JPS6232196A - Cloth softening liquid detergent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Application: The present invention relates to stable, built, enzyme-containing liquid detergent compositions suitable for laundry or presoak formulations. More particularly, the present invention relates to an aqueous enzyme-containing liquid detergent composition comprising one or more detergent bifluders and being a physically stable homogeneous liquid composition. It is characterized by

Prior Art: The formulation of stabilized enzyme-containing liquid detergent compositions has been the subject of much interest in the prior art. The desirability of incorporating enzymes into detergent compositions is primarily due to their ability to degrade proteinaceous and starchy materials found on contaminated fabrics, thereby eliminating contaminants such as meat juice stains, blood stains, chocolate stains, etc. due to the effectiveness of proteolytic and starch-degrading enzymes in removing them during washing. However, enzymatic materials suitable for use in laundry compositions, especially proteolytic enzymes, are relatively expensive. In fact, they are generally among the most expensive ingredients in typical commercial liquid detergent compositions, even though they are present in relatively small amounts. On top of that,
Enzymes are known to be unstable in aqueous compositions. It is for this reason that excess enzyme is required in liquid detergent formulations to compensate for the expected loss of enzyme activity during long-term storage. Accordingly, conventional methods include stabilizing enzyme-containing liquid detergent compositions, particularly builder-free liquid compositions, by using various substances that are incorporated into the composition to function as enzyme stabilizers. There are many proposals for this.

In the case of liquid detergent compositions containing builders, the problem of enzyme stability is particularly acute. Primarily this is because, even in compositions containing enzyme stabilizers that are effective at °C in builder-free formulations, detergent builders have a desensitizing effect on enzymes.

Moreover, the incorporation of builders into liquid detergent compositions poses additional problems, namely the ability to form stable single-phase compositions, such as the solubility of sodium tripolyphosphate in aqueous compositions. , and is relatively limited, especially in the presence of anionic and cationic properties.

British Patent Application G, B, 2,079,505 (i982
Published January 20, 2013) discloses an aqueous, builder-enzyme-containing liquid detergent composition stabilized by a mixture of polyols and boric acid. As observed in the examples of this British patent application, relatively large amounts of glycerin may be required to stabilize the enzyme in the composition. Moreover, as discussed herein below, the enzyme stabilizing effect provided by the mixture of glycerin and borax in a built aqueous liquid detergent composition is relatively mild.

European Patent Application Publication No. AD 1265D5 discloses an aqueous enzyme-containing liquid detergent composition comprising an enzyme stabilizing mixture of certain dicarboxylic acids and borax.

This dicarboxylic acid is recommended as a replacement for polyols such as glycerin in known enzyme stabilizing mixtures of glycerin and boron compounds. However, this dicarboxylic acid-borax mixture, in common with the aforementioned mixture of glycerin and borax, cannot provide anything more than the mildest stabilizing effect in current built liquid detergent compositions.

SUMMARY OF THE INVENTION The present invention provides a stabilized fabric softening builder-enzyme-containing liquid detergent composition comprising: from about 5 to 20% by weight of fat; selected from the group consisting of anionic, nonionic and amphoteric detergent compounds;
one or more surfactant detergent compounds; (bl selected from the group consisting of about 5 to 50% by weight of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates, and polyacetal carboxylates; one or more builder salts; (approximately 5 to 20% by weight C1 swellable bentonite clay; (d) an effective amount of an enzyme or enzymes selected from the group consisting of alkaline proteolytic enzymes and alpha-amylase enzymes; (e) l Based on the weight of the detergent composition, (i) about 1 to 10% glycerin; (ii) about 1 to 8% boric acid;
a boron compound selected from the group consisting of borax and alkali metal borates; and about 0.5% to 8% +iiD of mono-, di-, and/or poly-carboxylic acids having from 1 to 8 carbon atoms; an enzyme stabilizing system comprising: a water-soluble salt of; and (f) the balance weight consisting of water and optional soy sauce flavoring and other auxiliaries.

In a preferred embodiment of the invention, the liquid detergent composition is.

[al Approximately 5 to 15% of the alkyl groups are 12 to 1
Alkyl metal alkyl benzene sulfonates containing 5 carbon atoms; (bl about 0.5 to 5% of alkyl metal alkylbenzene sulfonates containing 10 to 18 carbon atoms and polyethoxy containing 6 to 11 ethylene oxide groups; I] fJ! Alkyl polyethoxy sulfate having a weight ratio of fat to (bl) of about 2:1 to about 6:1; (C1 about 5 to 2
0% sodium tripolyphosphate; Tdl approximately 1 to 1
(e) about 10 to 15% sodium bentonite; [fl an effective amount of Enzymes or enzyme mixtures as mentioned above; (
g+, based on the weight of the detergent composition, (i) about 1 to 5% glycerin; +B+ about 1 to 5% alkali metal borate; an enzyme stabilizing system containing; and the remainder weight consisting of fhl water and optional fragrance and other auxiliaries.

According to the method of the invention, washing of stained and/or contaminated substances is carried out by contacting these substances with an aqueous solution of a liquid detergent composition as defined above.

The described liquid detergents are capable of satisfactorily cleaning laundry containing both oily and particulate soils. A commercially acceptable heavy duty laundry detergent. Furthermore, the described compositions may be used for pre-treatment of heavily soiled areas such as collars and cuffs of articles to be laundered.

The present invention is based on the discovery of a three-component enzyme stabilization system as defined herein, which system provides the liquid detergent compositions of the present invention with the effects that can be achieved with conventional enzyme stabilizers. Provides enzyme stabilizing effects that go far beyond that. The enzyme stabilizing effect thus achieved reflects the synergism between the three components. According to the present invention, the enzyme stability provided by the mixture of glycerin and borax or a borax mixture and a dicarboxylic acid as disclosed in the prior art provides that the enzyme stability provided by the mixture of glycerin and borax or a borax mixture and a dicarboxylic acid as disclosed in the prior art is achieved in the liquid composition of the present invention by a ternary stabilizing system as defined herein. Synergistically improved by the use of either the glycerin and borax mixture, and the borax and dicarboxylic acid mixture, enzyme stabilization significantly exceeds the levels provided when used independently of each other as enzyme stabilizers. Increases stability level. For commercial purposes, the desired enzyme stability is generally about 1 at a temperature of 110"F'.
Equivalent to half a week's lifespan.

DETAILED DESCRIPTION OF THE INVENTION The enzyme stabilizing system of the present invention is a mixture of glycerin; a boron compound selected from borax, boric acid and alkali metal borates; and a carboxylic acid compound as defined herein. The weight of this stabilizing system in the built liquid detergent compositions of this invention is generally about 6 to 25%, preferably about 6 to 15% by weight. The weight ratio of glycerin to borax in the stabilizing system is generally about 0.5 to 5. A preferred amount of glycerin in the composition is about 1 to 5%, a preferred amount of boron compound is about 1 to 5%, and a preferred amount of carboxylic acid compound is about 0.5 to 4% by weight of the composition. be.

The carboxylic acid compounds useful in the enzyme stabilization systems of the present invention range from 1 to 8 carbon atoms, saturated and unsaturated mono-, di-, and poly-carboxylic acids, among them oxalic acid (HOOCCOOH ) Malonic acid (HOO
CCH2COOH), maleic acid (H○○CCH: C
HC○○H) and succinic acid (H○0CCH2CH2C
00H) is included. To this carboxylic acid! , IJ-f acid (HOOCCHOHCH2COOH).

Human mixic and amine substituents may be included, as exemplified by tartaric acid (dihydroxysuccinic acid), aspangic acid (aminosuccinic acid), and citric acid. Preferred carboxylic acids of the invention are succinic, maleic, malonic, and malic acids. From a commercial point of view, a particularly preferred carboxylic acid compound is citric acid and/or its salts due to its relatively low cost.

Alkaline proteolytic enzymes suitable for the present invention include a variety of liquid enzyme formulations adapted for use in detergent fabrics. Powdered enzyme preparations are also useful, although as a general rule they are not very convenient for incorporation into built liquid detergent compositions. For example, suitable liquid enzyme preparations include "Alcalase" and "Esperase", sold by Novo Industries, Copenhagen, Denmark, and "Maxtase" and "AZ-Protease", sold by Gistov Blockade, Delft, Netherlands. include.

Among suitable alpha-amylase liquid enzyme preparations are those sold by Novo Industries and Gist Prokate under the trademarks "Thermamil" and "Maxamil," respectively.

"Esperase" is particularly preferred for the compositions of the invention because of its optimized activity at high pH values comparable to built detergent compositions.

The preferred detergents for use in this invention are synthetic anionic detergent compounds, particularly mixtures of higher alkylbenzene sulfonates and alkyl polyethoxy sulfates. Other water-soluble higher alkylbenzene sulfonates,
Although, for example, potassium salts, in some cases ammonium salts or alkanol ammonium salts may be present in the formulations of the invention, it has been found that sodium salts are highly preferred, which indicates that the alkyl poly It has been discovered that the same is true for ethoxy sulfate detergent compositions. The alkylbenzene sulfate is one in which the higher alkyl has 12 to 15 carbon atoms, preferably 16 carbon atoms. Alkyl polyethoxy sulfates, which may also be referred to as sulfated polyethoxylated higher linear alcohols or sulfated condensation products of higher aliphatic alcohols and ethylene oxide or polyethoxyethylene glycol, are is 10 to 18, preferably 12 to 15, for example about 15, and 6 to 11, preferably 5 to 7, more preferably 6 to 5, most preferably 6. or about 6 ethylene oxide groups. The ratio of alkylbenzene sulfonate to polyethoxy sulfate in the detergent mixture is preferably about 2:1 to 6:1, most preferably about 2:1 to 4=1 by weight. At ratios greater than 5:1, the physical stability of the product may be adversely affected.

Under appropriate circumstances, other anionic detergents, such as fatty alcohol sulfates, paraffin sulfonates, olefin sulfonates, monoglyceride sulfates,
Sarcosinates and detergents of similar function may be present, preferably as salts of alkali metals such as sodium, and then in partial substitution of the aforementioned synthetic organic detergents, but usually the species, if present, is Can be present in addition to detergents. Usually, the replenishment detergent is a sulfated or sulfonated product (usually as an IJium salt).
and contains long-chain (8 to 20 carbon atoms) straight-chain or fatty alkyl groups. In addition to any replenishing anionic synthetic organic detergents, nonionic and amphoteric substances may be present, similar to Neodol, sold by Sheet [F] Roux Chemical Company, which
A condensation product of ethylene oxide and a higher aliphatic alcohol, such as Neodol [F]26-6.5, which is a condensation product of a higher aliphatic alcohol having 12 to 16 carbon atoms and 6.5 moles of ethylene oxide. It is a condensation product of The various detergents and types of detergents mentioned can be found in the reference book Surfactant Nu Volume U (by Schwartz, Berry and Birch).

Interscience Publications, 1958)
, the description of which is incorporated herein by reference.

The builder salt combination of the present invention, which has been found to satisfactorily improve the detergent properties of mixtures of synthetic anionic organic detergents and create the desired pH in liquid detergents and in wash water, consists of tripolyphosphate (IJ) and sodium carbonate. It is a mixture. The builder salt may be used in the compositions of the present invention in an amount generally from about 5 to 25% by weight. In a preferred Pyrgoo salt combination, sodium tripolyphosphate is present in an amount of about 5 to 20%, preferably 10 to 16%, and carbonated) +) Rum is present in an amount of about 1 to 10%, preferably 6 to 7% by weight. The weight ratio of tripolyphosphate to carbonate in the present and preferred builder is from 2:1 to 6=1, most preferably from about 2=1 to 4:1. As used herein, the term alkali metal "carbonates" or "carbonates" is meant to include the alkali metal carbonates, monobicarbonates, and sesquicarbonates.

For best processability, ease of mixing, and good end useability, it is preferred that the sodium tripolyphosphate has a low content of phase II tripolyphosphate.

For example, the content of Phase I tripolyphosphate is usually less than 50% of the tripolyphosphate used. Although incompletely neutralized tripolyphosphate may be used in some cases, the phosphate used is usually pentasodium tripolyphosphate Na5P30□0
You can think that. Of course, in some cases, such as when potassium salts of other substances are present, ion interexchange in the aqueous medium may result in the presence of salts other than tripolyphosphate, but the present invention For this purpose, tripolyphosphoric acid as the pentasodium salt is usually added to the mixture to form the liquid detergent of the invention.
l) Consider that rum is the tripolyphosphate used.

Other preferred builder salts that may be used in place of or in addition to sodium tripolyphosphate and carbonate include the polyacetal carboxylates and sodium nitrilotriacetate (NTA) described herein.

Of course, various mixtures of the above-mentioned water-soluble builder salts can be utilized. Nevertheless, the tripolyphosphate-carbonate mixture described above has been found to be the most preferred, although other builders and mixtures thereof are also operable. Other builders that can be used as supplements in addition to the Pyrgoo moieties mentioned above are tetrasodium or tetrapotassium pyrophosphate, sodium bicarbonate, sodium citrate, sodium gluconate, sodium silicate, and sesquicarbonate. Contains other phosphates such as um.

Among the water-soluble virgoos that may be used are zeolites, usually in the form of crystalline hydrates, although amorphous zeolites are also useful.
Zeolite) There are zeolites like A.

Polyacetal carboxylates are generally described in US Pat. Nos. 4,144.226 and 4,315,092. US Pat. No. 4,146,495 describes detergent compositions containing polyacetal carboxylates as builders.

Polyacetal carboxylates useful as builders herein may be considered as those described in U.S. Pat. No. 4,144,226, which may be made by the methods described therein. (C
HO)n-R2 000M, where M is an alkali metal, ammonium, an alkyl group having 1 to 4 carbon atoms, and a 4-carbon group having 1 to 4 carbon atoms in the alkyl group. selected from the group consisting of alkylammonium and alkanolamine groups, where n is on average at least 4, and R1 and R2
is any commercially stable group that stabilizes the polymer against rapid degradation in alkaline solutions. Preferably, the polyacetal carboxylate is such that M is an alkali metal such as sodium and n is from 50 to 20.
0, R1 or a mixture thereof, R2 is 0CH2CH3CHH3, and n is on average from 20 to 100, most preferably 30
80. The calculated weight average molecular weight of this polymer is usually 2,000 to 20,000, preferably 3,500 to io, ooo, more preferably 5
．． 9.000 from ODD, for example about 8.000.

Particularly preferred sodium polyacetal carboxylates are supplied by Monsando Company and include Builder U
known as. It has a calculated average molecular weight of about 8, ODD and an active polymer content of about 80%.

Preferred polyacetal carboxylates are described above, but may be wholly or partially supplemented with other polyacetal carboxylates or related organic builder salts as described in the aforementioned patents for such compounds, methods of their preparation, and compositions in which they are used. Of course, they may be replaced. In addition, various patents, especially U.S. Patent No. 4,144,2
The chain-terminating groups described in 26 may be utilized as long as they have the desired stabilizing properties, which depolymerize the above-mentioned builder in an acidic medium and aid its biodegradation in the waste stream. , but maintains stability of the antilayer solution in more alkaline media.

The bentonite used here is a colloidal clay (aluminum silicate) containing montmorillonite. Swellable bentonites are generally characterized as sodium bentonites, ie, bentonites in which the predominant cation is sodium □.

Among the sodium bentonite clays, those from Wyoming (commonly referred to as Western or Wyoming bentonite) are particularly preferred.

Bentonite's swelling capacity is generally related to its fabric softening properties. In water, the swelling capacity of sodium bentonite is from 6 to 20 m1/f, preferably from 7 to 15 m1/f.
115' and its viscosity typically ranges from 5 to 30 centivoise, preferably from 8 to 30 centivoise at a concentration of 6% in water.

A preferred swellable bentonite is sold by Josiah Kaolin Company under the trademark Hygel. These materials are the same as mineral colloids and bentonites previously sold under the trademarks Thixodiel. They are selectively mined and concentrated bentonites, and those considered most useful are Thixodiel &, 2
．． Hygel A corresponding to 3 and 4, 2. It can be obtained as a set. These materials have a maximum free water content (before addition to the liquid medium) of 4% to 8% and a specific gravity of about 2.6. Bentonite is preferably US Standard Sieve 2
00 mesh, preferably at least 90% of the particles pass through the Tsuta 325 sieve, so the equivalent diameter of the bentonite can be considered to be less than 74 microns, more preferably less than about 44 microns. A representative chemical analysis of some bentonites useful in making the liquid detergents of the present invention shows that 5in2 from 64.8 to 76.0%
．． 14-18% At2Q3.16-2.7% M
g0.

1, '5 to 3.1% Ca0, 2.3 to 6.4%)
Fe203°0.8-2.8% Na2O, and 0
．． Indicates that 4 to 7.0% contains 20%.

Although Western bentonite is preferred, Italian bentonite or similar bentonites containing relatively small proportions of exchangeable-valent metals (sodium and potassium) may be treated with an alkaline substance such as sodium carbonate to produce such products. Other bentonites can also be used, such as those that can be made by increasing cation exchange capacity. The Na2O content of the bentonite is at least about 5%, preferably at least 1%, more preferably at least 2%, while the clay has good softening and dispersing properties in aqueous suspension. It should be such that it swells.

Preferred swellable bentonites of the type described above are available under the trade names of Lapiosa and Winckelmann, such as Lapiosa AGB.
and Winkelmann G-15.

Another bentonite that is particularly useful for white or very bright light in the liquid detergent compositions of the present invention is Boralite KB525 from American Colloids Company.
．． California bentonite, and Georgia kaolin GK129.

Contains Mexican bentonite.

The viscosity of the liquid detergent of the present invention is about i, o o o to 10
．． 000 centiboise, preferably 2000-sooo
products of other suitable viscosities, although in the centiboise range, may also be useful. At the above viscosities, the liquid detergent is pourable, stable, non-separable and homogeneous. A pH of the liquid detergent suspension, typically from 7 to 1,5, preferably from 8 to 10.5, appears to help maintain product stability and pourability.

The following examples illustrate, but do not limit, the invention. Unless otherwise specified, all parts are by weight and temperatures are in °C.

Example 1 Ingredients Percent Pentasodium Tripolyphosphate 1,0 Bentonite (Jossia Kaolin 129) 12.0 Sodium Carbonate 2.0 Sodium Sesquicarbonate 2.0 Linear Sodium Tridecylbenzenesulfonate 81 Neck AEO
S” 3.0 Carboxymethylcellulose (C:MC) 0.2 Fluorescent brightener 0.3 Fragrance
0.4 Enzyme (Esperase 8.OL)”
, 0 glycerin 6.0 borax 2.5 citric acid 2.0 (i
1 alkyl has 12 to 15 carbon atoms,
Sodium alkyl polyethoxy sulfate, where the polyethoxy is of 5 ethoxy groups.

"Esperase" sold by Novo Industries has +21 8.0KNPU/P.

The composition shown above was made by the following procedure: 40″
30.0 parts of F' demineralized water was added to a suitable mixing device, such as a vertical cylindrical tank equipped with an agitator.

Adjust the stirrer to medium agitation and add 2.0 parts anhydrous soda ash, 2 parts sodium sesquicarbonate, and 0.1 parts 7
A mixture consisting of 50% sodium carboxymethylcellulose was incorporated into water. The stirrer speed was then increased to maximum agitation and 1.0 parts of pentasodium tripolyphosphate and 12.0 parts of pentasodium tripolyphosphate were added.
Slowly add 1 part of bentonite to the mixing device.
It was added over a period of minutes to form an off-white suspension. The stirring speed was then reduced to the low/medium setting while 8.64 parts of high At (about 55%) LTBS slurry was added. Then 0.3 parts of Chinovar LMS-X (Ciba Geigy)
A fluorescent brightener/colorant solution consisting of 0.99 parts colorant and 4.02 parts demineralized water was added. Once a homogeneous blue-green solution was obtained, 0.4 part of perfume was added to the mixture under stirring. Next, the two-component slurry of 6.0 parts glycerin and 2.0 parts borax was slowly added. Stirring was continued until the mixture was homogeneous in appearance, then 2.0 parts of citric acid and 90 parts of water were added slowly. Agitation of the mixture was then reduced while 10.95 parts of a mixed AI detergent base consisting of 5.7 parts of LTBS slurry (approximately 50% AI) and AEO3 (approximately 27.5% AI) were added to the mixture. Next, add 0 parts of proteolytic enzyme while continuing to stir.
Add slowly until all materials were completely dispersed or dissolved.

Example 2 Enzyme-containing builder liquid detergent compositions A to G were formulated as shown in Table 1 below. The percentages shown indicate weight %. The arrows indicate the extent to which compositions B to G are equivalent to composition A.

The enzyme activity of Compositions A through G was tested after 7 days of storage at 110"F. The enzyme activity measured for each composition after this storage period is shown in Tables 2 and 6 as initial values. Compositions mA, B.C.

The various carboxylic acids and salts used in the formulations of D, E and G are shown in Table 2 along with the corresponding enzyme activity for each composition.

Table 2 Enzyme Stability Active Enzyme Percentage A (Reference Standard) ND*B (
(with glycerin) NDC (with borax) NDD (with glycerin and borax) 50 Composition E (with carboxylic oxide) (i) Succinic acid ND (2)
) Malonic acid (3) Malic acid (41 Tartaric acid 〃 (51 Aspartic acid (6) Citric acid (71 Sodium tartrate (8) Sodium citrate *ND = Not detectable (Residual activity below i0%) 11)
Succinic acid 70(2) Malonic acid 70(3) Malic acid 78(4) Tartaric acid
75f5+ Aspartic acid
90(6) Citric acid
74(7) Sodium tartrate 66(
8) Sodium Citrate 52 As is evident from Table 2, the control composition A and compositions B and C, each containing glycerin and borax individually as stabilizers.
showed almost no enzyme activity after storage for 7 days under 110°C.

Enzyme activities below 10% are not measured accurately, so they are designated as l''N DJ. Compositions containing glycerin/borax without the presence of carboxylic acid compounds are composition A,
Improved enzyme stability compared to B and C, but more than 50% of the enzyme was deactivated. Various compositions E, containing various carboxylic acid compounds as indicated, did not exhibit any enzyme stability compared to composition A. However, Composition G formulated according to the present invention shows an unexpected and synergistic improvement in enzyme stability, which is due to the use of glycerin/borax in combination with carboxylic acid in the liquid detergent composition of the present invention. This will be achieved. Almost every one of the 17 compositions corresponding to composition G had an enzyme activity similar to that of composition D (
(containing glycerin and borax).

Composition D (glycerin/borax) and various compositions F (borax/
A comparison of the enzymatic activities obtained with carboxylic acid compounds) and G (formulated according to the invention) is shown in Table 6.

Table 6 D (Glycerin/borax) 45 5
0F (borax/malonic acid 15 45
G (glycerin, 'ldl? low/malonic acid) 91
70F (borax/aspartic acid)
39 72G (Glycerin/borax/asparagine e) 84 90F (borax/citric acid)
ND 42G (Glycerin/borax/citric acid) 6274 As shown in Table 6, various compositions G containing the ternary stabilizer system according to the invention are synergistic in enzyme activity compared to compositions R and F formulated according to conventional methods. Provided improvements.

Claims (1)

[Scope of Claims] 1. A stabilized fabric softening enzyme-containing builder liquid detergent composition comprising: (a) about 5 to 20% by weight of anionic, nonionic and amphoteric detergent compositions; one or more surfactant compounds selected from the group consisting of detergent compounds; (b) about 5 to 30% by weight of alkali metal tripolyphosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetals; one or more builder salts selected from the group consisting of carboxylates; (c) about 5 to 20% by weight swellable bentonite clay; (d) effective amounts of alkaline proteolytic enzymes and alpha-amylase enzymes. (e) an enzyme or enzyme mixture selected from the group consisting of: (i) from about 1% to 1%, based on the weight of the detergent composition;
0% glycerin; (ii) about 1 to 8% of a boron compound selected from the group consisting of boric acid, boron oxide, and alkali metal borates; and about 0.5 to 8% of a carbon atom number of 1 to 8%; an enzyme stabilizing system comprising: a carboxylic acid compound selected from the group consisting of eight mono-, di-, and/or polycarboxylic acids and water-soluble salts thereof; and (f) water and optionally perfumes and other auxiliaries. a composition consisting of; a residual weight consisting of; 2. A liquid detergent composition comprising: (a) about 5 to 15% of an alkali metal alkylbenzene sulfonate having 12 to 15 carbon atoms; (b) about 0.5 to 5% of an alkyl Groups 10 to 18
carbon atoms and the polyethoxy is of 3 to 11 ethylene oxide groups, wherein the weight ratio of (a) to (b) is from about 2:1 to about 6 : 1, (c) about 5 to 20% sodium tripolyphosphate, (d
) about 1 to 10% sodium carbonate, sodium bicarbonate, or mixtures thereof, with a weight ratio of (c) to (d) of about 2:1 to about 6:1; (e) about 10%; (f) an effective amount of the enzyme or enzyme mixture described above; (g) by weight of the detergent composition: (i) about 1 to 5% glycerin; (ii) about 1 to 5%. and (iii) about 0.5 to 4% of the above carboxylic acid compound;
and (h) a balance weight consisting of water and optionally small amounts of auxiliaries. 3. The above alkali metal alkylbenzene sulfonate is linear sodium tridecylbenzene sulfonate, and the above alkali metal alkyl polyethoxy sulfate has an alkali metal of sodium and an alkyl group having 12 to 15 carbon atoms. 3. A liquid detergent composition according to claim 2, wherein the polyethoxy contained is of about 3 ethylene oxide groups. 4. The liquid detergent composition of claim 3, wherein the ratio of tridecylbenzene sulfonate to polyethoxy sulfate is from about 2:1 to about 4:1. 5. The liquid detergent composition according to claim 2, wherein the boron compound is an alkali metal borate. 6. The liquid detergent composition according to claim 5, wherein the borate is borax. 3. The liquid detergent composition of claim 2, comprising 7,8 to 16% sodium tripolyphosphate and about 2 to 6% sodium carbonate, sodium bicarbonate or mixtures thereof. 8. The liquid detergent composition according to claim 2, wherein the carboxylic acid compound is aspartic acid or a water-soluble salt thereof. 9. The liquid detergent composition according to claim 2, wherein the carboxylic acid compound is tartaric acid or a water-soluble salt thereof. 10. The liquid detergent according to claim 2, wherein the carboxylic acid compound is citric acid or a water-soluble salt thereof. 11. The liquid detergent composition according to claim 2, wherein the carboxylic acid compound is malonic acid or a water-soluble salt thereof. 12. The liquid detergent composition according to claim 2, wherein the carboxylic acid compound is malic acid or a water-soluble salt thereof. 16. A method of laundering comprising contacting a stained and/or contaminated fabric to be laundered with a stabilized enzyme-containing builder liquid detergent composition, the composition comprising: (a) about 5% by weight; (b) about 5 to 30% by weight of an alkali metal triplicate; (b) about 5 to 30% by weight of an alkali metal triplicate; one or more builder salts selected from the group consisting of phosphates, alkali metal carbonates, alkali metal nitrilotriacetates, and polyacetal carboxylates; (c) about 5 to 20% by weight swellable bentonite clay; (d) an effective amount of an enzyme or enzyme mixture selected from the group consisting of alkaline proteolytic enzymes and alpha-amylase enzymes; (e) based on the weight of the detergent composition: (i) about 1% to 1%;
(ii) about 1 to 8% of a boron compound selected from the group consisting of boric acid, borax and alkali metal borates, and (iii) about 0.5 to 8% of the number of carbon atoms. an enzyme stabilizing system comprising a carboxylic acid compound selected from the group consisting of 1 to 8 mono-, di-, and/or polycarboxylic acids and water-soluble salts thereof; and (f) water and optionally perfume and other ingredients. A washing method comprising: a residual weight consisting of an auxiliary agent; 14. The liquid detergent composition comprises (a) about 5 to 15% of an alkali metal alkylbensulfonate whose alkyl group has 12 to 15 carbon atoms; (b) about 0.5 to 5% of an alkyl group; Groups 10 to 18
carbon atoms and the polyethoxy is of 3 to 11 ethylene oxide groups, wherein the weight ratio of (a) to (b) is from about 2:1 to about 6 :1; (c) about 5 to 20% sodium tripolyphosphate; (d
) about 1 to 10% of sodium carbonate, sodium bicarbonate, or mixtures thereof, with a weight ratio of (c) to (d) of about 2:1 to about 6:1; (e) about 10 to 15% sodium bentonite; (f) an effective amount of an enzyme or enzyme mixture as described above; (g) based on the weight of the detergent composition: (i) about 1 to 5% glycerin; (ii) about 1 an enzyme stabilizing system comprising from 5% to 5% alkali metal borate, and (iii) from about 0.5 to 4% of the carboxylic acid compound; and (h) the remainder consisting of water and optionally small amounts of auxiliaries. 14. The method of claim 13, comprising: weight. 15. The alkali metal alkylbenzene sulfonate is linear sodium tridecylbenzene sulfonate, the alkali metal alkyl polyethoxy sulfate has sodium as the alkali metal, and the alkyl group is 12 to 15.
15. The method of claim 14, wherein the polyethoxy contains about 3 carbon atoms and the polyethoxy is of about 3 ethylene oxide groups. 16. The method of claim 15, wherein the tridecylbenzene sulfonate to polyethoxy sulfate is about 2:1 to about 4:1. 17. The method according to claim 14, wherein the boron compound is borax. 18. The method of claim 14, wherein the liquid detergent composition comprises about 8 to 16% sodium tripolyphosphate and about 2 to 6% sodium carbonate, sodium bicarbonate, or mixtures thereof. 19. The method according to claim 14, wherein the carboxylic acid compound is aspartic acid or a water-soluble salt thereof. 20. The method according to claim 14, wherein the carboxylic acid compound is citric acid or a water-soluble salt thereof. 21. The method according to claim 14, wherein the carboxylic acid compound is malic acid or a water-soluble salt thereof. 22. The method according to claim 14, wherein the carboxylic acid compound is malonic acid or a water-soluble salt thereof.