US3697451A

US3697451A - Stable enzyme containing liquid detergent

Info

Publication number: US3697451A
Application number: US788628A
Authority: US
Inventors: Marvin L Mausner; Arnold Wiesenfeld
Original assignee: Witco Chemical Corp
Current assignee: Witco Corp
Priority date: 1969-01-02
Filing date: 1969-01-02
Publication date: 1972-10-10
Anticipated expiration: 1989-10-10
Also published as: NL165497C; DE2022064A1; CA921846A; DE2022064B2; FR2087745A5; NL165497B; DE2022064C3; BE751007A; NL7006468A; GB1293613A

Abstract

STABLE, LIQUID, CONCENTRATED DETERGENT COMPOSITION CONTAINING (A) FROM ABOUT 0.001 TO 5% BY WEIGHT OF ACTIVE ENZYME SELECTED FROM THE GROUP CONSISTING OF PROTEOLYTIC, AMYLOLTIC AND LIPOLYTIC ENZYMES AND MIXTURES OF SAID ENZYMES; AT LEAST ABOUT 88% BY WEIGHT OF A POLYFUNCTIONAL ESSENTIALLY 100% ACTIVE STABLE LIQUID DETERGENT, PARTICULARLY ONE COMPOSED OF A COMBINATIONL OF (I) AN ETHANOLAMINE SALT OF ALKYL BENZENE AND/OR ALKYL TOLUENE SULFONIC ACID, (II) AN EHOXYLATED OR PROPOXYALTED ETHER OF AN ALIPHATIC ALCOHOL AND/OR OF AN ALKYL PHENOL, AND (III) A FATTY ACID ALKANOLAMIDE.

Description

3,697,451" Patented Oct. 10, 1972 "United States Patent Office 3,697,451 STABLE ENZYME CONTAINING LIQUID DETERGENT Marvin L. Mausner, Teaneck, and Arnold Wiesenfeld, North Haledon, N.J., assignors to Witco Chemical Corporation, New York, N.Y. No Drawing. Filed Jan. 2, 1969, Ser. No. 788,628 Int. Cl. Clld 1/83 US. Cl. 252545 10 Claims ABSTRACT OF THE DISCLOSURE Stable, liquid, concentrated detergent compositions containing (A) from about 0.001 to 5% by weight of active enzyme selected from the group consisting of proteolytic, amylolytic and lipolytic enzymes and mixtures of said enzymes; at least about 88% by weight of a polyfunctional essentially 100% active stable liquid detergent, particularly one composed of a combination of (i) an ethanolamine salt of alkyl benzene and/or alkyl toluene sulfonic acid, (ii) an ethoxylated or propoxylated ether of an aliphatic alcohol and/or of an alkyl phenol, and (iii) a fatty acid alkanolamide.

This invention relates to novel enzyme-containing concentrated liquid detergent compositions marked by excellent long term stability and homogeneity.

In general, it has long been recognized that the use of enzymes in cleansing compositions offers certain distinct advantages. In US. Pat. No. 1,882,279, a soap-diastase composition with improved cleaning ability is disclosed. In East German Pats. Nos. 14,296; 16,501 and 20,291 there are disclosed combinations of enzymes with various inorganic surface active agents such as polyphosphates, pyrophosphates, sulfates and the like having improved detergent qualities.

Enzymes are of particular utility in laundry products where they are incorporated in soaking and prewashing compositions so as to take advantage of their ability to break down and hydrolyze certain soils and stains, especially those Which are derived from organic matters. Enzymes suitable for such purposes have heretofore been employed in dry powder laundry compositions, generally as mechanical mixtures of a pulverulent or finely divided enzyme powder with other granular or pulverulent substances.

Liquid detergent compositions containing enzymes have not heretofore been fully satisfactory because of the compatibility and stability problems involved. Furthermore, the large water content of the usual liquid detergent compositions is inimical to enzymes which might be incorporated therein because degradation of the enzymes results. A stable and compatible liquid detergent composition containing active enzymes is desirable from the point of view of handling, storage and application to soiled clothing and the like. When used as a pre-soak, for example, such a composition can be applied to the fabric full strength Without the need for first diluting the liquid with water. The treated fabric is then Soaked in Water. In addition, an enzyme-containing liquid detergent composition can be packaged for spray application in aerosol or manual spray devices.

In accordance with the present invention, there have been developed novel stable, concentrated, liquid detergent compositions which are highly useful and effective for the removal of various soils and stains from fabrics and the like. Such compositions comprise or consist essentially of (A) from about 0.001 to 5% of active enzymes selected from the group consisting of proteolytic, amylolytic and lipolytic enzymes and mixtures of two or more of said enzymes, (B) at least about 88% of a polyfunctional essentially 100% active stable liquid detergent composition, and (C) from essentially zero up to about 7% of water, said percentages being by weight.

The enzymes suitable for use in the liquid detergent compositions of the present invention generally comprise proteolytic, amylolytic and lipolytic enzymes which are active at a pH between about 3 and 10. These enzymes are generally classified as hydrolyzing enzymes. In the preferred liquid detergent compositions of the present invention, enzyme of all three types are utilized since these enzymes function dilferently in that they attack different types of stains. Proteolytic enzymes, as is known, break down protein-type stains caused by blood, eggs, infants formulae, grass and the like. Amylolytic enzymes are specific for starches and sugars as in the case of gravy, chocolate, ice cream and pudding stains. Lipolytic enzymes facilitate the removal of fat and grease stains such as are caused by bacon grease, butter, cooking oils and body oils.

Examples of suitable proteolytic enzymes for use in the liquid detergent composition of the present invention are pepsin, rennin, trypsin, chymotrypsins, elastase, papain, carboxypeptidase, keratinase and aminopeptidase. These enzymes degrade proteins and their degradation products, polypeptides, peptides and other substances by hydrolyzing --CO-NH linkages.

Amylolytic enzymes suitable for use in the liquid detergent compositions hereof are, for example, rat-amylase, fl-amylase, glucoamylase, amylo-1,6-a-glucosidase and oligo-l,6-a-glucosidase.

Lipase or lipolytic enzymes are known to catalyze the hydrolysis of fats and fatty acid esters, the end product of the degradation being glycerine or an alcohol and a fatty acid. Commercial lipases are generally derived from the pancreatic extracts of animals. Examples of lipolytic enzymes suitable for use in the liquid detergent compositions of the present invention are gastric lipase, pancreatic lipase, plant lipases and bacterial and fungal lipases. Lipolytic enzymes generally exhibit optimum activity in a pH range of 4 to 7. In this connection, it may be pointed out that the preferred polyfunctional essentially 100% active liquid detergent compositions of the present invention have relatively lower pH values than do conventional dry powder detergent formulations which commonly contain high proportions of quite alkaline polyphosphates. It may also be noted that it has heretofore been considered to be diflicult and, in at least certain instances, impractical effectively and satisfactorily to incorporate lipolytic enzymes into a detergent composition.

The enzymes whose utilization in the liquid detergent compositions of the present invention is particularly satisfactory are those which are active in a pH range of about 4 to 9 and at a temperature in the range of about 25 C. to C. and which are soluble in or miscible with water. Specific examples of such and other commercial enzymes or enzymatic products are shown in Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd ed., (1965), vol. 8, pp. 182188 (John Wiley and Sons, Inc., New York, N.Y.).

It may be noted, and as is well known in the art, that the commercially available enzymes or enzymatic prodnets are rarely sold in a pure or essentially pure state but are generally available in the form of a blend of pure enzyme and an inert carrier. Commercial enzyme compositions may contain between 2% and by weight of active enzyme blended with a vehicle such as calcium sulfate or sodium sulfate and sodium chloride. The great majority of enzymatic products on the market today contain from 6% to 10% by weight of pure or active enzymes. The term active enzyme is used herein to express the quantity of pure enzyme, regardless of the total weight of a commercial product, used in the compositions of the present invention.

The quantity of active enzymes utilized in the liquid detergent compositions in accordance with the present invention, as pointed out above, may vary from about 0.001 to by weight. Preferably the amount of active enzyme is from about 0.1 to 0.2%, based upon the weight of the finished liquid detergent composition. The amount of water present will generally be a function of the quantity of enzyme used. The amount of water used is advantageously only the minimum which is necessary to dissolve the enzyme and effectively carry it into the liquid detergent vehicle, and generally this will be an amount necessary to prepare at least about a 30% by weight solution or dispersion of the total quantity of commercial enzymatic product. The total amount of water in the final enzyme-containing liquid detergent composition should not exceed about 7% by weight of said composition.

The liquid essentially 100% active detergent compositions suitable for use in the practice of the present invention may be any stable, liquid, polyfunctional essentially 100% active detergent composition. Especially satisfactory are essentially anhydrous liquid polyfunctional organic detergent compositions of the present invention containing as essentialingredients, in the ranges of proportions set forth hereafter, (1) ethanolamine (i.e., monoethanolamine, diethanolamine and triethanolamine or mixtures of two or more thereof) salts of alkyl benzene sulfonic acids or alkyl toluene sulfonic acids, particularly the diethanolamine or triethanolamine salts of said sulfonic acids (2) certain ethanolamides or isopropanolamides, and (3) certain water-soluble nonionic organic detergents which are normally liquid or, in other words, liquid at usual room temperatures.

The alkyl benzene sulfonic acids and the alkyl toluene sulfonic acids, which are utilized in the form of their ethanolamine salts as stated above, are those in which the alkyl radical, which may be linear or branched chain, contains predominately from 8 to 16 carbon atoms and, better still, from 11 to 15 carbon atoms. Especially satisfactory are dodecyl benzene sulfonic acid and tridecyl benzene sulfonic acid, as well as mixtures thereof or mixtures in which one or the other or both predominate, in which the dodecyl and tridecyl radicals are essentially normal or straight chain. The alkyl benzene or alkyl toluene sulfonic acids are wellknown in the art and are conventionally made by alkylating benzene or toluene with normal or straight chain chloroparaifins, polypropylenes, or olefins, although other sources of alkyl radicals can, of course, be utilized. The ethanolamine salts of the aforesaid sulfonic acids are formed and incorporated in the manner described below.

The normally liquid water-soluble non-ionic surfactants which are utilized in the aforementioned liquid detergent compositions serve as primary surfactants as well as liquid carriers. They are, per se, well known and are exemplified mainly by ethylene oxide adducts or polyethenoxy ethers of (i) aliphatic monohydric alcohols, comprising straight chain and branched chain saturated and unsaturated alcohols containing at least 8 carbon atoms and generally up to 18 carbon atoms, particularly branched chain and fatty alcohols containing from 10 to 14 carbon atoms or (ii) alkyl phenols, particularly monoor di-alkyl phenols, in which the alkyl radicals contain a total of from 5 to 18 carbon atoms, especially mono-alkyl phenols in which the alkyl radical contains from 8 to 12 carbon atoms. The mol ratio of the ethylene oxide to the aforesaid alcohols or alkyl phenols in the adducts is variable within quite wide limits, generally being at least 4 to 20 or more mols of ethylene oxide to 1 mol of said alcohols or alkyl phenols, especially 6 to 10 mols of ethylene oxide to 1 of said alcohols or alkyl phenols. Propylene oxide can be substituted to some extent for the ethylene oxide or, in certain limited cases can replace ethylene oxide, or both ethylene oxide and propylene oxide can be used to produce the adducts, subject, however, to the adduct being normally liquid and water-soluble. In general, the especially desirable normally liquid non-ionic organic surfactants utilized will be the 6 to 10 mol ethylene oxide adducts of (i) straight chain or branched chain aliphatic monohydric alcohols or (ii) mono-alkyl phenols in which the alkyl radical contains from 8 to 12 carbon atoms.

The ethanolamides and/or isopropanolamides which are utilized in the aforementioned liquid detergent compositions are the fatty acid monoethanolamides, diethanolamides and isopropanolamides in which the fatty acid acyl radical contains from 10 to 16 carbon atoms. Said amides should be either normally liquid or have melting points not higher than about 60 C. Especially satisfactory are the diethanolamides derived from coconut oil mixed fatty acids or special fractions containing, for instance, very predominately C or C fatty acids, and wherein the mol ratio of the diethanolamine to the higher fatty acid is about 1:1.

The proportions of the ingredients, in terms of weight percent, comprising the foregoing liquid detergent compositions which are combined with the enzymes to produce the enzyme-containing liquid detergent compositions of the present invention are (A) from 30 to better still 45 to 75%, of the aforementioned ethanolamine salts of the alkyl benzeneor alkyl toluene-sulfonic acids, (B) from 5 to 35%, better still 15 to 30%, of the aforementioned non-ionic normally liquid, water-soluble surfactants, and (C) from 5 to 35%, better still 12 to 25%, of the aforementioned fatty acid amides of monoethanolamine, diethanolamine or isopropanolamine. Particularly desirable are those liquid detergent compositions wherein the aforesaid ethanolamine salts of the alkyl benzeneor alkyl toluene-sulfonic acids constitute from 52 to 64%, the aforesaid non-ionic surfactant constitutes from 22 to 30%, and the aforesaid fatty acid monoor diethanolamides or isopropanolamides constitute from 14 to 18% of the compositions.

In the preparation of the foregoing polyfunctional essentially active stable liquid detergent compositions, it is particularly advantageous first to form a substantially homogeneous solution of the non-ionic normally liquid water-soluble surfactant with an ethanolamine and then gradually add thereto, under conditions of agitation, the alkyl benzene sulfonic acid and/ or alkyl toluene sulfonic acid in an amount essentially to be neutralized by said ethanolamine thereby to form the ethanolamine salt of said sulfonic acid, the temperature of the mixture being controlled so as not to exceed approximately 50 C., and then add the ethanolamide and/or isopropanolamide, under conditions of agitation, until a clear, homogeneous liquid is obtained. An alternative procedure is first to form a mixture of the non-ionic surfactant and the sulfonic acid and then gradually add thereto the ethanolamine under conditions of agitation. Still other procedures can be used but the non-ionic surfactant must comprise the vehicle in which in situ formation of the ethanolamine salt of the sulfonic acid is effected. Thus, for instance, stable compositions cannot be formed if the ethanolamine salt of the sulfonic acid is sought to be formed in situ in the ethanolamide and/or isopropanolarnide per se. As indicated, non-ionic surfactant must be present during the in situ formation of the ethanolamine salt of the sulfonic acid.

While the foregoing type of essentially 100% active polyfunctional liquid detergent composition is especially suitable for use in the production of the enzyme-containing liquid detergent compositions of the present invention, other types can be employed. Thus, an essentially 100% active polyfunctional liquid detergent composition can be prepared by combining two of the aforesaid components in approximately equal parts by weight. Thus, a mixture of about 56% coconut oil diethanolamide and about 44% of a 6 mol ethylene oxide adduct of a mixture of C to C fatty alcohols; or a mixture of 50% diethanolamine dodecylbenzene sulfonate and 50% ethoxylated C to C aliphatic alcohol (6 to 8 mol ethylene oxide adduct), said sulfonate being formed in situ by addition of the dodecylbenzene sulfonic acid to the ethoxylated alcohol-diethanolamine mixture, can be utilized.

The stable, enzyme-containing liquid detergent com positions of the present invention are advantageously prepared by first admixing with or dissolving the enzyme or enzyme mixture in water so as to prepare an approximately 10 to 60% by weight solution or dispersion. Preferably at least about a 30% solution or dispersion should be prepared, but, of course, the solution or dispersion is desirably as concentrated as is reasonably possible. This aqueous enzyme solution or dispersion is then thoroughly intermixed with the liquid, essentially 100% active, polyfunctional detergent component as described above to form a stable homogeneous blend. No special equipment or mixing techniques are required and the preparation is easily carried out at room temperature.

In preparing the aqueous enzyme solution or dispersion, it is preferable to use water having a slight degree of hardness because, as is known in the enzyme art, water causes self-degeneration of enzymes and hard water, i.e. water containing calcium and magnesium ions, inhibits this breakdown. Soft water usually contains up to about 85 p.p.m. calcium or magnesium; very hard water is classified as that having a degree of hardness in excess of 510 p.p.m. While soft water can be used in preparing the enzyme solutions or dispersions, itis desirable to utilize water having a degree of hardness of about 150 p.p.m. in order to inhibit enzyme breakdown during the course of manufacture of the finished enzyme-containing liquid detergent compositions. Once the enzyme solution or dispersion and liquid detergent are combined, enzyme effectiveness remains substantially undiminished over long periods of time.

The enzyme-containing liquid detergent compositions of the present invention are particularly useful as a presoak or pre-wash cleansing composition for clothing containing stains not usually removed by conventional detergents, such as those due to proteins, starches, sugars and fats. The enzyme-containing liquid detergent compositions of the present invention may be directly applied to the fabric, which is then water-soaked, without the need for first preparing an aqueous solution as is required in the case with dry powder products. The enzyme-containing liquid detergent compositions are also useful in dishwashing for the removal of organic-based stains, especially burnt food stains on dishes and cookware.

Another advantage of the enzyme-containing liquid detergent compositions of the present invention is that they may be applied as a spray using aerosol or manual spray devices. The essential qualities of stability and homogeneity are retained when the said compositions are combined with a viscosity-lowering diluent and/ or an aerosol propellant. Suitable diluents include the lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol and the like as well as ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether and other lower molecular weight monoand dialkyl ethers of ethylene glycol. Other diluents include polyhydric alcohols such as ethyleneglycol and propylene glycol. Generally speaking, the diluent may be aliphatic lower molecular weight monohydric and polyhydric alcohols and ether alcohols containing from 1 to 8 carbon atoms. Addition of a small proportion of said diluent results in a product especially suited for use with a manual spray device.

Suitable propellants include the commonly used fluorinated hydrocarbons having a vapor pressure between about and 120 p.s.i.g. at 70 F. Examples are trichloro monofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, monochlorodifluoromethane, dichloromethane, 1 chloro 1,1 difiuoroethane, 1,1-difluoroethane, chloroethane, 1,2 dichloro 1,1,2,2-tetrafluoroethane, octafiuorocyclobutane, decafluorobutane and the like and mixtures of propellants. Suitable but less preferable are lower molecular weight hydrocarbons such as propane, isobutane and n-butane and lower molecular weight aliphatic ethers. Especially suitable and preferred is an aerosol system prepared by adding ethyl alcohol diluent and dichlorodifluoromethane propellant.

The ranges of proportions for said diluents and propellants, based upon the weight of the overall composition, will generally range from about 5% to 15% diluent and from about 5% to 15% propellant. Preferably, the aerosol composition will contain about 9% diluent and about 10% propellant. It has been found that this latter formulation, when applied in the form of an aerosol spray, results in a particularly soft foam that breaks down to give a good fabric-penetrating liquid.

The following examples include illustrative or particularly preferred embodiments of the present invention, but they are not to be construed as in any way limitative of the invention since numerous other embodiments can readily be evolved in the light of the guiding principles and teachings provided herein. All parts recited are by weight.

EXAMPLE 1 To 18 parts of a 6 mol ethylene oxide adduct of a mixture of C to C fatty alcohols was added 20 parts of diethanolamine. 40 parts of dodecyl benzene sulfonic acid was slowly added, under conditions of agitation, the temperature of the reactants and the reaction mixture being maintained below 50 C. and, better still, between about 20 and 30 C. Then 22 parts of coconut oil fatty acid diethanolamide was added with stirring until a clear, homogeneous liquid was obtained. To 99 parts of this liquid polyfunctional essentially 100% active detergent there Was added, with stirring, an aqueous solution of enzymes composed of 0.25 parts of proteolytic and amylolyt-ic enzymes (.a mixture sold under the designation Enzyme A by Monsanto Chemical Co.) and 0.15 parts of lipolytic enzyme (sold under the designation Lipase A by Enzyme Development Co.) and 0.75 parts of p.p.m. hard water. The blend was stored for 4 weeks and no separation was observed. Evaluation data are presented in Example 5.

EXAMPLE 2 Following the procedure of Example 1, 1.5 parts of lipolytic enzyme (sold under the designation Lipase B by Rohm & Haas Co.), 2.5 parts of proteolytic and amylolytic enzymes (sold under the designation Enzyme AP by Monsanto Chemical Co.), 7.5 parts of 150 p.p.m. hard water and 988.5 parts of the essentially100% active liquid detergent of Example 1 were admixed to form a homogeneous composition. It exhibited excellent stability.

EXAMPLE 3 Following the procedure of Example 1, 2.5 parts of Enzyme AP, 7.5 parts of 150 p.p.m. hard Water and 990 parts of the essentially 100% active liquid detergent of Example 1 were admixed to form a homogeneous composition.

EXAMPLE 4 Following the procedure of Example 1, 3 parts of lipolytic enzyme (a pancreatic extract sold under the designation Lipase 250 by Miles Chemical Co.), 2.5 parts of Monsanto Enzyme AP, 10 parts of 150 p.p.m. hard water and 984.5 parts of the liquid detergent of Example 1 were admixed. No separation was observed over a 3 week period.

EXAMPLE 5 Evaluation of the enzyme-containing pro-soak compositions prepared according to Examples 1, 2 and 4 was carried out by treating standard cotton test fabrics (sold by Test Fabrics, Inc.) which had been stained with (a) inkblood-milk, (b) cocoa, (c) hemoglobin and (d) a grease stain composed of olive oil and carbon black. For comparison purposes, a test fabric was pre-soaked with the liquid polyfunctional detergent component of Example 1 to which no enzyme had been added. This fabric was also detergent washed in order to further make comparison with fabrics which were enzyme treated and then deter ent washed.

In all pre-soaking procedures, a sample of enzymecontaining liquid was rubbed into the stained fabric which was then soaked in water for 1 hour at 50 C., and then detergent washed with a commercially available alkyl benzene sulfonate laundry powder for a period of 15 minutes, rinsed and dried.

The degree of stain removal was measured by utilization of the reflectance scale of a Hunter Colorimeter. With this scale, as the reflectance reading approaches 100, the color being measured approaches a pure white.

In the table set forth below, identically stained test fabrics were treated with test compositions A through D as described below. As can be readily seen, the degree of stain removal greatly exceeds that obtained by pre-soaking without enzymes and then detergent washing.

Test compositions and procedures listed in Table 1 (A)--The fabric was pre-soaked with the liquid detergent component of Example 1 to which no enzyme was added and then detergent washed.

(B)The fabric was pre-soaked with the enzyme composition of 'Example 1 and then detergent washed.

(C)The fabric was pro-soaked with the enzyme composition of Example 2 and detergent washed.

(B)The fabric was pre-soaked with the enzyme com- The following formulations were prepared and exhibited excellent qualities when used in an aerosol container, and also retaining stability and homogeneity.

Grams Component A B C Monsanto Enzyme AP" 0.25 0.25 0.25 Miles Lipase 250 0. 80 0. 30 0.30 100% active liquid detergent component;

of Example 1 79. 45 79. 45 89. 45 150 p.p.m. hard water 1.0 1.0 1.0 Ethyl alcohol 9. 4. 0 1.6 Butyl Cellosolve 7. 2 Methyl Cellosolve b 4. 7 Diehloro difiuorometh ane. 13. 2 13. 2 13. 2

Total 103. 20 102. 90 113. 00

I Trademark for ethylene glycol monobutyl ether. b Trademark for ethylene glycol monomethyl ether.

The following are further examples of polyfunctional essentially 100% active stable liquid detergent compositions which can be admixed with the enzymes to produce the enzyme-containing liquid detergent compositions of the present invention. .I

EXAMPLE 7 To 26 parts of the condensation product or adduct of 6 mols of ethylene oxide and 1 mol of a linear fatty alcohol having mainly 10 to 14 carbon atoms there was added 20 parts of diethanolamine. Then 40 parts of dodecyl benzene sulfonic acid (88% minimum activity) was slowly added, under conditions of agitation, the temperature of the reactants and the reaction mixture being maintained below 50 C. and, better still, between about 20 and 30 C. The aforementioned amount of diethanolamine is the stoichiometric quantity required to neutralize the dodecyl benzene sulfonic acid. When the neutralization was complete, 14 parts of a superamide (made from 1 mol of coconut oil fatty acids and 1 mol of diethanolamine) was added, under conditions of agitation, until a clear, homogeneous liquid was obtained.

EXAMPLE 8 Parts Diethanolamine 20 Linear dodecyl benzene sulfonic acid (88% active) 40 6-mol ethylene oxide adduct of C C fatty alcohols 18 Coconut oilfatty acid diethanolamide (1:1 mol ratio) 22 EXAMPLE 9 Triethanolamine 25 Linear dodecyl benzene sulfonic acid (88% actlve) 35 9-mol ethylene oxide adduct of octyl phenol 22 Laurie acid diethanolamide (1:1 mol ratio) 18 EXAMPLE 10 Diethanolamine 14 Alkyl benzene sulfonic acid (98% active-branched chain alkyl radical containing predominately 11 carbon atoms) 4l 6-mo1 ethylene oxide adduct of 12-car-bon atom secondary alcohol 30 Coconut oil fatty acid diethanolamide (1:1 mol ratio) 15 EXAMPLE l1 Diethanolamine 20 Branched chain dodecyl benzene sulfonic acid (88% active) 30 Branched chain mixed C -C alkyl benzene sulfonie acids (88% active) 10 6-mol ethylene oxide adduct of C fatty alcohol 26 Coconut oil fatty acid diethanolamide (1:1 mol ratio) 14 EXAMPLE 12 Parts Diethanolamine 20 Linear tridecyl benzene sulfonic acid 40 8-mol ethylene oxide adduct of nonyl phenol 24 Laurie acid diethanolamide (1:1 mol ratio) l6 EXAMPLE 13 Diethanolamine 20 Linear dodecyl benzene sulfonic acid (88% active) 40 7-mol ethylene oxide adduct of n-dodecyl alcohol 25 Coconut oil fatty acid diethanolamide (1:1.1) 15 The compositions of Examples 8-13 are made in the manner described in Example 7.

In the preparation of polyfunctional essentially 100% active stable liquid detergent composition component of the enzyme-containing liquid detergent compositions of the present invention, it is advisable, for optimum results, that no water be deliberately added during such preparation. However, some water may enter into the liquid detergent composition component by reason of its presence in small proportions in one or more of the ingredients utilized in the preparation of said component. In any event, the method of preparation and the selection of ingredients should so be controlled that the water content of the liquid detergent composition component does not exceed 2% of the total weight of said liquid detergent composition component. The water content of up to about 7% in the finished enzyme-containing liquid detergent compositions of the present invention comprises mainly the water present in the enzyme solution or dispersion which is blended into or with the essentially 100% active polyfunctional liquid detergent component.

What is claimed is:

1. A stable enzyme-containing liquid detergent composition consisting essentially of (a) from about 0.001 to by weight of active enzyme selected from the group consisting of proteolytic, amylolytic and lipolytic enzymes and mixtures of at least two of said enzymes; (b) at least about 88% by weight of a polyfunctional essentially 100% active stable liquid detergent composition which consists essentially of (I) 30 to 90% by weight of an ethanolamine salt of a member selected from the group consisting of alkylbenzene and alkyl toluene sulfonic acids in which the alkyl radical contains from 8 to 18 carbon atoms, (II) 5 to 35% by weight of a nonionic, normally liquid water soluble surfactant selected from the group consisting of ethoxylated and propoxylated ethers of aliphatic monohydric alcohols containing from 8 to 18 carbon atoms and alkyl phenols in which the alkyl radicals are 1 to 2 in number and contain a total of from 5 to 18 carbon atoms and (HI) 5 to 35% by weight fatty acid amides of a member selected from the group consisting of monoethanolamine, diethanolamine and isopropanolamine in which the fatty acid acyl radical contains from to 16 carbon atoms, said ethanolamine salt component of said (b) ingredient being formed by in situ neutralization in the presence of said nonionic surfactant component, and (0) up to about 7% by weight of water.

2. A stable enzyme-containing liquid detergent composition according to claim 1, wherein the alkyl radical of said -I ingredient contains from 11 to carbon atoms, and wherein the II ingredient is a 6 to 10 mol ethylene oxide adduct of a member selected from the group consisting of (i) a fatty alcohol containing from 10- to 14 carbon atoms and (ii) an alkyl phenol in which the number of alkyl radicals is 1 to 2 and the total number of carbon atoms in said alkyl radicals is between 8 and 12.

3. A stable enzyme-containing liquid detergent composition according to claim 2, in which the I ingredient constitutes 45 to 75%, the II ingredient constitutes 15 to 30%, and the III ingredient constitutes 12 to 25%.

4. A stable enzyme-containing liquid detergent composition according to claim 1, in which the I ingredient is an ethanolamine salt of a member selected from the group consisting of dodecyland tri-decyl benzene sulfonic acid, the II ingredient is a 6 to 10 mol ethylene oxide adduct of a member selected from the group consisting of (i) a C -C fatty alcohol and (ii) a C to C mono-alkyl phenol, and the III ingredient is C -C fatty acid diethanolamides.

5. A stable enzyme-containing liquid detergent composition according to claim 4, in which the I ingredient constitutes frorn 52 to 64%, the II ingredient constitutes from 22 to 30%, and the III ingredient constitutes from 14 to 18%.

6. A stable enzyme-containing liquid detergent composition according to claim 4, in which the I ingredient is a diethanolamine salt of a linear tri-decyl benzene sulfonic acid, and the II ingredient is an approximately 8 mol ethylene oxide adduct of nonyl phenol.

7. A stable enzyme-containing liquid detergent composition according to claim 4, in which the I ingredient is a diethanolamine salt of a linear dodecyl benzene sulfonic acid, and the II ingredient is an approximately 7 mol ethylene oxide adduct of n-dodecyl alcohol.

8. A stable enzyme-containing liquid detergent composition according to claim 1, wherein said active enzyme comprises from about 0.1 to 0.2% by weight of said composition.

9. A stable enzyme-containing liquid detergent composition according to claim 1, having a pH of from about 4 to 9.

10. A sprayable liquid detergent composition which consists essentially of at least about by weight of the composition of claim 1, and a viscosity lowering amount of a diluent selected from the group consisting of monohydric and polyhydric alkanols containing from 1 to about 8 carbon atoms and lower monoand di-alkyl ethers of ethylene glycol.

References Cited UNITED STATES PATENTS 2,602,778 7/19'52 Snyder et a1 2528.55 B 3,239,468 3/1966 Herrick 252-152 3,451,935 6/19'69' Roald et al. 252 3,472,783 10/ 1969 Smillie 25289 3,031,408 4/1962 Perlman et al. 252-154 3,519,570 7/ 1970 McCarty 252l35 OTHER REFERENCES Detergent Age, December 1968, pp. 38-39. Soap & Chemical Specialties, July 1962, p. 159. Worne, Detergent Age, September 1968, pp. 19-22, 81.

LEON D. ROSDOL, Primary Examiner H. A. PITLICK, Assistant Examiner US. Cl. X.R.

-63, 68; 252--544, 54 8, DIG 12, DIG l4