CA1336895C

CA1336895C - Heavy duty liquid detergents containing anionic and nonionic surfactant, builder and proteolytic enzyme

Info

Publication number: CA1336895C
Application number: CA000599421A
Authority: CA
Inventors: Michael Stanford Showell; William Conrad Wertz
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1988-05-12
Filing date: 1989-05-11
Publication date: 1995-09-05
Anticipated expiration: 2012-09-05
Also published as: EP0342177A3; EP0342177A2; AU3473289A; DE68923398T2; DK232889D0; AU631793B2; PT90535A; BR8902223A; KR900018349A; PT90535B; EP0342177B1; DE68923398D1; KR960012272B1; JPH0251596A; JP2716522B2; DK232889A; MX170133B; IE891559L; NZ229079A

Abstract

Heavy duty liquid laundry detergent compositions containing synthetic anionic and ethoxylated nonionic surfactant, detergency builder, specific proteolytic enzyme, an enzyme stabilization system, and water are disclosed. The compositions have a pH in a 10% by weight solution in water at 20°C of between about 7.0 and 9.0, a Critical Micelle Concentration of less than or equal to about 200 ppm, and an air/water Interfacial Tension above the Critical Micelle Concentration of less than or equal to about 32 dynes/cm at 35°C in distilled water. The compositions are preferably clear, homogeneous, stable, and provide good cleaning performance, particularly through-the-wash on enzyme-sensitive stains.

Description

133~89S
HEAVY DUTY LIQUID LAUNDRY DETERGFNTS
CONTAINING ANIONIC AND NONIONIC SURFACTANT, BUILDER AND PROTEOLYTIC ENZYME

TECHNICAL FIELD
The present invention relates to heavy duty liquid laundry detergent compositions containing synthetic anionic and ethoxylated nonionic surfactant, detergency builder, specific proteolytic enzyme, an enzyme stabilization system, and water.
The compositions have a pH in a 10% by weight solution in water at 20C of between about 7.0 and 9.0, a Critical Micelle Concentration of less than or equal to about 200 ppm, and an air/water Interfacial Tension above the Critical Micelle Concentration of less than or equal to about 32 dynes/cm at 35 C
in distilled water. The compositions are preferably clear, homogeneous, and stable and provide good cleaning performance, particularly through-the-wash on enzyme-sensitive stains.
BACKGROUND OF THE INVENTION
Laundry detergents containing high levels of anionic sur-factant and builder, and capable of providing superior cleaningperformance, are currently on the market. Some of these compositions contain enzymes to enhance removal of enzyme-sensitive stains. The stabilization of enzymes is particularly difficult in these compositions because anionic sur-factants, especially alkyl sulfates, tend to denature enzymes andrender them inactive. Detergency builders can also sequester the calcium ion needed for enzyme activity and/or stability.
There is a continuing need for the development of new enzymes that provide improved performance and better stability in heavy duty liquid detergent compositions, particularly those containing high levels of anionic surfactant and builder. Once these enzymes are developed, it is then difficult to formulate a composition containing them that is clear, homogeneous and phase stable, maintains enzyme stability over time in product, and is an excellent fabric cleaner.
European Patent Application 130,756, Bott et al., published January 9, 1985, discloses specific proteolytic enzymes and methods for their preparation. The enzymes of this reference are said to be useful in laundry detergents, both liquid and granular.
They can be combined with surfactants (including anionics), builders, bleach and/or fluorescent whitening agents.
European Patent Application Serial No. 199,404, Venegas, published October 29, 1986, discloses heavy duty liquid laundry detergents containing a specific protease referred to as "Protease A", anionic surfactant, detergency builder, and calcium ion. The compositions provide improved cleaning performance, particularly through-the-wash, of enzyme-sensitive stains such as grass, blood, gravy and chocolate pudding.
European Patent Application Serial No. 199,405, Venegas, published October 29, 1986, discloses liquid detergent compositions containing synthetic surfactant, the same Protease A, boric acid or a boron compound capable of forming boric acid in the composition, and calcium ion. The compositions exhibit improved enzyme stability because the boric acid stabilizes the Protease A to a greater degree than it does other proteolytic enzymes. Preferred laundry detergent compositions containing anionic surfactant and detergency builder also provide improved cleaning performance, particularly through-the-wash, on enzyme-sensitive stains.
An improved proteol~vtic enzyme referred to herein as "Protease B" is described in European Patent Publication No. EP-A 251446, published November 23, 1988. Protease B differs from the above cited Protease A in that it has a leucine substituted for the tyrosine in position 217 on the protein backbone.

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U.S. Patent 4,507,219, Hughes, issued March 26, 1985, discloses heavy duty liquid laundry detergents which may contain proteolytic enzyme along with anionic surfactant, optional quaternary ammonium, amine or amine oxide surfactants, saturated fatty acid, polycarboxylate builder, a neutralization system, and a solvent system. The compositions are isotropic liquids.
International Patent Publication No. W087/04461, Stabinsky, published July 30, 1987, discloses a specific enzyme and methods for its preparation. The difference between the European application enzyme structure and the present enzyme structure is - replacement of the asparagine residue in the 218 position on the protein backbone with serine, valine, threonine, cysteine, glutamine or isoleucine. Said replacement is claimed to impart improved pH and heat stability to the enzyme.
U.S. Patent 4,670,179, Inamorato et al., issued June 2, 1987;
UK Patent Application 2,178,054, published February 4, 1987; UK
Patent Application 2178055, published February 4, 1987; U.S.
Patent 4,661,287, Crossin, issued April 28, 1987; U.S. Patent 4,529,525, Dormal et al., issued July 16, 1985; and U.S. Patent 4,652,394, Inamorato et al., issued March 24, 1987, disclose stabilized, single-phase liquid detergent compositions containing proteolytic enzymes, an enzyme stabilization system, nonphosphate builder salts, and/or polymeric soil removal/release systems.
U.S. Patent 4,608,189, Koch et al., issued August 26, 1986, discloses aqueous detergent compositions, essentially free of inorganic builder salts, which contain proteolytic enzymes and polyoxyethylene surfactants.
The following references disclose various stabilization systems in liquid detergent compositions containing enzymes: U.S.
Patent 4,261,868, Hora et al, issued April 14, 1981; U.S. Patent 4,404,115, Tai, issued September 13, 1983; U.S. Patent 4,318,818, Letton et al., issued March 9, 1982; U.S. Patent 4,243,543, Guilbert et al, issued January 6, 1981; U.S. Patent 4,529,525, 133689~

Dormal et al., issued July 16, 1985; and U.S. Patents 4,537,706 and 4,537,707, both Severson, Jr., issued August 27, 1985.
It is an object of this invention to provide heavy duty liquid detergent compositions comprising a proteolytic enzyme which have improved cleaning performance.
It is also an object of this invention to provide heavy duty liquid detergent compositions comprising a proteolytic enzyme which are clear, homogeneous suspensions that are stable at room temperature.
It is further an object of this invention to provide heavy duty liquid detergent compositions comprising a proteolytic enzyme which have improved enzyme stability.
It is yet another object of this invention to provide heavy duty liquid detergent compositions comprising a proteolytic enzyme which clean enzyme-sensitive stains, such as grass, blood, gravy and chocolate pudding stains, as well as or better than currently available heavy duty liquid detergent compositions comprising proteolytic enzymes.
These and other objects are attained as a result of formulating certain levels of Protease B, synthetic anionic surfactant, ethoxylated nonionic surfactant, detergency builder, a conventional enzyme stabilization system, and water at a pH in a 10% by weight solution in water at 20-C of between about 8.0 and 8.5. This composition is preferably clear, homogeneous, and phase stable, and has good cleaning performance and enzyme stability.
SUMMARY OF THE INVENTION
The present invention relates to a heavy duty liquid laundry detergent composition comprising, by weight:
(a) from about 10% to about 50% of a synthetic anionic surfactant;
(b) from about 2% to about 14% of an ethoxylated nonionic surfactant;
(c) from about 5% to about 20% of a detergency builder;

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(d) from about 0.01% to about 5% of the proteolytic enzyme characterized by the following amino acid sequence:
Ala Gln Ser Val Pro Tyr Gly Val Ser Gln Ile Lys Ala Pro Ala Leu His Ser Gln Gly Tyr Thr Gly Ser Asn Val Lys Val Ala Val Ile Asp Ser Gly Ile Asp Ser Ser His Pro Asp Leu Lys Val Ala Gly Gly Ala Ser Met Val Pro Ser Glu Thr Asn . 60 70 Pro Phe Gln Asp Asn Asn Ser His Gly Thr His Val Ala Gly Thr Val Ala Ala Leu Asn Asn Ser Ile Gly Val Leu Gly Val Ala Pro Ser Ala Ser Leu Tyr Ala Val Lys Val Leu Gly Ala Asp Gly Ser Gly Gln Tyr Ser Trp Ile Ile Asn Gly Ile Glu Trp Ala Ile Ala Asn Asn Met Asp Val Ile Asn Met Ser Leu Gly Gly Pro Ser Gly Ser Ala Ala Leu Lys Ala Ala Val Asp 2Lys Aia Val Ala Ser Gly Val Val Val Val Ala Ala Ala Gly Asn Glu Gly Thr Ser Gly Ser Ser Ser Thr Val Gly Tyr Pro Gly Lys Tyr Pro Ser Val Ile Ala Val Gly Ala Val Asp Ser Ser Asn Gln Arg Ala Ser Phe Ser Ser Val Gly Pro Glu Leu Asp Val Met Ala Pro Gly Val Ser Ile Gln Ser Thr Leu Pro Gly Asn Lys Tyr Gly Ala Leu Asn Gly Thr Ser Met Ala Ser 133~89~

Pro His Val Ala Gly Ala Ala Ala Leu Ile Leu Ser Lys His Pro Asn Trp Thr Asn Thr Gln Val Arg Ser Ser Leu Glu Asn Thr Thr Thr Lys Leu Gly Asp Ser Phe Tyr Tyr Gly Lys Gly Leu Ile Asn Val Gln Ala Ala Ala Gln; (referred to herein as Protease B) (e) from about 0.5% to about 1570 of an enzyme stabilization system; and (f) from about 30% to about 80% of water;
said composition containing (a) and (b) in a ratio of from 1:1 to 5:1; having a pH, in a 10% by weight solution in water at 20-C, of from about 7.0 to about 9.0; and having a Critical Micelle Concentration of less than or equal to about 200 ppm, and an air/water Interfacial Tension above the Critical Micelle Concentration of less than or equal to about 32 dynes/cm at 35-C
in distilled water.
DESCRIPTION OF THE INVENTION
The instant compositions contain six essential ingredients which are: (1) synthetic anionic surfactant, (2) ethoxylated nonionic surfactant, (3) detergency builder, (4) a specific proteolytic enzyme, (5) an enzyme stabilization system, and (6) water. The weight ratio of synthetic anionic surfactant to ethoxylated nonionic surfactant is from about 1:1 to about 5:1.
The compositions have a pH in a 10% by weight solution in water at 20 C of from about 7.0 to about 9.0, a Critical Micelle Concentration of less than or equal to about 200 ppm, and an air/water Interfacial Tension at the Critical Micelle Concentration of less than or equal to about 32 dynes/cm at 35 C
in distilled water. The compositions are preferably clear, homogeneous and phase stable, and have good cleaning performance and enzyme stability.

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A. SYnthetic Anionic Surfactant The compositions of the present invention contain from about 10% to about 50%, preferably from about 15% to about 50%, more preferably from about 20% to about 40%, and most preferably from about 20% to about 30%, by weight of a synthetic anionic surfactant. Suitable synthetic anionic surfactants are disclosed in U.S. Patent 4,285,841, Barrat et al., issued August 25, 1981, and in U.S. Patent 3,929,678, Laughlin et al., issued December 30, lg75 Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about lO to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of aryl groups.) Examples of this group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-Clg carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the alkylbenzene sulfonates in which the alkyl group contains from about 9 to about l5 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U. S. Patents 2,220,099 and 2,477,383.
Especially valuable are linear straight chain alkylbenzene sul-fonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14.
Other anionic surfactants herein are the water-soluble salts of: paraffin sulfonates containing from about 8 to about 24 (pre-ferably about 12 to 18) carbon atoms; alkyl glyceryl ether sul-fonates, especially those ethers of Cg 18 alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from about l to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing about 1 to about 4 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group.
Other useful anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy- alkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Preferred anionic surfactants are the Clo-Clg alkyl sulfates and alkyl ethoxy- sulfates containing an average of up to about 4 ethylene oxide units per mole of alkyl sulfate, Cll-C13 linear alkylbenzene sulfonates, and mixtures thereof.
B. EthoxYlated Nonionic Surfactant A second essential ingredient is from about 2% to about 14%, preferably from about 2% to about 8%, most preferably from about 3% to about 5% by weight, of an ethoxylated nonionic surfactant.
The weight ratio of synthetic anionic surfactant (on an acid basis) to nonionic surfactant is from about 1:1 to about 5:1, preferably from about 2:1 to about 5:1, most preferably from about 3:1 to about 4:1. This is to ensure the formation and adsorption of sufficient hardness surfactants at the air/water interface to provide good greasy/oily soil removal.
The ethoxylated nonionic surfactant is of the formula Rl(OC2H4)n0H, wherein Rl is a C10-cl6 alkyl group or a Cg-C12 alkyl phenyl group, n is from about 3 to about 9, and said nonionic surfactant has an HLB (Hydrophilic-Lipophilic Balance) of from about 6 to about 14, preferably from about 10 to about 13.
These surfactants are more fully described in U.S. Patents 4,285,841, Barrat et al., issued August 25, 1981, and 4,284,532, Leikhim et al., issued August 18, 1981. Particularly preferred are condensation products of 13~689~
.9 C12-C1s alcohols with from about 3 to about 8 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
' - C. Optional Cosurfactants Optional cosurfactants for use with the above ethoxylated nonionic surfactants include amides of the formula Rl - C - N - R3 wherein Rl is an alkyl, hydroxyalkyl or alkenyl radical containing from about 8 to about 20 carbon atoms, and R2 and R3 are selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, and said radicals additionally containing up to about 5 ethylene oxide units, provided at least one of R2 and R3 contains a hydroxyl group.
Preferred amides are the Cg-C20 fatty acid alkylol amides in which each alkylol group contains from 1 to 3 carbon atoms, and additionally can contain up to about 2 ethylene oxide units.
Particularly preferred are the C12-C16 fatty acid monoethanol and diethanol amides.
If used, amides are preferably present at a level such that the above ethoxylated nonionic surfactant and amide surfactant is in a weight ratio of from about 4:1 to 1:4, preferably from about 3:1 to about 1:3.
Preferred and optional cosurfactants, used at a level of from about 0.15% to about 1%, are the quaternary ammonium, amine and amine oxide surfactants described in U.S. Patent 4,507,219, Hughes, issued March 26, 1985.
Of the above, the Clo-C14 alkyl trimethylammonium salts are preferred, e.g., decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride and methylsulfate. From about 0.2% to about 0.8% of monoalkyl trimethylammonium chloride is preferred.
D. DeterqencY Builder The compositions herein contain from about 5% to about 20%, preferably from about 10% to about 15%, by weight of a detergency builder which can be a fatty acid containing from about 10 to about 18 carbon atoms and/or a polycarboxylate, polyphosphonate and/or polyphosphate builder. Preferred are from 0 to about lO~o (more preferably from about 3% to about 10%) by weight of sat-urated fatty acids containing from about 12 to about 14 carbon atoms, along with from 0 to about 10%, more preferably from about 2% to about 8%, most preferably from about 2% to about 5%, by weight of a po1ycarboxylate builder, most preferably citric acid, in a weight ratio of from 1:1 to 3:1.
Since the proteolytic enzymes herein appear to provide optimum performance benefits versus other enzymes when the builder to water hardness ratio is close to one, the compositions preferably contain sufficient builder to sequester from about 2 to about 10, preferably from about 3 to about 8, grains per gallon of hardness.
Suitable saturated fatty acids can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil and coconut oil) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process). Examples of suitable saturated fatty acids for use in the compositions of this invention include capric, lauric, myristic, coconut and palm kernel fatty acid.
Preferred are saturated coconut fatty acids; from about 5:1 to 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid; mixtures of the above with minor amounts (e.g., 1%-30% of total fatty acid) of oleic acid; and palm kernel fatty acid.
The compositions herein preferably also contain the polycarboxylate, polyphosphonate and polyphosphate builders described in U.S. Patent 4,284,532, Leikhim et al., issued August 18, 1981. Water-soluble polycarboxylate builders, particularly citrates, are preferred of this group. Suitable polycarboxylate builders include the various aminopolycarboxylates, cycloalkane polycar-boxylates, ether polycarboxylates, alkyl polycarboxy-lates, epoxy polycarboxylates, tetrahydrofuran polycarboxylates, benzene polycarboxylates, and polyacetal polycarboxylates.
Examples of such polycarboxylate builders are sodium and potassium ethylenediaminetetraacetate; sodium and potassium nitrilotriacetate; the water-soluble salts of phytic acid, e.g., sodium and potassium phytatese, disclosed in U.S. Patent 1,739,942, Eckey, issued March 2i, 1956; the polycarboxylate materials described in U.S. Patent 3,364,103; and the water-soluble salts of polycarboxylate polymers and copolymers described in U.S.
Patent 3,308,067, Diehl, issued March 7, 1967.
Other useful detergency builders include the water-soluble salts of polymeric aliphatic polycarboxylic acids having the following structural and physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (3) at least 45 mole percent.of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms: (d) the site of attachment of the polymer chain of any carboxyl- containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical.
Specific examples of such builders are the polymers and copolymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid.
Other suitable polycarboxylate builders include the water-soluble salts, especially the sodium and potassium salts, of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid and oxydisuccinic acid.
Other polycarboxylates are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al., and U.S. Patent 4,146,495, issued March 27, 1979 to Crutchfield et al.
Other detergency builders include the aluminosilicate ion exchange material described in U.S. Patent 4,405,483, Kuzel et al., issued September 20, 1983.
Other preferred builders are those of the general formula R-CH(COOH)CH2(COOH), i.e. derivatives of succinic acid, wherein R
is Clo-C20 alkyl or alkenyl, preferably C12-C16, or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents. These succinate builders are preferably used in the form of their water soluble salts, including the sodium, potassium 2 and alkanolammonium salts. Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, and the like.
E. Tartrate Succinate Builder The compositions herein preferably contain from 0 to about 2 10%, preferably from 0 to about 6%, by weight on an acid basis, of a tartrate succinate builder material selected from the group consisting of:
i ) HOCH - CH - O - CH - CHz COOX COOX COOX COOX
wherein X is a salt-forming cation;
ii) CH2 - CH - O - CH - CH - O - CH - CH2 COOX COOX COOX COOX COOX COOX
wherein X is a salt-forming cation; and iii) mixtures thereof.

The tartrate succinate compounds used herein are described in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987.

F. Neutralization SYstem The present compositions can also optionally contain from about 0 to about 0.04 moles, preferably from about 0.01 to about 0.035 moles, more preferably from about 0.015 to about 0.03 moles, per 100 grams of composition of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, trietha-nolamine, and mixtures thereof. Low levels of the alkanolamines, particularly monoethanolamine, are preferred to enhance product stability, detergency performancet and odor. However, the amount of alkanolamine should be minimized for best chlorine bleach compatibi-lity.
In addition, the compositions contain sodium ions, and preferably potassium ions, at a level sufficient to neutralize the anionic species and provide the desired product pH.
G. ProteolYtic EnzYme The compositions of the present invention contain from about 0.01% to about 5%, preferably from about 0.1% to about 2%, by weight of the proteolytic enzyme referred to herein as Protease B.
This proteolytic enzyme, and methods for its Preparation, is described in European Patent Publication No. 251,446, published January 7, 1988. Methods for its preparation are also described in European Patent Publication 130,756, Bott et al., published January 9, 1985.
The described proteolytic enzyme is preferably included in an amount sufficient to provide an activity of from about 0.05 to about 1.0, more preferably from about 0.1 to about 0.75, most preferably from about 0.125 to about 0.5, mg of active enzyme per gram of composition.

H. EnzYme Stabilization SYstem An enzyme stabilization system, comprising calcium ion, boric acid, propylene glycol and/or short chain carboxylic acids, is the fifth essential element of the instant heavy duty liquid detergent composition. The enzyme stabilization system comprises from about 0.5% to about 15% by weight of the composition.
The composition preferably contains from about 0.01 to about 50, preferably from about 0.1 to about 30, more preferably from 0 about 1 to about 20, millimoles of calcium ion per liter. The level of calcium ion should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, etc., in the composition. Any water-soluble calcium salt can be used as the source of calcium ion, including calcium chloride, calcium formate, and calcium acetate.
A small amount of calcium ion, generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water. From about 0.03% to about 0.6% of calcium formate is preferred.
A second preferred enzyme stabilizer is polyols containing only carbon, hydrogen and oxygen atoms. They preferably contain from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups. Examples include propylene glycol (especially 1,2 propanediol, which is preferred), ethylene glycol, glycerol, sorbitol, mannitol, and glucose. The polyol generally represents from about 0.5% to about 15%, preferably from about 1.5% to about 8%, by weight of the composition. Preferably, the weight ratio of polyol to any boric acid added is at least 1, more preferably at least about 1.3.
The compositions preferably also contain the water-soluble, short chain carboxylates described in U.S. Patent 4,318,818, Letton et al., issued March 9, 1982. The formates are preferred and can be used at levels of from about 0.05%
to about 5%, preferably from about 0.2% to about 2%, most preferably from about 0.4% to about 1.5%, by weight of the composition. Sodium formate is preferred.

-The compositions herein also optionally contain from about 0.25% to about 5%, most preferably from about 0.5% to about 3%, by weight of boric acid. The boric acid may be, but is preferably ' - not, formed by a compound capable of forming boric acid in the composition. Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid) can also be used in place of boric acid.
I. Water Finally, the compositions herein contain from about 30% to about 80%, preferably from about 35% to about 60%, by weight of water.
J. Suds Suppressor Another optional component for use in the liquid detergents herein is from 0 to about 1.5%, preferably from about 0.5% to about 1.0%, by weight of silicone based suds suppressor agent.
Silicones are widely known and taught for use as highly effective suds controlling agents. For example, U.S. Patent 3,455,839 relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
Useful suds controlling silicones are mixtures of silicone and silanated silica as described, for instance, in Canadian Patent Application 947,608.
Silicone defoamers and suds controlling agents have been successfully incorporated into granular detergent compositions by protecting them from detergent surfactants as in U.S. Patent 3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987.
A preferred silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:

1336g95 (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs. at 25-C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3 Sil/2 units and SiO2 units in a ratio of from (CH3)3 SiOl/2 units and to SiO2 units of from about 0.6:1 to about 1.2:1;
and (iii)from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel;
By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will control the suds to the extent desired. The amount of suds control will vary with the detergent surfactant selected. For example, with high sudsing surfactants, relatively more of the suds controlling agent is used to achieve the desired suds control than with low foaming surfactants.
K. Other Optional ComDonents Other optional components for use in the liquid detergents herein include soil removal agents, soil release polymers, antire-deposition agents such as tetraethylene pentamine ethoxylate (from about 0.5% to about 3%, preferably from about 1% to about 3%, by weight), suds regulants, hydrotropes such as sodium cumene sulfonate, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners known in the art. Such optional components generally represent less than about 15%, preferably from about 0.5X to about 10%, more preferably from about 1% to about 10%, by weight of the composition.
The compositions may contain from 0% to about 8%, preferably from 0% to about 5%, by weight of a C12-C14 alkenyl succinic acid or salt thereof. These materials are of the general formual R-CH(COOX)CH2(COOX), wherein R is a C12-C14 alkenyl group and each X is H or a suitable cation, such as sodium, potassium, ammonium or alkanolammonium (e.g., mono-, di-, or tri-ethanolammonium).

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Specific examples are 2-dodecenyl succinate (preferred) and 2-tetradecenyl succinate.
The compositions herein optionally contain from about 0.1% to about 1%, preferably from about 0.2% to about 0.6%, by weight of water-soluble salts of ethylenediamine tetramethylenephosphonic acid, diethylenetriamine pentamethylenephosphonic acid, ethyl-enediamine tetraacetic acid (preferred), or diethylenetriamine pentaacetic acid (most preferred) to enhance cleaning performance when pretreating fabrics.
The compositions herein preferably contaln up to about 10% of ethanol.
L. Other Requirements The instant composition has a pH, in a 10% by weight solution in water at 20'C, of from about 7.0 to about 9.0, preferably from about 8.0 to about 8.5.
The instant compositions also have a Critical Micelle Concentration (CMC) of less than or equal to about 200 parts per million (ppm), and an air/water Interfacial Tension above the CMC
of less than or equal to about 32, preferably less than or equal to about 30, dynes per centimeter at 35C in distilled water.
These measurements are described in "Measurement of Interfacial Tension and Surface Tension - General Review for Practical Man", C. Weser, GIT Fachzeitschrift fvr das Laboratorium, 24 (1980) 642-648 and 734-742, FIT Verlag Ernst Giebeler, Darmstadt, and Interfacial Phenomena - Equilibrium and DYnamic Effects, C.A.
Miller and P. Neogi, Chapter 1, pp. 29-36 (1985), Marcel Dekker, Inc. New York.
Enzyme activity can be measured using the PNA assay, according to reaction with the soluble substrate succinyl-alanine-alanine-proline-phenylalanine-para-nitrophenol, which is described in the Journal of American Oil Chemists Society, Rothgeb, T.M., Goodlander, B.D., Garrison, P.H., and Smith, L.A., JAOCS, 65, No. 5, May 1988, pages 806-810.

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13368~5 The following examples illustrate the compositions of the present invention. All parts, percentages and ratios used herein are by weight unless otherwise specified.
- EXAMPLE I
A heavy duty liquid laundry detergent composition of the present invention is as follows:
ComPonent Active Weight %
C13 linear alkylbenzene sulfonic acid 8.00 C14 15 alkyl polyethoxylate (2.25) sulfonic acid 12.00 1,2 Propanediol 3.50 Sodium diethylenetriamine pentaacetate 0.30 Monoethanolamine 2.00 C12 13 alcohol polyethoxylate (6.5)* 5.00 Ethanol - 8.50 Sodium hydroxide ~~ 3.85 Potassium hydroxide 1.80 C12 14 fatty acid 10.00 Citric acid 4.00 20 Calcium formate 0.12 Sodium formate 0.86 C12 alkyltrimethylammonium chloride 0.50 Tetraethylene pentamine ethoxylate (15-18) 2.00 Water 37.14 Dye 0.08 Perfume 0.25 Protease~ B** 0.099 *Alcohol and monoethoxylated alcohol removed.
**mg active enzyme/g (@27 mg active enzyme/g stock) The ingredients listed above are added to a mixing tank with a single agitator in the order in which they appear below. Before the proteolytic enzyme, dye and perfume are added, the pH of the mix is adjusted so that a 10% by weight solution in water at 20C
has a pH of about 8.5.

13368g5 Stock Material Weight Percent C13 linear alkyl benzene sulfonic acid (96%) 8.33 Alkyl polyethoxylate paste mixture 24.80 C14 15 alkyl polyethoxylate (2-25) 48.38 sulfonic acid Ethanol (92%) 16.20 Sodium hydroxide 5.12 Water 30.30 1,2 Propanediol Sodium diethylenetriamine pentaacetate (41%) 0.73 Brightener premix 6.70 Brightener 3.07 Monoethanolamine 7.46 C12 13 alcohol polyethoxylate (6.5)* 29.82 Water 59.65 Monoethanolamine 1.50 C12 13 alcohol polyethoxylate (6.5)* 2.93 Sodium hydroxide (50%) 5.16 Potassium hydroxide (45%) 4.00 C12 14 fatty acid 10.00 Citric acid (50~O) 8.00 Ethanol (92%) 4.87 Calcium formate (10%) 1.20 Sodium formate (30%) 2.87 C12 alkyltrimethylammonium chloride (37%) 1.62 Tetraethylene pentamine ethoxylate (15-18)(80%) 2.50 Water 10.86 Dye 0.08 30 Perfume 0.25 Protease B** 0.099 *Alcohol and monoethoxylated alcohol removed.
**mg active enzyme/g (27 mg active enzyme/g stock) This formula is clear, homogeneous, and stable, and has a Critical Micelle Concentration of about 200 ppm and an air/water Interfacial Tension above this CMC of about 25 dynes/cm at 35 C in distilled water. The composition with Protease~ B provides superior cleaning of enzyme-sensitive stains, even when compared to Protease A (described above) at 0.25 mg active enzyme/g product -- in a 60-F (15.6C) wash at 5 grains per gallon (gpg) hardness (3:1 Ca/Mg).
Protease B also shows superior enzyme stability in the composition of Example I versus other proteolytic enzymes such as Protease A and Alcalase~ B (Novo Industries, Copenhagen, Denmark):
10Enzyme Activity*
(after 1 week storage at 37.8C) % ActivitY Half Life (daYs) Protease B 58.4 9.1 Protease A 33.6 4.5 Alcalase B 13.7 2.5 *PNA assay EXAMPLE II
A heavy duty liquid composition of the present invention is as follows:
ComPonent Active Weight %
C13 linear alkylbenzene sulfonic acid 3.80 C11.g linear alkylbenzene sulfonic acid 3.80 C14 15 alkyl polyethoxylate (2.25) sulfonic acid 11.41 C12 1~ alkyl polyethoxylate (6.5)* 3.80 C12 alkyl trimethyl ammonium chloride 0.28 Sodium cumene sulfonate 2.38 Ethanol 2.61 1,2 Propanediol 2.85 Brightener 0.12 30 Monoethanolamine 1.66 Potassium hydroxide 0.19 Sodium hydroxide 3.85 C12 14 fatty acid 3 33 Citric acid 3.80 35 Tartrate succinate 3.80 133~8~

Sodium formate 0.92 Calcium formate 0.04 Tetraethylene pentamine ethoxylate (15-18) 1.66 Water 48.04 Soil release polymer 1.10 Dye 0.08 Perfume 0.30 Protease B** 0.175 *Alcohol and monoethoxylated alcohol removed ** mg active enzyme/g (@ 27 mg active enzyme/g stock) The ingredients listed above are added to a mixing tank with a single agitator in the order which they appear below. Before addition of soil release polymer, dye, perfume, and proteolytic enzyme, the pH of the mixture is adjusted such that a 10% by weight solution in water has a pH of about 8.5.
Stock Material Weiqht Percent Alkyl polyethoxylate paste mixture 28.28 C14 15 alkyl polyethoxylate (2.25) 40.34 sulfonic acid Ethanol 40-b 4.98 Sodium hydroxide 5.13 1,2 Propanediol 6.89 Monoethanolamine 2.84 Sodium formate 1.65 Water 38.17 Sodium amine sulfonate (45%) 5.29 Ethanol (92%) 1.31 1,2 Propanediol o.go Brightener premix 2.59 Brightener 4.63 Monoethanolamine 10.62 C12 13 alcohol polyethoxylate (6.5)* 42.38 Water 42.37 3 C12 13 alcohol polyethoxylate (6.5)* 2.70 133689~

Monoethanolamine 0.58 Potassium hydroxide (45%) 0.42 Sodium hydroxide (50%) 4.80 C13 linear alkyl benzene sulfonic acid (96X) 3.96 C11.g linear alkyl benzene sulfonic acid (97%) 3.92 C12 14 fatty acid 3 33 Citric acid 6.96 Tartrate succinates (34.3%) 11.08 Sodium formate (307O) 3.08 -Calcium formate (10Z) 0.38 C12 alkyl trimethylammonium chloride (37%) 0.76 -~
Tetraethylene pentamine ethoxylate (15-18) (80%) 2.08 Water 15.92 Soil release polymer 1.10 Dye 0.08 Perfume 0.30 Protease B** 0.175 ~`
*Alcohol and monoethoxylated alcohol removed ** mg active enzyme/g (@ 27 mg active enzyme/g stock) The above formula is clear, stable, and homogeneous, and has a Critical Micelle Concentration of about 100 ppm and an air/water Interfacial Tension above that CMC of about 30 dynes/cm at 35-C in distilled water. The composition with Protease B provides protease-sensitive stain removal equal to that achieved with the same formula using 0.35 mg active enzyme/g product of Protease A
(described above).
Protease B also shows superior enzyme stability in the composition of Example II versus other proteolytic enzymes such as Protease A and Alcalase B (Novo Industries, Copenhagent Denmark).
Enzyme Activity*
(After 4 weeks storage at 37.8-C) % ActivitY Half Life (daYs) Protease B 16.2 10.7 Protease A 4.2 6 Alcalase B 0.00 *PNA assay EXAMPLE III
A heavy duty liquid laundry detergent composition of the present invention is as follows:
ComDonent Active Weiqht %
C13 linear alkylbenzene sulfonic acid 13.00 C13 14 alkyl sulfuric acid 13.00 C12 13 alcohol polyethoxylate (6.5)* 6.00 Sodium cumene sulfonate 6.30 Ethanol (92%) 2.50 1,2 Propanediol 7.50 Brightener 0.12 Monoethanolamine - Z.00 Potassium hydroxide 0.15 Sodium hydroxide 4.29 C12 14 fatty acid 1.0 20 Tartrate succinate 10.0 Citric acid 4.0 Calcium formate 0.04 Sodium formate 0.86 C12 alkyltrimethylammonium chloride 0.50 Tetraethylene pentamine ethoxylate (15-18) 1.65 Water 25.36 Soil release polymer 1.00 Dye 0.08 Perfume 0.25 30 Protease B** 0.397 *Alcohol and monoethoxylated alcohol removed.
**mg active enzyme/g (@ 27 mg active enzyme/g stock) The composition is prepared as in Example II.

l336~95 EXAMPLE IV
A heavy duty liquid laundry detergent composition of the present invention is as follows:
Com w nent Active Weiqht %
C13 linear alkylbenzene sulfonic acid 4.23 C11.g alkylbenzene sulfonic acid 4.23 C14 15 alkyl polyethoxylate (2.25) sulfonic acid 8.46 C12 13 alkyl polyethoxylate (6.5)* 3.39 Sodium cumene sulfonate 5.45 Ethanol (92%) 1.18 Propanediol 2.89 Brightener 0. 11 Monoethanolamine 1.57 Tartrate succinate 9.62 15 Calcium formate 0.102 Formic acid 0.51 C12 Trimethylammonium chloride 0.51 Tetraethylene pentamine ethoxylate (15-18) 0.96 Water 55.57 20 Soil release polymer 0.90 Silicone suds suppressor 0.10 Protease B** 0.221 *Alcohol and monoethoxylated alcohol removed.
**mg active enzyme/g (@ 27 mg active enzyme/g stock) The composition is prepared as in Example II.
The above formula is clear, stable, and homogeneous, and has a Critical Micelle Concentration of about 100 ppm and an air/water Interfacial Tension above that CMC of about 30 dynes/cm at 35C in distilled water. The composition with Protease B provides protease-sensitive stain removal equal to that achieved with the same formula using 0.35 mg active enzyme/g product of Protease A
(described above).
Protease B also shows superior enzyme stability in the composition of Example IY versus other proteolytic enzymes such 133~895 as Protease A and Alcalase B (Novo Industries, Copenhagen, Denmark).
Enzyme Activity*
(After 2 weeks storage at 37.8-C) % ActivitY Half Life (daYs) Protease B 64.0 20.7 Protease A 50.0 13.8 Alcalase B --- 3.3 *PNA assay EXAMPLE V

A heavy duty liquid laundry detergent composition of the present invention is as follows:
ComDonent Active Weight %
C1o 15 Linear alkylbenzene sulfonic acid 12.86 Sodium C12 14 alkyl sulfate 2.00 1,2 Propanediol 2.00 Diethylenetriamine pentamethylene phosphonic acid 0.70 C14-15 alcohol polyethoxylate (E07) 7.77 20 Ethanol 4.60 Sodium hydroxide 7.00 Soil release polymer 0.46 C12 14 alkenyl succinic acid 11.44 Brightener 0.163 25 Oleic acid 1.80 Citric acid (monohydrate) 2.90 Calcium chloride 0.014 Boric acid 1.00 Silane 0.03 30 Water & miscellaneous Balance Protease B* 0.28 *419 active enzyme/liter of enzyme Stock Material Premix 1 Water 23.68 Sodium hydroxide 11.50 Citric acid 5.674 Ethanol 4.00 C12 14 alkenyl succinic acid 10.74 C10 15 Linear alkylbenzene sulfonic acid 6.70 62.294 Premix 2 1,2 Propanediol 0.493 Brightener 0.163 C14 15 alcohol polyethoxylate (E07) 1.70 2.356 Premix 3 Water 4.44 Boric acid 1.0 Sodium hydroxide 2.4 Diethylene triamine pentamethylene phosphonic aid 1.4 9.244 Premix 4 Citric acid 0.126 Calcium chloride 0.015 0.141 Premix 5 Soil release polymer 0.46 Water 0.46 0.92 Finished Product Premix 1 62.294 1,2 Propanediol 1.507 Clo l5 Linear alkyl benzene sulfonate 6.70 3S C14 15 alcohol polyethoxylate (E07) 6.07 Premix 2 2.356 133689~

Premix 3 9.244 Sodium C12 14 alkyl sulfate 6.66 Oleic acid 1.80 Premix 4 0.141 Premix 5 0.92 Silane 0.03 Protease B 0.28 Water Balance The ingredients listed above in "Finished Product" are added to a mixing tank with a single agitator in the order in which they appear. The pH of the mix is adjusted so that the pH is from 7.5 to 7.8.
The composition with Protease B provides 61% retained 5 protease activity after three weeks storage at 35-C.
EXAMPLE VI
A heavy duty liquid laundry detergent composition of the present invention is as follows:
Component Active Weight %
C10 lsLinear alkylbenzene sulfonic acid 10.25 Triethanolamine C12 14 alkyl sulfate 3.88 1,2 Propanediol 1.50 Diethylenetriamine pentamethylene phosphonic acid 0.765 Triethanolamine (free) 4.335 C14 15 alcohol polyethoxylate (E07) 11.620 Ethanol 5.510 Sodium hydroxide 3.400 Cg 18 fatty acid 10.68 Oleic acid 3.88 30 Citric acid (anhydrous) 0.83 Calcium chloride 0.0167 Sodium formate 0.972 Tetraethylene pentamine ethoxylate (15-18) 0.30 Dye 0.0032 35 Opacifier 0.224 Perfume 0.30 133~89S

Soil release polymer 0.50 N-(ethylene diaminoethyl) aminopropyltrimethoxy silane 0.030 Silicone suds suppressor 0.0025 Brightener 0.148 Water & miscellaneous Balance Protease B* 0.28 Amylase** 0.183 *419 active enzyme/liter of enzyme.
**125 PGU active enzyme/gram amylase solution.
The ingredients listed above are added to a mixing tank with a single agitator. The pH of the mix is adjusted so that it is between about 8.0 and 8.5.

WHAT IS CLAIMED IS:

Claims

1. A heavy duty liquid laundry detergent composition comprising, by weight:
(a) from about 10% to about 50% of a synthetic anionic surfactant;
(b) from about 2% to about 14% of an ethoxylated nonionic surfactant;
(c) from about 5% to about 20% of a detergency builder;
(d) from about 0.01% to about 5% of the proteolytic enzyme characterized by the following amino acid sequence:

(e) from about 0.5% to about 15% of an enzyme stabilization system; and (f) from about 30% to about 80% of water;
said composition containing (a) and (b) in a ratio of from 1:1 to 5:1; having a pH, in a 10% by weight solution in water at 20°C, of from about 7.0 to about 9.0; and having a Critical Micelle Concentration of less than or equal to about 200 ppm, and an air/water Interfacial Tension above the Critical Micelle Concentration of less than or equal to about 32 dynes/cm at 35°C
in distilled water.

2. A heavy duty liquid laundry detergent composition according to Claim 1 comprising from about 15% to about 50% by weight of anionic surfactant selected from the group consisting of alkyl sulfates containing from about 10 to about 18 carbon atoms, alkyl ethoxy sulfates containing from about 10 to about 18 carbon atoms and an average of up to about 4 ethylene oxide units per mole of alkyl sulfate, linear alkylbenzene sulfonates containing from about 11 to about 13 carbon atoms, and mixtures thereof.

3. A heavy duty liquid laundry detergent composition according to Claim 2 wherein said ethoxylated nonionic surfactant comprises from about 3% to about 5% by weight of an ethoxylated nonionic surfactant of the formula R1(OC2H4)nOH, wherein R1 is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, n is from about 3 to about 9, and having an HLB (Hydrophilic-Lipophilic Balance) of from about 6 to about 14.

4. A heavy duty liquid laundry detergent composition according to Claim 3 wheleill said ethoxylated nonionic surfactant comprises from about 3% to about

5% of an ethoxylated nonionic surfactant which is a condensation product of C12-C15 alcohols with from about 3 to about 8 moles of ethylene oxide per mole of alcohol.

5. A heavy duty liquid laundry detergent composition according to Claim 3 further comprising from about 0.15% to about 1% by weight of a surfactant selected from the group consisting of quaternary ammonium, amine and amine oxide surfactants, and mixtures thereof.

6. A heavy duty liquid laundry detergent composition according to Claim 5 wherein the further surfactant comprises from about 0.2% to about 0.8% of monoalkyl trimethylammonium chloride.

7. A heavy duty liquid laundry detergent composition according to Claim 1 wherein the detergency builder comprises from 0 to about 10% by weight of a saturated fatty acid builder containing from about 12 to about 14 carbon atoms and from 0 to about 10% by weight of a water-soluble polycarboxylate builder.

8. A heavy duty liquid laundry detergent composition according to Claim 7 wherein said polycarboxylate builder comprises from 2% to about 8% by weight of citric acid.

9. A heavy duty liquid laundry detergent composition according to Claim 8 further comprising from 0% to about 10% by weight on an acid basis of a tartratesuccinate builder material selected from the group consisting of:

i) wherein X is a salt-forming cation;

ii) wherein X is a salt-forming cation; and iii) mixtures thereof.

10. A heavy duty liquid laundry detergent composition according to Claim 8 additionally comprising from about 0.2% to about 0.6% by weight of water-solublesalts of ethylenediamine tetraacetic acid or diethylenetriamine pentaacetic acid.

11. A heavy duty liquid laundry detergent composition according to Claim 3 comprising from about 0.1% to about 2% by weight of said proteolytic enzyme.

12. A heavy duty liquid laundry detergent composition according to Claim 11 further comprising from about 0.01 to about 50 millimoles of calcium ion per liter of composition.

13. A heavy duty liquid laundry detergent composition according to Claim 12 wherein the calcium ion comprises from about 0.03% to about 0.6% by weight of calcium formate.

14. A heavy duty liquid laundry detergent composition according to Claim 13 further comprising from about 0.5% to about 15% by weight of a polyol containing only carbon, hydrogen and oxygen atoms.

15. A heavy duty liquid laundry detergent composition according to Claim 14 wherein the polyol comprises from about 1.5% to about 8% by weight of propylene glycol.

16. A heavy duty liquid laundry detergent composition according to Claim 15 further comprising from about 0.05% to about 5% by weight of a formate.

17. A heavy duty liquid laundry detergent composition according to Claim 16 wherein the formate comprises from about 0.4% to about 1.5% by weight of sodium formate.

18. A heavy duty liquid laundry detergent composition according to Claim 17 further comprising from about 0.5% to about 3% by weight of tetraethylene pentamine ethoxylate.

19. A heavy duty liquid laundry detergent composition according to Claim 18 further comprising from 0 to about 0.04 moles per 100 grams of composition of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, and mixtures thereof.

20. A heavy duty liquid laundry detergent composition according to Claim 11 further comprising from 0 to about 15% by weight of a silicone based suds suppressor agent.