KR940010118B1 - Stabilized fabric softening built liquid detergent composition containing enzymes - Google Patents

Abstract

No content.

Description

Stabilized Enzyme-Containing Enhanced Liquid Detergent Composition and Washing Method Using the Same

The present invention relates to stable and enhanced enzyme-containing liquid detergent compositions suitable for laundry or preimmersion formulations. More specifically, the present invention relates to an aqueous enzyme-containing liquid detergent composition which contains one or more detergent enhancers and is characterized as being a physically stable homogeneous liquid detergent composition.

The formulation of stabilized enzyme-containing liquid detergent compositions has been of much interest to date. The reason for incorporating enzymes into detergent compositions is primarily due to the proteolytic and starch degrading enzymes in the degradation of proteins and starches found on contaminated fabrics, such as scavenger stains, blood stains and chocolate stains during washing. This is because it is effective to facilitate the removal of stains. However, suitable enzymes, particularly proteases, for laundry compositions are relatively expensive. Indeed, although they are present in relatively small amounts, they are generally among the most expensive components in representative commercial liquid detergent compositions. Moreover, enzymes are known to be labile in aqueous compositions. This is because excess enzymes are generally required in liquid detergent formulations to compensate for the loss of enzymatic activity expected during delayed storage periods. Thus, the prior art is full of proposals for stabilizing enzyme-containing liquid detergent compositions, especially non-enhanced liquid compositions, by incorporating into the composition various materials that act as enzyme stabilizers.

In the case of liquid detergent compositions containing enhancers, the problem of enzyme instability is particularly serious. The main reason is that even in compositions containing enzyme stabilizers, detergent enhancers have destabilizing effects on enzymes and are otherwise effective in non-enhanced formulations. In addition, incorporation of the enhancer into the liquid detergent composition has the ability to form so-called stable single-phase compositions; For example, there is an additional problem that the solubility of sodium tripolyphosphate is limited, especially in the presence of anionic and nonionic detergents in aqueous compositions.

In British Patent Specification G.B 2,079,305, published January 20, 1982, an aqueous enhanced enzyme-containing liquid detergent composition stabilized by a mixture of polyols and boric acid is disclosed. As described in the examples of the British specification, relatively large amounts of glycerol are required to stabilize the enzymes in the composition. However, as described later herein, the enzyme stabilizing effect provided by the mixture of glycerin and borax in the enhanced aqueous liquid detergent composition is relatively most suitable.

In European Patent Specification Publication No. 0326505, an aqueous enzyme-containing liquid detergent composition containing an enzyme stabilizer mixture consisting of certain dicarboxylic acids and borax is described. Dicarboxylic acids are recommended as a substitute for polyols such as glycerol in known enzyme stabilizer mixtures consisting of glycerol and boron compounds. However, such dicarboxylic acid-borax mixtures cannot provide anything other than an optimal stabilizing effect in the present enhanced liquid detergent compositions, such as the above-mentioned mixtures of glycerin and borax.

The present invention relates to an stabilized fabric softening enhanced, enzyme-containing liquid detergent composition consisting of:

(a) about 5-20% by weight of one or more surfactant detergent compounds selected from the group consisting of nonionic, anionic and amphoteric detergent compounds;

(b) about 5-30% by weight of one or more enhancer salts selected from the group consisting of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxylates;

(c) about 5-20% by weight of swelling bentonite clay;

(d) an effective amount of an enzyme or enzyme mixture selected from the group consisting of alkaline protease enzymes and alpha-amylase enzymes;

(e) about 1-10% of glycerin by weight of the detergent composition; (Ii) about 1-8% of a boron compound selected from the group consisting of boric acid, boric acid oxides and alkali metal borate salts; (Iii) an enzyme-stabilizing agent containing about 0.5-8% of a carboxylic acid compound selected from the group consisting of mono, di and / or polycarboxylic acids having 1-8 carbon atoms and water soluble salts thereof; And

(f) the remainder is water and optionally spices and other auxiliaries.

In a preferred embodiment of the invention, the liquid detergent composition consists of:

(a) about 5-15% of an alkali metal alkylbenzene sulfonate in which the alkyl group contains 12-15 carbon atoms;

(b) an alkali metal alkylpoly having an alkyl group of 10-18 carbon atoms and a polyethoxy of 3-11 ethylene oxide groups, wherein the weight ratio of (a) :( b) is about 2: 1-about 6: 1 Ethoxy sulfate about 0.5-5%;

(c) about 5-20% sodium tripolyphosphate;

(d) sodium carbonate, sodium bicarbonate, or mixtures thereof, wherein the neutral ratio of (c) :( d) is about 2: 1- about 6: 1; about 1-10%;

(e) about 10-15% sodium bentonite;

(f) an effective amount of the above-mentioned enzyme or enzyme mixture;

(g) enzyme stability containing (i) about 1-5% glycerin (ii) about 1-5% alkali metal borate and (iii) about 0.5-4% of said carboxylic acid compound, based on the weight of the detergent composition issue ; And

(h) The remainder is water and optional fragrances and other supplements.

According to the method of the present invention, washing is achieved by contacting the stained and / or contaminated material with an aqueous solution of the liquid detergent composition as defined above.

The liquid detergents described are commercially acceptable heavy laundry detergents that can satisfactorily clean laundry items containing both oily and particulate contaminants. In addition, the described compositions can be used for the pretreatment of heavily contaminated sites, such as the collar and cuff of the item to be washed.

The present invention is based on the discovery of a three-component enzyme stabilization system as defined herein, which provides the liquid detergent composition of the present invention with a greater enzyme stabilization effect than can be obtained with conventional enzyme stabilizers. The enzyme stabilizing effect thus obtained reflects the synergy between the three components. According to the present invention, in order to significantly increase the level of enzyme stability provided when using a mixture of glycerin and borax or a mixture of borax and dicarboxylic acid independently as an enzyme stabilizer, the three-component stabilization system defined herein is Use in the composition can synergistically enhance the enzyme stability provided by a mixture of glycerin and borax or a mixture of borax and dicarboxylic acid. Preferred enzyme stability for commercial purposes generally corresponds to a half-life of about one week at a temperature of 43 ° C. (110 ° F).

The enzyme stabilization system of the present invention is a mixture of glycerin and a boron compound selected from boric acid, boric oxide and alkali metal borate and a carboxylic acid compound as defined herein. The weight of the stabilizing system in the present enhanced liquid detergent composition is generally about 3-25% by weight, preferably about 6-15% by weight. The weight ratio of glycerin to borax in the stabilization mixture is generally about 0.5-3. The preferred amount of glycerin in the composition is about 1-5% by weight of the composition, the preferred amount of boron compound is about 1-5%, and the preferred amount of carboxylic acid compound is about 0.5-4%.

Carboxylic acid compounds useful in the enzyme stabilization system of the present invention include those saturated with unsaturated mono, di and polycarboxylic acids having 1-8 carbon atoms, including oxalic acid (HOOCCOOH) and malonic acid (HOOCCH ₂ COOH). , Maleic acid (HOOCCH: CHCOOH), and succinic acid (HOOCCH ₂ CH ₂ COOH). Carboxylic acids may contain hydroxy or amino substituents, as illustrated by malic acid (HOOCCHOHCH ₂ COOH), tartaric acid (dihydroxysuccinic acid), aspartic acid (aminosuccinic acid) and citric acid. Preferred carboxylic acids of the present invention are aspartic acid, tartaric acid, malonic acid and malic acid. From a commercial standpoint, particularly preferred carboxylic acids are citric acid and / or salts thereof due to their relatively low cost.

Suitable alkaline proteases for the present compositions include various commercial liquid enzyme preparations suitable for use in detergent compositions. Although generally less convenient for incorporation into enhanced liquid detergent compositions, enzyme preparations in powder form are also useful. Thus, suitable liquid enzyme preparations include "Alcalase" and "Esperase" sold by Denmarac Copenhagen Novo Industries, and "Maxatase" and "AZ-Protease" sold by Delft Gist-Brocadez, The Netherlands.

Among the suitable α-amylase liquid enzyme preparations are those sold under the trade names “Ter-mamyl” and “Maxamyl” by Novo Industries and Gist-Brocades, respectively.

"Esperase" is particularly preferred for the present compositions because it has optimum activity at high pH corresponding to enhanced detergent compositions.

Preferred detergents for use in the present liquid compositions are synthetic nonionic detergent compounds, in particular mixtures of higher alkylbenzene sulfonates and alkyl polyethoxy sulfates. Other water soluble higher alkylbenzene sulfonates, such as potassium salts and in some cases suitable ammonium or alkanol ammonium salts, may also be present in this formulation, but where appropriate, sodium salts have been found to be highly preferred, which is an alkylpolyethoxy sulfate The same is true of the detergent ingredients. Alkylbenzene sulfonates are those in which the higher alkyl has 12-15 carbon atoms, preferably 13 carbon atoms. Alkylpolyethoxy sulfates, which may also be referred to as sulfated condensation products of sulfated polyethoxylated higher linear alcohols or higher fatty alcohols with ethylene oxide or polyethoxylene glycols, are alkyl having from 10 to 18 carbon atoms, Preferably it has 12-15 carbon atoms, such as about 13 carbon atoms, 3-11 ethylene oxide groups, preferably 3-7, more preferably 3-5, most preferably 3 or about 3 It contains an ethylene oxide group. The alkylbenzene sulfonate: polyethoxy sulfate weight ratio in the detergent mixture is preferably about 2: 1-6: 1 and most preferably about 2: 1-4: 1. At a ratio of about 5: 1 or greater, the physical stability of the product can be adversely affected.

, 예컨대 약 12-13개 탄소원자의 고급지방알콜과 약 6.5몰의 에틸렌 옥사이드와의 축합생성물인

23-6.5와 같이, 비이온 및 양쪽성 물질이 또한 존재할 수 있다. 언급된 다양한 세제 및 세제의 종류에 대한 설명이 Surface Active Agents, Vol.II. by Schwartz, Perry and Berch(Interscience Publishers. 1958) 본문에 나와 있다.Fatty alcohol sulfates, paraffin sulfonates, olefin sulfonates, monoglyceride sulfates, sarcosinates and similarly functioning detergents, preferably alkali metals, such as sodium salts in suitable circumstances, are sometimes synthesized as described above. It may be present as a partial substitute for organic detergents, but usually in addition to such detergents. Usually, supplemental detergents are sulfated or sulfonated products (usually in the form of sodium salts) and contain long chain (8-20 carbon atoms) straight or fatty alkyl groups. In addition to any supplementary anionic synthetic organic detergents, commercially available from Shell Chemical Kampati, a condensation product of ethylene oxide and higher fatty alcohols

For example, a condensation product of higher fatty alcohols of about 12-13 carbon atoms with about 6.5 moles of ethylene oxide.

As with 23-6.5, nonionic and amphoteric materials may also be present. A description of the various detergents and the types of detergents mentioned is given in Surface Active Agents, Vol. by Schwartz, Perry and Berch (Interscience Publishers. 1958).

The enhancer salt formulations of the present invention, which are known to have a synthetic anionic organic detergent mixture to satisfactorily improve washability and form a desirable pH in liquid detergent and wash water, are a mixture of sodium tripolyphosphate and sodium carbonate. Enhancer salts are generally used in amounts of about 5-25% by weight in the composition. In a preferred enhancer salt formulation, sodium tripolyphosphate is present in an amount of about 5-20% by weight, preferably 10-16% by weight and sodium carbonate is present in about 1-10% by weight, preferably 3-7% by weight. And the weight ratio of tripolyphosphate: carbonate in the preferred enhancer mixture is about 2: 1-6: 1, most preferably about 2: 1-4: 1. As used herein, the term alkali metal "carbonates" or "carbonates" is meant to include carbonates, bicarbonates and seskey carbonates in the alkali gold.

It is desirable that the sodium tripolyphosphate content of the Phase I tripolyphosphate is low for optimum processing, easy mixing and good end use properties. Therefore, the content of phase I tripolyphosphate should normally be 30% or less of the tripolyphosphate used. Although incompletely neutralized tripolyphosphate may be used in some cases, the phosphate commonly used may be considered to be sodium tripolyphosphate, Na ₅ P ₃ O ₁₀ . Of course, in some cases, such as when potassium salts of other substances are present, ion exchange in an aqueous medium may result in salts other than sodium tripolyphosphate, but for the purposes of this specification it is usually incorporated into a mixer to prepare the liquid detergent. Sodium tripolyphosphate as the sodium salt is believed to be the tripolyphosphate used.

Other preferred enhancer salts that may be used instead of or in addition to sodium tripolyphosphate and sodium carbonate include triacetate (NTA) with polyacetal carboxylate and sodium nitrile described herein. Of course, mixtures of the above water-soluble enhancer salts may also be used. However, although other enhancers and mixtures thereof are also effective, the described tripolyphosphate-carbonate mixtures have been published as most preferred. Other enhancers that can be used as supplements in addition to the ratios of the above mentioned enhancers include tetrasodium pyrophosphate or other phosphates such as potassium tetrapyrophosphate, sodium bicarbonate, sodium citrate, sodium gluconate, sodium silicate and sodium sesquicarbonate. Included. Among the water insoluble enhancers that can be used are zeolites such as zeolite A, although amorphous zeolites are also useful, usually in their crystalline hydrate form.

Polyacetal carboxylates are generally described in US Pat. Nos. 4,144,226 and 4,315,092. US Patent No. 4,146,495 describes detergent compositions containing polyacetal carboxylate as an enhancer.

Polyacetal carboxylates useful herein as enhancers are those described in US Pat. No. 4,144,226 and are prepared by the methods mentioned therein. Typical such products are formulas

Has

Wherein M is selected from the group consisting of alkali metal, ammonium C _1-4 alkyl group, tetraalkyl ammonium group and alkanolamine group, both having 1-4 carbon atoms in the alkyl group, n is at least 4 R ₁ and R ₂ are any chemically stable groups that stabilize the polymer against rapid depolymerization in alkaline solution.

Preferred polyacetal carboxylates are those in which M is an alkali metal such as sodium, n is 50-200, and R ₁ is

또는

or

Or a mixture thereof, R ₂ is

N is on average 20-100, more preferably 30-80. The calculated weight average molecular weight of the polymer is usually in the range of 2,000-20,000, preferably 3,500-10,000, more preferably 5,000-9,000, such as about 8,000.

Particularly preferred sodium polyacetal carboxylates are supplied by Monsanto Campani and are known as enhancer U. It has a calculated average molecular weight of about 8,000 and an active polymer content of about 80%.

Preferred polyacetal carboxylates have been described above, but in whole or in part by other such polyacetal carboxylates or related organotensifier salts described in the patents cited above for the compounds, their preparation and the compositions in which they are used. Of course, it can be replaced. In addition, a variety of patents can be used, especially the chain terminators described in US Pat. No. 4,144,226, provided that they depolymerize the above-mentioned enhancers in acidic media and facilitate their biodegradation in waste streams, but with alkaline media such as laundry solutions. Within it should have desirable stabilizing properties to maintain their stability.

Bentonite used here is colloidal clay (aluminum silicate) containing montmorillonite. Swelling bentonite is generally characterized by sodium bentonite, ie bentonite, where the predominant cation is sodium. Of sodium bentonite clay, those of Wyoming (generally referred to as Western or Wyoming bentonite) are particularly preferred.

Bentonite's swelling ability is generally associated with its fabric softening properties. The swelling capacity of sodium bentonite in water is 3-20 ml / g, 7-15 ml / g, and its viscosity in a 6% aqueous solution usually ranges from 3-30 centipoas, preferably 8-30 centipoas. .

Preferred swelling bentonite is marketed under the HI-JEL trade name by Georgia Kaolin. These materials are identical to bentonite previously marketed under the MINERAL COLLOID and THIXO-JEL trade names. These are selectively mined and benefited bentonites, the most useful of which are available as HI-JEL Nos. 1, 2, 3, etc. and correspond to Nos. 1, 2, 3 and 4 of THIXO-JEL. These materials have a 4% -8% maximum free moisture content (before addition to the liquid medium) and a specific gravity of about 2.6. Bentonite is preferably passed through a 200 mesh USSieve Series sieve, most preferably at least 90% of particles pass through No. 325 sieve, thus the bentonite has an equilateral diameter of 74 microns or less, more preferably about 44 It can be considered to be less than a micron.

Typical chemical analysis of some bentonites useful for preparing this liquid detergent has shown that bentonites are 64.8-73.0% SiO ₂ , 14-18% Al ₂ O ₃ , 1.6-2.7% MgO, 1.3-3.1% CaO, 2.3 -3.4% Fe ₂ O ₃ , 0.8-2.8% Na ₂ O and 0.4-7.0% K ₂ O.

Although Western bentonite is preferred, other bentonites that increase the cation exchange capacity of the product, prepared by treating Italian or similar bentonite containing relatively small proportions of exchangeable monovalent metals (sodium and potassium) with alkaline materials such as sodium carbonate It is also possible to use. The bentonite Na ₂ O content should be at least about 0.5%, preferably 1%, more preferably at least 2% so that the clay is considered to swell satisfactorily with good softening and dispersing properties in the aqueous suspension. Preferred swelling bentonites of the type described above are commercially available under the trade names Laviosa and Winkelmann, such as Laviosa AGB and Winkelmann G-13.

Other bentonites that are particularly useful for this liquid detergent composition because of their white or very bright color include Polarite KB 325 (American Colloid Company) and GK 129 (Mexican Bentonite) from Georgian Kaolin.

The viscosity of the present liquid detergent is usually in the range of about 1000-10,000 centipoas, preferably 2,000-7,000 centipoas, although other suitable viscosities may also be useful. At the viscosities mentioned the liquid detergent is pourable and stable and is not separated but uniform. Usually the pH of the liquid detergent suspension in the range 7-11.5, preferably 8-10.5, appears to help maintain product stability and flowability.

The following examples illustrate the invention and do not limit it.

Unless otherwise indicated, all weights and temperatures are in degrees Celsius.

EXAMPLE

(1) Alkyl polyethoxysulfate, wherein alkyl has 12-15 carbon atoms and polyethoxy contains three ethoxy groups

(2) "Esperase" sold by Novo Industries with an activity of 8.0 KNPU / gram

The composition was prepared by the following method.

30.0 parts of 40 ° F deionized water are added to a suitable mixing device such as a vertical cylindrical tank equipped with a stirrer. The stirrer is set to medium stirring and a mixture consisting of 2.0 parts of anhydrous sodium ash, 2.0 parts of sodium seskicarbonate and 0.2 parts of sodium carboxymethyl cellulose is incorporated into the water.

The stirrer speed is then raised to maximum stirring and a mixture consisting of 11.0 parts of sodium tripolyphosphate and 12.0 parts of bentonite is slowly added to the mixing apparatus over 10-15 minutes to form a yellowish white suspension. Next, add 8.64 parts of high AI (about 55%) LTBS slurry while lowering the stirring speed to slow / middle adjustment. Next, a fluorescent brightener / color solution consisting of 0.3 parts of Tinopal LMS-X (Ciba-Geigy), 0.99 parts of colorant and 4.02 parts of deionized water is added. Once a uniform cyan solution is obtained, 0.4 part of fragrance is added to the mixture while stirring the mixture. Next, 3.0 parts of glycerin and 2.5 parts of borax are gradually added as a two-component slurry. Stirring is continued until the mixture is uniform in appearance, then 2.0 parts citric acid and 9.0 parts water are added slowly. Next, the mixture was agitated and 10.95 parts of mixed AI detergent base consisting of LTBS slurry (about 30% AI) and AEOS (about 27.5% AI) were added to the mixture. This is followed by the slow addition of 1.0 part of protease with continuous stirring until all material is fully dispersed or dissolved.

Example 2

Enzyme-containing enhanced liquid detergent compositions A-G were combined as given in Table 1 below. Percentages refer to weight percentages. The arrow means that composition B-G indicates the same degree as composition A.

TABLE 1

(1) Alkylpolyethoxy sulfate in which alkyl has 12-15 carbon atoms and polyethoxy contains 3 ethoxy groups.

(2) "Esperase" sold by Novo Industries with an activity of 8.0 KNPU / gram (kilo novoprorease units / gram)

Enzymatic activity of Compositions A-F was measured after 7 days storage at 110 ° F. The enzyme activity measured for each composition after this storage period is shown as a percentage of the initial value in Table 2. The various carboxylic acids and salts used in the general formulation of Compositions A, B, C, D, E and G are shown in Table 2 with the enzymatic activity corresponding to each composition.

TABLE 2

Enzyme stability

As evident from Table 2, the comparative composition, Composition A, with Compositions B and C containing separate stabilizers of glycerin and borax, showed little enzymatic activity after 7 days storage at 100 ° F., respectively.

Enzyme activity below 10% is indicated as "ND" because it cannot be measured accurately. Composition D containing glycerin / borax without carboxylic acid compound provided an increase in enzyme stability compared to composition A, but about 50% of the enzyme was inactivated. As can be seen, various compositions E containing various carboxylic acid compounds have absolutely no improvement in enzyme activity over composition A.

However, composition G formulated according to the invention shows an unexpected synergistic improvement in the enzyme stability obtained using glycerin / borax in combination with the carboxylic acid compound in the present liquid detergent composition.

It is noted that most of the compositions corresponding to composition G show a marked improvement in enzymatic activity compared to composition D (containing glycerin and borax).

Comparators of enzymatic activity obtained with composition D (glycerine and borax) and various compositions F (borax / carboxylic acid compound) and G (formulated according to the invention) are given in Table 3 below.

TABLE 3

Enzyme stability

As shown in Table 3, various compositions G containing a three component stabilizer system according to the present invention provide a synergistic improvement in enzyme stability compared to compositions D and F formulated according to the prior art.

Claims (22)

(a) about 5-20% by weight of one or more surfactant detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds, (b) alkali metal tripolycarbonates, alkali metal carbonates, alkali metal nitrilotriles About 5-30% by weight of one or more enhancer salts selected from the group consisting of acetates and polyacetalcarboxylates, (c) about 5-20% by weight of swollen bentonite clay, (d) alkaline protease enzymes and alpha- An effective amount of an enzyme or enzyme mixture selected from the group consisting of amylase enzymes, (e) about 1-100% glycerin, based on the weight of the detergent composition, (ii) boric acid, borate oxides and alkali metal borate salts A boron compound selected from the group consisting of about 1-8%, and (iii) mono, di and / or polycarboxylic acids having 1-8 carbon atoms and water soluble salts thereof. From containing from about 0.5-8% acid compound selected enzyme-stabilization system, and (f) the remainder consisting of water and optionally a fragrance, and other aids, fabric softening stabilized enzyme-containing liquid detergent compositions enhancement. The process according to claim 1, wherein (a) about 5-15% of an alkali metal alkylbenzene sulfonate containing 12-15 carbon atoms, (b) an alkyl group containing 10-18 carbon atoms and a polyethoxy 3- About 0.5-5% of an alkali metal alkylpolyethoxysulfate consisting of eleven ethylene oxide groups and having a weight ratio of (a) :( b) of about 2: 1-about 6: 1, (c) sodium tripolyphosphate about 5- 20%, (d) sodium carbonate, sodium bicarbonate or mixtures thereof, wherein the weight ratio of (c) :( d) is about 2: 1-about 6: 1) about 1-10%, (e) sodium bentonite about 10- 15%, (f) an effective amount of the enzyme or enzyme mixture, (g) about 1-5% glycerin, (ii) about 1-5% alkali metal borate based on the weight of the detergent composition and (iii) ) An enzyme stabilizing system containing about 0.5-4% of said carboxylic acid compound, and (h) the remainder consisting of water and an optional minor amount of adjuvants. 3. The alkali metal alkyl benzene sulfonate of claim 2 is a linear sodium tridecylbenzene sulfonate, the alkali metal alkyl polyethoxy sulfate is an alkali metal is sodium and the alkyl group contains 12-15 carbon atoms and Is about 3 ethylene oxide groups. 4. The liquid detergent composition of claim 3, wherein the ratio of tridecylbenzenesulfonate, polyethoxy sulfate is about 2: 1- about 4: 1. The liquid detergent composition according to claim 2, wherein the boron compound is an alkali metal boride salt. The liquid detergent composition according to claim 5, wherein the borate is borax. The liquid detergent composition of claim 2, comprising about 8-16% sodium tripolyphosphate and about 2-6% sodium carbonate, sodium bicarbonate, or mixtures thereof. The liquid detergent composition according to claim 2, wherein the carboxylic acid compound is aspartic acid or a water-soluble salt thereof. The liquid detergent composition according to claim 2, wherein the carboxylic acid compound is tartaric acid or a water-soluble salt thereof. The liquid detergent composition according to claim 2, wherein the carboxylic acid compound is citric acid or a water-soluble salt thereof. The liquid detergent composition according to claim 2, wherein the carboxylic acid compound is malonic acid or a water-soluble salt thereof. The liquid detergent composition according to claim 2, wherein the carboxylic acid compound is malic acid or a water-soluble salt thereof. (a) about 5-20% by weight of one or more interfacial sulfur detergent compounds selected from the group consisting of anionic, nonionic and amphoteric detergent compounds, (b) alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriles About 5-30% by weight of one or more enhancer salts selected from the group consisting of acetates and polyacetalcarboxylates, (c) about 5-20% by weight of swollen bentonite clay, (d) alkaline protease enzymes and alpha- An effective amount of an enzyme or enzyme mixture selected from the group consisting of amylase enzymes, (e) based on the weight of the detergent composition, (iii) about 1% -10% glycerin, (ii) boric acid, borate oxides and alkali metal borate salts A boron compound selected from the group consisting of about 1-8%, and (iii) mono, di and / or polycarboxylic acids having 1-8 carbon atoms and water-soluble salts thereof. Enzyme-stabilizing agents containing about 0.5-8% of the selected carboxylic acid compound, and (f) the remainder consisting of water, optional flavorings and other auxiliaries, and a stabilized enzyme-enhanced liquid detergent composition A laundry method comprising contacting a stained and / or contaminated fabric to be made. The liquid detergent composition of claim 13, wherein the liquid detergent composition comprises (a) about 5-15% of an alkali metal alkylbenzenesulfonate salt containing 12-15 carbon atoms, and (b) an alkyl group containing 10-18 carbon atoms and About 0.5-5% of an alkali metal alkylpolyethoxysulfate consisting of 3-11 ethylene oxide groups and having a weight ratio of (a) :( b) of about 2: 1-about 6: 1, (c) tripoly Sodium phosphate about 5-20%, (d) sodium carbonate, sodium bicarbonate or mixtures thereof, wherein the weight ratio of (c) :( d) is about 2: 1-about 6: 1) about 1-10%, (e) Sodium bentonite about 10-15, (f) an effective amount of the enzyme or enzyme mixture, (g) about 1-5% glycerin, (ii) about 1-5% alkali metal, based on the weight of the detergent composition A borate salt, and (iii) an enzyme stabilization system containing about 0.5-4% of said carboxylic acid compound, and (b) the remainder consisting of water and an optional minor amount of adjuvant. 15. The method according to claim 14, wherein the alkali metal alkylbenzene sulfonate is straight-chain sodium tridecylbenzenesulfonate, the alkali metal alkylpolyethoxysulfate is sodium alkali metal and the alkyl group contains 12-15 carbon atoms and polyethoxy Is about 3 ethylene oxide groups. 16. The method of claim 15, wherein the tridecylbenzenesulfonate salt, polyethoxy sulfate, is in a ratio of about 2: 1- about 4: 1. The method of claim 14, wherein the boron compound is borax. 15. The method of claim 14, wherein the liquid detergent composition contains about 8-16% sodium tripolyphosphate and about 2-6% sodium carbonate, sodium bicarbonate, or mixtures thereof. The method according to claim 14, wherein the carboxylic acid compound is aspartic acid or a water-soluble salt thereof. The method according to claim 14, wherein the carboxylic acid compound is citric acid or a water soluble salt thereof. The method according to claim 14, wherein the carboxylic acid compound is malic acid or a water soluble salt thereof. The method according to claim 14, wherein the carboxylic acid compound is malonic acid or a water-soluble salt thereof.