.2 (2) 10 enzyme 1

- * V V V V V V

glycerol - 4-4--4 borax - - 3 3 - 3 3 carboxylic acid compound - - - - 2 2 2 water and auxiliaries -REST- 15 (1) sodium alkyl polyethoxysulfate, the alkyl group containing 12-15 carbon atoms and the polyethoxy from 3 ethoxy groups exist.

(2} "Esperase" sold by Novo Industries with an activity of 8.0 KNPCJ / g (kg Novo protease units / g).

The enzyme activities of compositions A-G were examined after storage at 43 ° C for 7 days. The measured enzyme activity for each composition after this storage period is reported in Table B and Table C as a percentage of the initial value. The various carboxylic acids and salts used in the formulations of compositions A, B, C, D, Ξ, and G are listed in Table B, as are the enzyme activities associated with each composition.

TABLE B

Enzyme stability ,,. Percentage of active enzyme

Compound, after 7 days at 43 ° C

30 A (control) ND *

B (with glycerol) ND

C (with borax) ND

D (with glycerol and borax) 45 86C13 2 § -14-

Composition E (with carboxylic acid compound) Percentage of active enzyme

wherein the carboxylic acid compound consists of: after 7 days at 43 ° C

(1) succinic acid ND *

(2) malonic acid ND

5 (3) malic acid ND

(4) oxalic acid ND

(5) maleic acid ND

(6) tartaric acid ND

(7) aspartic acid ND

10 (8) citric acid ND

(9) glycine ND

(10) alanine ND

(11) sodium succinate

(12) sodium formate ND

15 (13) sodium acetate ND

(14) sodium tartrate ND

(15) sodium citrate ND

(16) sodium glycolate ND

(17) sodium tetrahydroxysuccinate ND

20 ND * = undetectable (below 10% residual activity): -30 1 9 2-3 -15-

Composition G (with glycerol / borax / carbon- Percentage of active enzyme acid compound), where the carboxylic acid after 7 days at 43 ° C

compound consists of; _ __ (1) sodium succinate 60 5 (2) succinic acid 94 (3) malonic acid 91 (4) malic acid 79 (5) oxalic acid 31 (6) maleic acid 38 10 (7) tartaric acid 63 (8) aspartic acid 84 (9 ) citric acid 62 (10) glycine 80 (11) alanine 79 15 (12) sodium formate 57 (13) sodium acetate 50 (14) sodium tartrate 54 (15) sodium citrate 57 (16) sodium glycolate 50 20 (17) sodium tetrahydroxysuccinate 61

As shown in Table B, composition A, the control composition, as well as compositions B and C, containing glycerol and borax as individual stabilizers, respectively, showed almost no enzyme activity after 7 days of storage at 43 ° C. Since an enzyme activity below 10% cannot be accurately measured, it is referred to as "ND".

Composition D containing glycerol / borax in the absence of a carboxylic acid compound improved enzyme stability over compositions A, B and C, but more than 50% of the enzyme was inactivated.

The various compositions E, which contain a plurality of carboxylic acid compounds, as indicated, showed absolutely no improvement in enzyme stability over compositions A, B and C.

However, compositions G blended according to the invention unexpectedly showed a synergistic improvement in enzyme stability achieved using glycerol / borax in combina-. 3192: -V.

-16- with the carboxylic acid compound in the present liquid detergent compositions * It is noted that in each of the 17 compositions, corresponding to composition G, that were tested, the enzyme activity relative to composition D (containing glycerol and borax) was improved.

A comparison of the enzyme activities achieved with compositions D (glycerol / borax) and different compositions F (borax / carboxylic acid compound) and G (mixed according to the invention) is shown in Table C below.

10 TABLE C

Enzyme stability

Percentage of active enzyme

Composition after 7 days at 43 ° C

D (glycerol / borax) 45 15 F (borax / malonic acid) 13 G (glycerol / borax / malonic acid) 91 F (borax / apartic acid) 39 G (glycerol / borax / aspartic acid) 84 F (borax / citric acid) ND * 20 G (glycerol / borax / citric acid) 62 ND * = undetectable (below 10% residual activity).

As shown in Table C, the various compositions G containing a 3-component stabilizer system of the invention provided a synergistic improvement in enzyme stability over compositions D and F mixed in the prior art.

-t. λ Λ * 1 f * O%

Claims (22)

A stabilized enzyme-containing formulated liquid detergent composition, comprising: (a) about 5-20% by weight of one or more surfactant surfactants selected from the group consisting of anionic, nonionic and amphoteric detergent compounds ; (b) about 5-30% by weight of one or more builder salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxylates; (c) an effective amount of an enzyme or an enzyme-10 mixture selected from the group consisting of alkaline protease enzymes and α-amylase enzymes; (d) an enzyme stabilizing system based on the weight of the detergent (i) about 1-10% glycerol; (ii) about 1-8% of a boron compound selected from the group consisting of boric acid, boron oxide and alkali metal borates and (iii) about 0.5-8% of a carboxylic acid compound selected from the group consisting of mono-, di- and / or polycarboxylic acids with 1-8 carbon atoms and water-soluble salts thereof; and (e) with residual water and optionally perfume and other additives. A liquid detergent according to claim 1 consisting of (a) about 5-15% of an alkali metal alkylbenzene sulfonate, the alkyl group containing 12-15 carbon atoms; (b) about 2-5% of an alkali metal alkyl polyethoxy sulfate, the alkyl group containing 10-18 carbon atoms and the polyethoxy consisting of 3-11 ethylene oxide groups, the weight ratio of (a) and (b) about 2: 1 to about 8: 1; (o) about 5-20% sodium tripolyphosphate; (d) about 1-10% sodium carbonate, the weight ratio of (c) to (d) being about 2: 1 to about 6: 1; (e) an effective amount of said enzyme or enzyme mixture; (f) the enzyme stabilizing system, which based on the weight of the detergent composition (i) is about 3-7% glycerol; 3 6 0 1 s' 2 -18- (ii) contains about 1-5% of an alkali metal borate and (iii) contains about 0.5-4% of said carboxylic acid compound; and (g) with residual water and optionally minor auxiliary substances. Detergent according to claim 2, characterized in that said alkali metal alkyl benzene sulfonate is sodium straight tridecyl benzene sulfonate and said alkali metal alkyl polyethoxy sulfate is a compound in which the alkali metal is sodium, the alkyl group contains 12-15 carbon atoms and the polyethoxy consists of about 3 ethylene oxide groups. Liquid detergent according to claim 3, characterized in that the ratio of tridecylbenzene sulfonate to polyethoxy sulfate is from about 3: 1 to about 5: 1. Detergent according to claim 2, characterized in that said boron compound is an alkali metal borate. Detergent according to claim 5, characterized in that said borate is borax. Detergent according to claim 2, characterized in that it contains about 10-16% sodium tripolyphosphate and about 3-7% sodium carbonate. Detergent according to claim 2, characterized in that said carboxylic acid is succinic acid or a water-soluble salt. Detergent according to claim 2, characterized in that said carboxylic acid is maleic acid or a water-soluble salt thereof. Detergent according to claim 2, characterized in that said carboxylic acid is citric acid or a water-soluble salt thereof. A detergent according to claim 2, characterized in that said carboxylic acid is malonic acid or a water-soluble salt thereof. Detergent according to claim 2, characterized in that said carboxylic acid is malic acid or a hydrocarbon-soluble salt thereof. 13. A method of washing laundry comprising contacting the stained and / or soiled items or fabrics to be washed with a stabilized enzyme-containing formulated liquid detergent comprising: (a) about 5-20 wt. % of one or more surfactants selected from the group consisting of anionic, nonionic and amphoteric detergent compounds; (B) about 5-30% by weight of one or more builder salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxylates; 350 1 92 S <C -19- (c) an effective amount of an enzyme or an enzyme mixture selected from the group consisting of alkaline protease enzymes and α-amylase enzymes; (d) containing an enzyme stabilizing system based on the weight of the detergent (i) about 1-10% glycerol; (ii) about 1-8% of a boron compound selected from the group consisting of boric acid, boron oxide and alkali metal borates and (iii) about 0.5-8% of a carboxylic acid compound selected from the group consisting of mono-, di- and / or polycarboxylic acids with 1-8 carbon atoms and water-soluble salts thereof; and (e) with residual water and optionally perfume and other aids. A method according to claim 13, characterized in that said liquid detergent comprises: 15 (a) about 5-15% of an alkali metal alkylbenzene sulfonate, wherein the alkyl group contains 12-15 carbon atoms; (b) about 2-5% of an alkali metal alkyl polyethoxy sulfate, the alkyl group containing 10-18 carbon atoms and the polyethoxy consisting of 3-11 ethylene oxide groups, the weight ratio of (a) to (b) being about 2: 1 to about 8: 1; (c) about 5-20% sodium tripolyphosphate; (d) about 1-10% sodium carbonate, the weight ratio vein (c) to (d) being about 2: 1 to about 6: 1; (e) an effective amount of said enzyme or enzyme mixture; Cf) the enzyme stabilizing system, which, based on the weight of the detergent composition (i), is about 3-7% glycerol; (ii) about 1-5% of an alkali metal borate and (iii) about 0.5-4% of said carboxylic acid compound; and 30 (g) with residual water and optionally minor auxiliary substances. 15. A method according to claim 14, characterized in that said alkali metal alkyl benzene sulfonate is sodium straight tridecyl benzene sulfonate and said alkali metal alkyl polyethoxy sulfate is a sulfate, the alkali metal being sodium, the alkyl group containing 12-15 carbon atoms and the polyethoxy being about 3 ethylene oxide groups; ) 1 9 2 e * · m -20- A method according to claim 15, characterized in that the ratio of tridecylbenzene sulfonate to polyethoxy sulfate is about 3: 1 to about 5: 1. 17. Method according to claim 14, characterized in that said boron compound is borax. A method according to claim 14, characterized in that the liquid detergent contains about 10-16% sodium tripolyphosphate and about 3-7% sodium carbonate. 19. A method according to claim 14, characterized in that the carbon-10 acid compound is succinic acid or a water-soluble salt thereof. A method according to claim 14, characterized in that the carboxylic acid compound is citric acid or a water-soluble salt thereof. A method according to claim 14, characterized in that the carboxylic acid compound is maleic acid or a water-soluble salt thereof. A method according to claim 14, characterized in that the carboxylic acid compound is malonic acid or a water-soluble salt thereof. 8801926