CA1302925C - Liquid detergents containing surfactant, proteolytic enzyme and boric acid - Google Patents
Liquid detergents containing surfactant, proteolytic enzyme and boric acidInfo
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- CA1302925C CA1302925C CA000506568A CA506568A CA1302925C CA 1302925 C CA1302925 C CA 1302925C CA 000506568 A CA000506568 A CA 000506568A CA 506568 A CA506568 A CA 506568A CA 1302925 C CA1302925 C CA 1302925C
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- composition according
- boric acid
- surfactant
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38663—Stabilised liquid enzyme compositions
Abstract
LIQUID DETERGENTS CONTAINING
SURFACTANT, PROTEOLYTIC ENZYME AND BORIC ACID
Abstract of the Disclosure Liquid detergent compositions containing synthetic surfactant, specific proteolytic enzyme, boric acid or a boron compound capable of forming boric acid in the composition, and calcium ion are disclosed. The composi-tions exhibit improved enzyme stability because boric acid stabilizes the proteases herein to a greater degree than it does other proteases. Preferred laundry deter-gent compositions containing anionic surfactant and detergency builder also provide improved cleaning per-formance, particularly through-the-wash, on enzyme-sensitive stains.
SURFACTANT, PROTEOLYTIC ENZYME AND BORIC ACID
Abstract of the Disclosure Liquid detergent compositions containing synthetic surfactant, specific proteolytic enzyme, boric acid or a boron compound capable of forming boric acid in the composition, and calcium ion are disclosed. The composi-tions exhibit improved enzyme stability because boric acid stabilizes the proteases herein to a greater degree than it does other proteases. Preferred laundry deter-gent compositions containing anionic surfactant and detergency builder also provide improved cleaning per-formance, particularly through-the-wash, on enzyme-sensitive stains.
Description
33 ~?
13~292S
LIQUID DETERGENTS CONTAINING
SURFACTANT, PROTEOLYTIC ENZYME AND BORIC ACID
~anuel G~ Venegas Technical Field The present invention relates to liquid detergent compositions containing synthetic surfactant, specific proteolytic enzyme, boric acid or a boron compound capable of forming boric acid in the composition, and calcium ion. The compositions exhibit improved enzyme stability because boric acid stabilizes the proteases herein to a greater degree than it does other proteases.
The compositions are preferably heavy-duty liquid laundry detergents, but can also be light-duty liquid detergents suitable for dishwashing or washing fine fabrics, deter-gent pretreatment compositions or all-purpose household liquid cleaners. Preferred laundry detergent composi-tions containing a relatively high level of anionic surfactant and detergency builder also provide improved cleaning performance, particularly through-the-wash, of enzyme-sensitive stains such as gras~, blood, gravy and chocolate pudding.
Laundry detergents containing high levels of anionic surfactant and builder, and capable of providing superior cleaning performance, are currently available. Some of these compositions also contain enzymes to enhance removal of enzyme-sensitive stains. However, it is believed that such compositions are enzyme-limited in that they can denature and expose stains to enzymatic action faster than currently availa~le enzymes can cleave and break up the stains.
Enzyme performance can also be limited by a lack of adequate stability in liquid detergents. The stabiliza-tion of enzymes is particularly difficult in built, heavy-duty liquid detergents containing high levels of anionic surfactant and water. Anionic surfactants, especially alkyl sulfates, tend to denature enzymes and ~302925 render them inactive. Detergent builders can sequester the calcium ion needed for enzyme activity and/or stability.
Thus, there is a continuing need for the development of new enzymes that provide improved performance and better stability in liquid detergent compositions, particularly those containing high levels of anionic surfactant and builder.
Background Art U.S. Patent 4,261,868, Hora et al, issued April 14, l9~1, discloses liquid detergents containing enzymes and, as an enzyme-stabilizing system, 2-25% of a polyfunc-tional amino compound selected from diethanolamine, triethanolamine, di-isopropanolamine, triisopropanolamine and tris(hydroxymethyl) aminomethane, and 0.25-15% of a boron compound selected from boric acid, boric oxide, borax, and sodium ortho-, meta- and pyroborate. The compositions can contain 10-60% surfactant, including anionics, and up to 40% builder.
U.S. Patent 4,404,115, Tai, issued September 13, 1983, discloses li~uid cleaning compositions, preferably built liquid detergents, containing enzyme, 1-15% alkali metal pentaborate, 0-15% alkali metal sulfite, and 0-15%
of a polyol having 2-6 hydroxy groups. The compositions can contain 1-60% surfactant, preferably a mixture of anionic and nonionic in a weight ratio of 6:i to 1:1, with or without soap. The compositions also preferably contain 5-50% builder.
U.S. Patent 4,318,818, Letton et al, issued March 9, 1982, discloses liquid detergents containing enzymes and an enzyme-stabilizing system comprising calcium ion and a low molecular weight carboxylic acid or salt, preferably a formate. The compositions preferably contain from about 20% to 50% surfactant, which can be anionic. In a preferred embodiment, the compositions contain about 3%
~30292S
to 15~ of a saturated fatty acid. They are otherwise substantially free of builders, but can contain minor amounts of sequestrants.
European Patent Application 130,756, published January 9, 1985, discloses the proteolytic enzymes herein and methodc for their preparation. The enzymes are said to be useful in laundry d~tergents, both liquid and granular. They can be combined with surfactants (includ-ing anionics), builders, bleach and/or fluorescent whitening agents, but there is no disclosure of specific detergent compositions.
Summar _of the Invention This invention relates to liquid detergent composi-tions comprising, by weight:
15(a) from about 1% to about 75% of a synthetic detergent surfactant;
(b) 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 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 Lys Ala Val Ala Ser Gly Val Val ~al Val Ala Ala Ala Gly Asn Glu Gly Thr Ser Gly Ser Ser Ser Thr Val Gly Tyr Pro 170 180 0 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 Tyr Asn Gly Thr Ser Met Ala Ser Pro His Val Ala Gly Ala Ala Ala Leu Ile Leu Ser Lys His 240 250 0 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; ~hereinafter referred to as Protease A); or wherein the Gly at posi-tion 166 is replaced with Ser or Asn, the Gly at position 169 is replaced with Ser, or the Met at position 222 is replaced with Phe;
(c) from about 0.1% to about 10% of boric acid or a boron compound capable of forming boric acid in the composition;
(d) from about 0.01 to about 50 millimoles of calcium ion per liter of composition; and (e) from about 10% to about 95% of water;
Detailed Description of the Invention The liquid detergents of the present inventioncontain, as essential components, synthetic detergent surfactant, specific proteolytic enzyme, boric acid or a boron compound capable of forming boric acid in the composition, calcium ion, and water. The compositions exhibit improved enzyme stability because boric acid stabilizes the proteases herein to a greater degree than it does other proteases. This is particularly surprising given that the proteases herein do not exhibit improved stability in the absence of boric acid.
While not intending to be limited by theory, it is believed that boric acid and calcium form intramolecular bonds which cross-link or staple the enzyme molecule together, thereby holding it in its active spatial conformation. This mechanism is apparently more effec-tive for the proteases herein than for other proteases.
It is also believed that the relatively high level of anionic surfactant and builder in the preferred compositions herein provides an effective matrix for denaturing stains and exposing sites to enzymatic action.
The anionic surfactant is believed to be the primary denaturing agent, whereas the builder controls water hardness that would otherwise complex the anionic surfactant and interfere with its dena~uring action.
Once the stains are denatured, enzymes bind to the exposed sites and clip chemical bonds before returning to solution to begin the cycle again. After a sufficient number of clips are made, the stained fragments are removed and/or solubilized by the surfactants. However, it is believed that the preferred surfactant and builder matrix herein can denature and expose more sites on stains than currently available enzymes can cleave during the washing process. This is particularly true at low washing temperatures (e.g., in the range of 154C to 354C) where enzymes are catalytically slow. The present proteolytic enzymes appear to be ~superior to other proteases in catalytic efficiency. They ~hus can take advantage of the stain denaturing power of the preferred compositions herein and provide significant stain removal benefits. In contrast, they provide little or no stain removal benefits in detergent compositions containing less anionic surfactant and builder.
Synthetic Surfactan_ The compositions of the present invention contain from about 1% to about 75%, preferably from about 5% to about 50%, and most preferably from about 15% to about 35%, by weight of a synthetic surfactant, which can be an anionic, nonionic, cationic, zwitterionic or ampholytic surfactant, or mixtures thereof. Suitable synthetic 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, 1975.
Preferred compositions herein contain from about 7%
to about 50%, preferably from about 10% to about 40%, more preferably from about 15% to about 30%, by weight of an anionic synthetic surfactant.
Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkyl-olammonium (e.g., monoethanolammonium or triethanolam-monium) salts, of organic sulfuric reaction productshaving in their molecular structure an alkyl group containing from about 10 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 (C8-C18 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 15 carbon atoms, in , ~ .
130292~i 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 sulfonates 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 Ipreferably about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C8 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 l 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 C10-C18 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.
~302925 The compositions preferably contain from about 1% to about 5%, more preferably from about 2% to about 4%, by weight of unethoxylated alkyl sulfate. These alkyl sulfates are desired for best detergency performance, in S part because they are very denaturing to stains.
A preferred cosurfactant, used at a level of from about l~ to about 25%, preferably from about 3% to about 15%, by weight of the composition, is an ethoxylated nonionic surfactant of the formula R (OC2H4)nOH, wherein R is a ClO-Cl6 alkyl group or a C8-Cl2 alkyl phenyl group, n is from about 3 to about 9, and said nonionic surfactant has an HLB (hydrophile-lipophile balance) of from about ~ 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. Parti¢ularly preferred are condensatqon products of Cl2-Cl5 alcohols with from about 3 to about 8 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol con densed with about 6.5 moles of ethylene oxide per mole of alcohol.
Preferred cosurfactants for use with the above ethoxylated nonionic surfactants are amides of the formula O R
Rl _ C - I - 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 hydro-gen, 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.
~30292S
Preferred amides are the C8-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.
Certain compositions herein preferably contain from about 5% to about 20%, preferably from about 6% to about 15~, more preferably from about 7% to about 12%, by weight of a mixture of the above ethoxylated nonionic surfactant and amide surfactant in a weight ratio of from about 4:1 to 1:4, preferably from about 3:1 to about 1:3, more preferably from about 2:1 to about 1:2. In addi-tion, the weight ratio of anionic synthetic surfactant (on an acid basis) to the total nonionic surfactant (both the ethoxylated nonionic and the amide) should be from about 2:1 to about 4:1, preferably from about 2.5:1 to about 3.5:1, to ensure the formation and adsorption of sufficient hardness surfactants at the oil/water inter-face to provide good greasy/oily soil removal.
Other preferred cosurfactants, used at a level of from about 0.5% to about 3%, preferably from about 0.7~
to about 2%, by weight are the quaternary ammonium, amine or amine oxide surfactants described in U.S. Patent 4,507,219, Hughes, issued March 26, 1985.
While the compositions herein can contain di-long chain quaternary ammonium cationic surfactants (e.g., those having 2 chains, each containing an average of from about 16 to about 22 carbon atoms), such as disclosed in ~ritish Patent 2,041,968, Murphy, published September 19, 1979, the co~positions preferably contain less than about 2%, more preferably less than about 1%, by weight of such surfactants. Most preferably, the compositions are substantially free of such surfactants because they appear to be detrimental to the stability of the proteolytic enzymes herein.
1~0292S
Optional Detergency Builder The compositions also preferably contain from about 5~ to about 40%, more preferably from about 8% to about 30%, most preferably from about 10~ to about 25%, by weight of a detergent builder material. In addition, the composition preferably contain at least about 20%, more preferably from about 25% to about 60%, most preferably from about 30% to about 50%, by weight of the anionic synthetic surfactant and builder. 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 pref-erably contain sufficient builder to sequester from about 2 to about 10, preferably from about 3 to about 8, grains per gallon of hardness.
Useful builders are fatty acids containing from about 10 to about 22 carbon atoms. Preferred are satur-ated fatty acids containing from about 10 to about 18, preferably from about 10 to about 14, carbon atoms. When present, the fatty acid preferably represents about 5% to about 20~, more preferably from about 8% to about 16%, by weight of the composition.
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 synthetic-ally prepared (e.g., via the oxidation of petroleum or by hydrogenatio~ 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%-3~% of total fatty acid) of oleic acid; and palm kernel fatty acid.
~302g2S
~ etergent builders useful herein also include the polycarboxylate, polyphosphonate and polyphosphate builders described in U.S. Patent 4,284,532, Leikhim et al, issued August 18, 1981.
Water-soluble Polycarboxylate ~uilders, particularly citrates, are preferred of this group.
Polycarboxylate builders preferably represent from about 1% to about 20% by weight of the composition.
Suitable polycarboxylate builders include the various aminopolycarboxylates, cycloalkane poly-carboxylates, ether polycarboxylates, alkyl polycarboxyl-ates, epoxy polycarboxylates, tetrahydrofuran poly-carboxylates, 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 phytates, dis-closed in U.S. Patent 1,739,942, Eckey, issued March 27, 1956; the polycarboxylate materials described in -U. S. Patent 3,364,103;
and the water - soluble salts of polycarboxylate polymers and copolymers des-cribed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967.
Useful detergent builders also include the water-soluble salts of polymeric aliphatic polycarboxylic acids having the following structural and physical characteris-tics: (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 mor~ 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 130;~92S
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, carboxy-methyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclopentane-tetracarboxylic acid and oxydisuccinic acid.
Other polycarboxylates for use herein 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 detergent builders useful herein include the aluminosilicate ion exchange material described in U.S.
Patent 4,405,483, Xuzel et al, issued September 20, 1983.
As part of the builder system, the compositions herein preferably contain from about 0.1% to about 1~, more preferably from about 0.2% to about 0.6%, by weight of water~soluble salts of ethylenediamine tetramethylene-phosphonic acid, diethylenetriamine pentamethylenephos-phonic acid, ethylenediamine tetraacetic acid, or diethylenetriamine pentaacetic acid to enhance cleaning performance when pretreating fabrics.
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 composition of Protease A
as previously defined, or variants thereof in which the ~ ' .
13~1z392~
Gly at position 166 is replaced with Ser or Asn, the Gly at position 169 is replaced with Ser, or the Met at position 222 is replaced with Phe.
These proteases, and methods for their preparation, are described in European Patent Application 130,756, published January 9, 1985.
The above enzyme is preferably included in an amount sufficient to provide an activity of from about 0.001 to about 0.1, more preferably from about 0.005 to about 0.07, most preferably from about 0.01 to about 0.04, Anson units per gram of composition.
The proteases herein are preferably purified, prior to incorporation in the finished composition, so that they have no detectable odor at a concentration of less than about 0.002 Anson units per gram in distilled water.
They preferably have no detectable odor at a concen-tration of less than about 0.0025, more preferably less than about 0.003, ~nson units per gram of distilled water.
Proteases herein can be odor purified by any method known in the art. Examples include the solvent pre-cipitation methods described in PreciPitatlon of the EnzYmes and Their Stability in High Alcohol Concentra-tions by Bauer et al in the Israel J. Chem. 5(3), pages 25 llt-20 (1967) and Enzyme Preparations by Sugiura et al and Yakusaigaku 1967, Volume 27(2), pages 135-9.
Solvent initiated precipitation of a crude commer-cial enzyme solution results in most of the enzymatic activity being precipitated from solution and most of the odor and color impurities remaining in the supernatant liquid. Decantation or centrifugation of the supernatant liquid from the precipitated enzyme results in an enzyme fraction with enriched enzymatic activity/gram and improved odor and color.
~30292S
Various solvents or solvent pair combinatio~s can be used to effect the desired precipitation. For example, methanol, ethanol, acetone, other organic solvents, and combinations of organic solvents with and without water can be used. A highly preferred solvent is a combination of water and 30-70% by weight ethanol. This appears to be optimal to prevent enzyme deactivation and maximum recovery of activity.
Purification of protease enzymes also provide benefits in the area of product color stability.
Boric Acid The compositions of the present invention also contain from about 0.1% to about 10%, more preferably from about 0.25% to about 5%, most preferably from about 0.5% to about 3~, by weight of boric acid or a compound capable of forming boric acid in the composition (calcu-lated on the basis of the boric acid). 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.
Calcium Ion The composition also contains from about 0.01 to about 50, preferably from about 0.1 to about 30, more preferably from about l 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, gener-ally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the ensyme slurry and formula water.
Water Finally, the compositions herein contain from about 10% to about 95~, preferably from about 20~ to about 70~, more preferably from about 30% to about 50%, by weight of S water.
Other Optional Components Other preferred enzyme stabilizers for use in the present compositions are 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 propane diol, which is preferred), ethylene glycol, glycerol, sorbitol, mannitol, and glucose. The polyol generally represents from about 1% to about 15%, preferably from about 1.5% to about 10%, by weight of the composition.
Preferably, the weight ratio of polyol to boric acid is at least 1, more preferably at least about 1.3.
The compositions can 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 prefer-ably from about 0.4% to about 1.5~, by weight of the composition.
The compositions herein preferably have an initial pH of from about 6.5 to about 10.0, preferably from about 7 to about 8.5, most preferably from about 7.2 to about 8.0, at a concentration of 0.2% by weight in distilled water at 20C. Preferred pH buffers include monoethanol-amine and triethanolamine. Monoethanolamine and trieth-anolamine also further enhance enzyme stability, and preferably are included at levels of from about 0.5~ to about 10%, preferably from about 1% to about 4%, by weight of the composition.
Other optional components for use in the liquid detergents herein include soil removal agents, antire-deposition agents, suds regulants, hydrotropes, opaci-fiers, antioxidants, bactericides, dyes, perfumes, and brighteners known in the art. Such optional components generally represent less than about 15%, preferably from about 1% to about 10%, by weight of the composition.
Particularly preferred stable isotropic liquid detergents herein are described in U.S. Patent 4,507,219, Hughes, issued March 26, 1985.
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
The following detergent compositions were prepared.
Component Wt. %
A B C D E
C13 linear alkylbenzene sulfonic acid 7.2 8.0 - _ 8.0 C14-1s alkYl polyethoxyl-ate (2.25) sulfuric acid 10.8 12.0 - - 12.0 C12-14 alkyl polyethoxyl-ate (1) sulfuric acid - - 8.8 (Alkyl sulfuric acid) (2.5) (2.8) (3.9) - (2.8) C12-13 alcohol polyethoxyl_ ate (6.5) 6.5* 5.0* 21.5 - 5.0*
C14_15 alcohol polyethoxyl-ate (7)* - - - 18.0 30 C12 alkyl trimethylammon-ium chloride 1.2 0.6 - - 0.6 Ditallowalkyl dimethyl ammonium chloride - - - 3.6 C12-14 alkyl dimethyl amine oxide - - _ 4.0 .. ~, .
i302g2s C12-14 fatty acid 13.0 10.0 - - 7.7 Palm kernel fatty acid - - - - 3.3 Oleic acid 2.0 0.5 - - 2.0 Citric acid (anhydrous) 4.0 4.0 - - 4.0 Sodium diethylenetri-amine pentaacetate 0.3 0.3 - 0.3 Protease enzyme -- -As indicated ---Amylase enzyme (325 Am. U/g) - - - - 0.16 15-18** 1.5 2.0 - 1.5 2.0 Soil release compound**** - - - - 2.5 Monoethanolamine 2.0 2.0 - - 1.0 Sodium hydroxide 1.7 4.0 - - 2.0 Potassium hydroxide 4.0 1.6 - - 5.4 1,2 Propane diol 7.25 4.0 - - 6.5 Ethanol 7.75 8.5 5.7 7.5 7.0 Boric acid -- As indicated Sodium formate 1.0 1.0 1.6 1.2 1.0 Total calcium ion*** (mm/l) 9.65 9.65 0.25 0.25 9.65 Minors and water Balance to 100 20 Initial pH of 0.2% solution in distilled water at 20C 7.5 7.5 7.2 7.2 7.5 * Alcohol and monoethoxylated alcohol removed.
** Tetraethylene pentaimine ethoxylated with 15-18 moles (avg.) of ethylene oxide at each hydrogen site.
*** Includes estimated 0.25 millimoles of calcium ion per liter from enzyme slurry and formula water.
**** A compound having a range of copolymers of the formula:
CH3 - ~OCH2CH2tl6 O O CH
~0 -- C ~ C - CH2 - CHtU
O O
~O - C ~ C - O t ~CH2CH2O~16 CH3 in which about 20% by weight of the material has a value of u higher tha~ 5 is dissolved at about 15% level in anhydrous ethanol; cooled to about 10C; the insoluble portion (~ 20%) is filtered; and enough ethanol is distilled to reduce the ethanol level to within the level in the formula.
The following proteases were added to the above Compositions B, C and D at a level to provide an initial activity of 0.015 Anson units per gram. Protease sta~
bility, in terms of percent retained activity, was then determined after storage of the compositions for the indicated number of weeks. The results were as follows.
% Retained activity at 37.7C
Composition 1 wk 2 wk 3 wk 4 wk 5 wk 6 wk 8 wk B + Alcalase* 13 0 B + Maxatase** 15 0 B + Protease A 10 0 B + 1.25% boric acid + Alcalase 63 39 25 16 7 5 2 20 B + 1.25% boric acid + Maxatase 67 39 24 13 6 6 2 B + 1.25% boric acid + ProteaseA 98 75 53 50 33 30 18 C + Alcalase 94 88 76 70 60 66 C + Protease A 10091 80 71 61 63 D + Alcalase 93 96 92 82 71 77 D + Protease A 10090 62 64 54 64 *Trademark of Novo Industries A.S.
**Trademark of GistBrocades N.V.
% Retained activity at 21.1~C
Composition 1 wk 2 wk 3 wk 4 wk 5 wk 6 wk . _ . _ B + Alcalase 89 85 85 95 85 89 B + Maxatase 92 94 92 lQ0 100 100 B + Protease A 100 100 100 100 100 100 B + 1.25% boric acid + Alcalase 92 99 96 96 95 100 ,~ , 1~02925 B + 1.25% boric acid + Maxatase98100 100 98 93 100 B + 1.25% boric acid +ProteaseA 100100 100 97 100 100 C + Alcalase 100100100 99 93 100 C + Protease A 100 100 100 100 100 100 D + Alcalase 10095 87 85 88 100 D + Protease A 100 100 100 100 100 100 The above results demonstrate that all three proteases quickly lost activity in Composition B at 37.7C. The addition of 1.25~ boric acid to Composition B improved the stability of all three proteases, but to a much greater degree for Protease A. At 37.7C, the stability of Protease A was comparable to Alcalase in Composition C, and slightly worse in Composition D. All three proteases were stable in Compositions B, C and D at 21.1C.
The stability of Protease A and Maxatase in Composition B with varying levels of boric acid was as ~ollows.
Maxatase - % Retained Activity at 26.6C
Boric acid 0 wk1 wk2 wk3 wk4 wk5 wk 6 wk 0~ 10098 93 92 95 90 83 0.25% 100100 89 90 96 94 87 0.50% 100100 100 99 95 95 88 0.75% 10095 87 85 85 84 87 1.0% 10099 84 84 92 95 88 1.25% 10098 96 96 90 92 82 Protease A - % Retained Activit~ at 26.6C
Boric acid 0 wk1 wk2 wk3 wk4 wkS wk 6 wk 0% 100100 90 87 89 87 82 0.25% 100100 90 89 90 90 89 0.50% 10097 95 95 93 92 92 0.75% 10098 97 100 98 100 90 1.0% 100100 98 100 98 100 93 1.25% 100100 100 100 100 98 97 ~029~S
Maxatase - % Retained Activity at 32.2C
Boric acid 0 wk l wk 2 wk 3 wk 4 wk S wk 6 wk __ _ 0% 100 69 53 40 40 32 20 0.25% 100 84 66 60 46 42 36 0.50% lO0 86 74 69 60 54 45 0.75% 100 87 73 73 67 64 53 1.0% lO0 93 79 80 70 68 61 1.25% 100 94 83 79 77 70 61 Protease A - ~ Retained Activity at 32.2C
Boric acid 0 wk1 wk2 wk 3 wk 4 wk 5 wk 6 wk -0% lO0 67 42 30 22 20 12 0.25% lO0 85 70 72 60 52 45 0.50% 100 86 72 67 68 67 60 0.75% 100 97 79 90* 79 80 75 1.0% 100 97 92 90 92 90 79 1.25% 100100 95 92 85 ~9 80 *Apparently erroneous data.
Maxatase - % Retained ActivitY at 37.7C
Boric acid 0 wk1 wk2 wk 3 wk 4 wk 5 wk 6 wk_ _ _ _ _ _ 0% 1002.4 0.5 0.4 0.4 0.4 0.1 0.25% 100 12 3.6 1.2 0.7 0.8 0.4 0.50% 100 26 11 6 3 1 2 0.75% 100 34 15 8 3 2 1.0% 100 45 24 16 10 6 4 1.25% 100 46 29 20 14 7 5 Protease A - % Retained Activity at 37.7C__ Boric acid 0 wk l wk 2 wk 3 wk 4 wk 5 wk 6 wk . _ 0% 1001.6 0.8 0.3 0.2 0.3 0 0.25% 100 21 8 1.6 1 0.5 0.3 0.50% 100 40 19 11 8 3 2 0.75% 100 56 31 30 18 11 7 1.0% 100 67 48 40 35 17 15 1.25% 100 72 57 48 38 33 21 Protease A and Maxatase had comparable stability in Composition B without boric acid. The addition of boric acid improved the stability of both proteases, but to a much greater degree for Protease A, particularly at longer storage times and higher temperatures.
In Composition C, Protease A, Alcalase and Maxatase had simi~ar stability. The addition of boric acid improved the stability of Protease A, and decreased the stability of Alcalase and Maxatase, as demonstrated by the following results.
_ Retained Activity at 37.7C
Protease A + O wk 1 wk _ 3 wk 4 wk S wk 6 wk 0% boric acid 100 88 63 50 46 41 32 0.5% boric acid 100 90 93 87 80 77 76 1.25% boric acidlOO 97 97 79 89 82 78 Alcalase +
0% boric acid 100 93 6636* 50 41 42 0.5% boric acid 100 81 56 54 30 23 17 1.25% boric acidlOO 73 44 22 19 14 12 Maxatase +
0% boric acid 100 86 7222* 51 47 44 0.5% boric acid 100 83 63 43 35 31 23 1.25% boric acidlOO 86 53 33 27 17 14 *Apparently erroneous data.
In Composition D, Alcalase and Maxatase were sig-nificantly more stable than Protease A. However, theaddition of boric acid directionally improved the stabil-ity of Protease A but decreased the stability of Alcalase and Maxatase, as demonstrated by the following results.
% Retained Activity at 37.7C
Protease A + O wk 1 wk 2 wk 3 wk 4 wk 5 wk 6 wk .
0% boric acid 100 16 3 0.80.5 0.3 0.2 0.5% boric acid 100 37 3 0.6 0.1 0.3 0.1 1.25% boric acidlOO 50 7 1 0.4 0 0.1 Alcalase +
0% boric acid 100 76 S9 43 34 26 24 0.5% boric acid 100 16 7 5 5 4 0.2 1.25% boric acidlOO 22 10 8 7 6 5 130~925 Maxatase +
0% boric acid 100 74 50 35 30 20 16 0.5% boric acid 100 18 7 4 4 2 1.25% boric acidlOO 25 10 6 6 4 2 The above results demonstrate that Protease A has a substantially diferent stability profile in combination with boric acid than does Alcalase or Maxatase.
In Composition B with boric acid, protease A and variants of Protease A in which the Gly at position 166 is replaced with Ser or Asn, the Gly at position 169 is replaced with Ser, or the Met at position 222 is replaced with Phe, also exhibited improved stability versus Alcalase and the variant of Protease A in which the Met at position 222 is replaced with Gln, as demonstrated by the following results.
% Retained activity at 37.7C
0% Boric Acid+ O wk 1 wk 2 wk 3 wk Alcalase100 10 0.9 0.2 Protease A100 5 0.5 0 Asn-166 100 21 9 Gln-222 100 18 2 Ser-169 100 4 0.7 Phe-222 100 6 Ser-16S 100 18 1.25% B.A. +O wk1 wk 2 wk3 wk 4 wk5 wk 6 wk Alcalase100 62 43 29 17 12 10 Protease A100 77 73 53 48 40 35 Asn-166 100 78 70 68 51 46 41 Gln-222 100 93 36 6 3 2 0 Ser-169 100 49 47 37 33 26 21 Phe-222 100 - - 52 40 40 32 Ser-166 100 77 83 77 66 60 54 Compositions A and E of the present invention contain 0.75~ of a slurry of Protease A, providing an activity of 0.015 Anson units per gram of composition, and 1.25% boric acid in place of water.
i30292S
The invention herein can also be utilized in light-duty liquid detergent compositions, such as those described in U.S. Patent 3,634,266, Thiele et al, U~S.
Patent 3,799,879, Francke et al, U.S. Patent 3,707,505, Maeda et al, U.S. Patent 4,316,824, Pancheri, and U.S.
Patent 4,457,856, Mitchell et al, and in hard surface cleaning compositions, such as described in U.S. Patent 3,981,826, Munro, and U.S. Patent 3,985,668, Hartman.
.
13~292S
LIQUID DETERGENTS CONTAINING
SURFACTANT, PROTEOLYTIC ENZYME AND BORIC ACID
~anuel G~ Venegas Technical Field The present invention relates to liquid detergent compositions containing synthetic surfactant, specific proteolytic enzyme, boric acid or a boron compound capable of forming boric acid in the composition, and calcium ion. The compositions exhibit improved enzyme stability because boric acid stabilizes the proteases herein to a greater degree than it does other proteases.
The compositions are preferably heavy-duty liquid laundry detergents, but can also be light-duty liquid detergents suitable for dishwashing or washing fine fabrics, deter-gent pretreatment compositions or all-purpose household liquid cleaners. Preferred laundry detergent composi-tions containing a relatively high level of anionic surfactant and detergency builder also provide improved cleaning performance, particularly through-the-wash, of enzyme-sensitive stains such as gras~, blood, gravy and chocolate pudding.
Laundry detergents containing high levels of anionic surfactant and builder, and capable of providing superior cleaning performance, are currently available. Some of these compositions also contain enzymes to enhance removal of enzyme-sensitive stains. However, it is believed that such compositions are enzyme-limited in that they can denature and expose stains to enzymatic action faster than currently availa~le enzymes can cleave and break up the stains.
Enzyme performance can also be limited by a lack of adequate stability in liquid detergents. The stabiliza-tion of enzymes is particularly difficult in built, heavy-duty liquid detergents containing high levels of anionic surfactant and water. Anionic surfactants, especially alkyl sulfates, tend to denature enzymes and ~302925 render them inactive. Detergent builders can sequester the calcium ion needed for enzyme activity and/or stability.
Thus, there is a continuing need for the development of new enzymes that provide improved performance and better stability in liquid detergent compositions, particularly those containing high levels of anionic surfactant and builder.
Background Art U.S. Patent 4,261,868, Hora et al, issued April 14, l9~1, discloses liquid detergents containing enzymes and, as an enzyme-stabilizing system, 2-25% of a polyfunc-tional amino compound selected from diethanolamine, triethanolamine, di-isopropanolamine, triisopropanolamine and tris(hydroxymethyl) aminomethane, and 0.25-15% of a boron compound selected from boric acid, boric oxide, borax, and sodium ortho-, meta- and pyroborate. The compositions can contain 10-60% surfactant, including anionics, and up to 40% builder.
U.S. Patent 4,404,115, Tai, issued September 13, 1983, discloses li~uid cleaning compositions, preferably built liquid detergents, containing enzyme, 1-15% alkali metal pentaborate, 0-15% alkali metal sulfite, and 0-15%
of a polyol having 2-6 hydroxy groups. The compositions can contain 1-60% surfactant, preferably a mixture of anionic and nonionic in a weight ratio of 6:i to 1:1, with or without soap. The compositions also preferably contain 5-50% builder.
U.S. Patent 4,318,818, Letton et al, issued March 9, 1982, discloses liquid detergents containing enzymes and an enzyme-stabilizing system comprising calcium ion and a low molecular weight carboxylic acid or salt, preferably a formate. The compositions preferably contain from about 20% to 50% surfactant, which can be anionic. In a preferred embodiment, the compositions contain about 3%
~30292S
to 15~ of a saturated fatty acid. They are otherwise substantially free of builders, but can contain minor amounts of sequestrants.
European Patent Application 130,756, published January 9, 1985, discloses the proteolytic enzymes herein and methodc for their preparation. The enzymes are said to be useful in laundry d~tergents, both liquid and granular. They can be combined with surfactants (includ-ing anionics), builders, bleach and/or fluorescent whitening agents, but there is no disclosure of specific detergent compositions.
Summar _of the Invention This invention relates to liquid detergent composi-tions comprising, by weight:
15(a) from about 1% to about 75% of a synthetic detergent surfactant;
(b) 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 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 Lys Ala Val Ala Ser Gly Val Val ~al Val Ala Ala Ala Gly Asn Glu Gly Thr Ser Gly Ser Ser Ser Thr Val Gly Tyr Pro 170 180 0 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 Tyr Asn Gly Thr Ser Met Ala Ser Pro His Val Ala Gly Ala Ala Ala Leu Ile Leu Ser Lys His 240 250 0 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; ~hereinafter referred to as Protease A); or wherein the Gly at posi-tion 166 is replaced with Ser or Asn, the Gly at position 169 is replaced with Ser, or the Met at position 222 is replaced with Phe;
(c) from about 0.1% to about 10% of boric acid or a boron compound capable of forming boric acid in the composition;
(d) from about 0.01 to about 50 millimoles of calcium ion per liter of composition; and (e) from about 10% to about 95% of water;
Detailed Description of the Invention The liquid detergents of the present inventioncontain, as essential components, synthetic detergent surfactant, specific proteolytic enzyme, boric acid or a boron compound capable of forming boric acid in the composition, calcium ion, and water. The compositions exhibit improved enzyme stability because boric acid stabilizes the proteases herein to a greater degree than it does other proteases. This is particularly surprising given that the proteases herein do not exhibit improved stability in the absence of boric acid.
While not intending to be limited by theory, it is believed that boric acid and calcium form intramolecular bonds which cross-link or staple the enzyme molecule together, thereby holding it in its active spatial conformation. This mechanism is apparently more effec-tive for the proteases herein than for other proteases.
It is also believed that the relatively high level of anionic surfactant and builder in the preferred compositions herein provides an effective matrix for denaturing stains and exposing sites to enzymatic action.
The anionic surfactant is believed to be the primary denaturing agent, whereas the builder controls water hardness that would otherwise complex the anionic surfactant and interfere with its dena~uring action.
Once the stains are denatured, enzymes bind to the exposed sites and clip chemical bonds before returning to solution to begin the cycle again. After a sufficient number of clips are made, the stained fragments are removed and/or solubilized by the surfactants. However, it is believed that the preferred surfactant and builder matrix herein can denature and expose more sites on stains than currently available enzymes can cleave during the washing process. This is particularly true at low washing temperatures (e.g., in the range of 154C to 354C) where enzymes are catalytically slow. The present proteolytic enzymes appear to be ~superior to other proteases in catalytic efficiency. They ~hus can take advantage of the stain denaturing power of the preferred compositions herein and provide significant stain removal benefits. In contrast, they provide little or no stain removal benefits in detergent compositions containing less anionic surfactant and builder.
Synthetic Surfactan_ The compositions of the present invention contain from about 1% to about 75%, preferably from about 5% to about 50%, and most preferably from about 15% to about 35%, by weight of a synthetic surfactant, which can be an anionic, nonionic, cationic, zwitterionic or ampholytic surfactant, or mixtures thereof. Suitable synthetic 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, 1975.
Preferred compositions herein contain from about 7%
to about 50%, preferably from about 10% to about 40%, more preferably from about 15% to about 30%, by weight of an anionic synthetic surfactant.
Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkyl-olammonium (e.g., monoethanolammonium or triethanolam-monium) salts, of organic sulfuric reaction productshaving in their molecular structure an alkyl group containing from about 10 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 (C8-C18 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 15 carbon atoms, in , ~ .
130292~i 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 sulfonates 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 Ipreferably about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C8 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 l 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 C10-C18 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.
~302925 The compositions preferably contain from about 1% to about 5%, more preferably from about 2% to about 4%, by weight of unethoxylated alkyl sulfate. These alkyl sulfates are desired for best detergency performance, in S part because they are very denaturing to stains.
A preferred cosurfactant, used at a level of from about l~ to about 25%, preferably from about 3% to about 15%, by weight of the composition, is an ethoxylated nonionic surfactant of the formula R (OC2H4)nOH, wherein R is a ClO-Cl6 alkyl group or a C8-Cl2 alkyl phenyl group, n is from about 3 to about 9, and said nonionic surfactant has an HLB (hydrophile-lipophile balance) of from about ~ 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. Parti¢ularly preferred are condensatqon products of Cl2-Cl5 alcohols with from about 3 to about 8 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol con densed with about 6.5 moles of ethylene oxide per mole of alcohol.
Preferred cosurfactants for use with the above ethoxylated nonionic surfactants are amides of the formula O R
Rl _ C - I - 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 hydro-gen, 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.
~30292S
Preferred amides are the C8-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.
Certain compositions herein preferably contain from about 5% to about 20%, preferably from about 6% to about 15~, more preferably from about 7% to about 12%, by weight of a mixture of the above ethoxylated nonionic surfactant and amide surfactant in a weight ratio of from about 4:1 to 1:4, preferably from about 3:1 to about 1:3, more preferably from about 2:1 to about 1:2. In addi-tion, the weight ratio of anionic synthetic surfactant (on an acid basis) to the total nonionic surfactant (both the ethoxylated nonionic and the amide) should be from about 2:1 to about 4:1, preferably from about 2.5:1 to about 3.5:1, to ensure the formation and adsorption of sufficient hardness surfactants at the oil/water inter-face to provide good greasy/oily soil removal.
Other preferred cosurfactants, used at a level of from about 0.5% to about 3%, preferably from about 0.7~
to about 2%, by weight are the quaternary ammonium, amine or amine oxide surfactants described in U.S. Patent 4,507,219, Hughes, issued March 26, 1985.
While the compositions herein can contain di-long chain quaternary ammonium cationic surfactants (e.g., those having 2 chains, each containing an average of from about 16 to about 22 carbon atoms), such as disclosed in ~ritish Patent 2,041,968, Murphy, published September 19, 1979, the co~positions preferably contain less than about 2%, more preferably less than about 1%, by weight of such surfactants. Most preferably, the compositions are substantially free of such surfactants because they appear to be detrimental to the stability of the proteolytic enzymes herein.
1~0292S
Optional Detergency Builder The compositions also preferably contain from about 5~ to about 40%, more preferably from about 8% to about 30%, most preferably from about 10~ to about 25%, by weight of a detergent builder material. In addition, the composition preferably contain at least about 20%, more preferably from about 25% to about 60%, most preferably from about 30% to about 50%, by weight of the anionic synthetic surfactant and builder. 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 pref-erably contain sufficient builder to sequester from about 2 to about 10, preferably from about 3 to about 8, grains per gallon of hardness.
Useful builders are fatty acids containing from about 10 to about 22 carbon atoms. Preferred are satur-ated fatty acids containing from about 10 to about 18, preferably from about 10 to about 14, carbon atoms. When present, the fatty acid preferably represents about 5% to about 20~, more preferably from about 8% to about 16%, by weight of the composition.
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 synthetic-ally prepared (e.g., via the oxidation of petroleum or by hydrogenatio~ 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%-3~% of total fatty acid) of oleic acid; and palm kernel fatty acid.
~302g2S
~ etergent builders useful herein also include the polycarboxylate, polyphosphonate and polyphosphate builders described in U.S. Patent 4,284,532, Leikhim et al, issued August 18, 1981.
Water-soluble Polycarboxylate ~uilders, particularly citrates, are preferred of this group.
Polycarboxylate builders preferably represent from about 1% to about 20% by weight of the composition.
Suitable polycarboxylate builders include the various aminopolycarboxylates, cycloalkane poly-carboxylates, ether polycarboxylates, alkyl polycarboxyl-ates, epoxy polycarboxylates, tetrahydrofuran poly-carboxylates, 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 phytates, dis-closed in U.S. Patent 1,739,942, Eckey, issued March 27, 1956; the polycarboxylate materials described in -U. S. Patent 3,364,103;
and the water - soluble salts of polycarboxylate polymers and copolymers des-cribed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967.
Useful detergent builders also include the water-soluble salts of polymeric aliphatic polycarboxylic acids having the following structural and physical characteris-tics: (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 mor~ 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 130;~92S
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, carboxy-methyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclopentane-tetracarboxylic acid and oxydisuccinic acid.
Other polycarboxylates for use herein 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 detergent builders useful herein include the aluminosilicate ion exchange material described in U.S.
Patent 4,405,483, Xuzel et al, issued September 20, 1983.
As part of the builder system, the compositions herein preferably contain from about 0.1% to about 1~, more preferably from about 0.2% to about 0.6%, by weight of water~soluble salts of ethylenediamine tetramethylene-phosphonic acid, diethylenetriamine pentamethylenephos-phonic acid, ethylenediamine tetraacetic acid, or diethylenetriamine pentaacetic acid to enhance cleaning performance when pretreating fabrics.
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 composition of Protease A
as previously defined, or variants thereof in which the ~ ' .
13~1z392~
Gly at position 166 is replaced with Ser or Asn, the Gly at position 169 is replaced with Ser, or the Met at position 222 is replaced with Phe.
These proteases, and methods for their preparation, are described in European Patent Application 130,756, published January 9, 1985.
The above enzyme is preferably included in an amount sufficient to provide an activity of from about 0.001 to about 0.1, more preferably from about 0.005 to about 0.07, most preferably from about 0.01 to about 0.04, Anson units per gram of composition.
The proteases herein are preferably purified, prior to incorporation in the finished composition, so that they have no detectable odor at a concentration of less than about 0.002 Anson units per gram in distilled water.
They preferably have no detectable odor at a concen-tration of less than about 0.0025, more preferably less than about 0.003, ~nson units per gram of distilled water.
Proteases herein can be odor purified by any method known in the art. Examples include the solvent pre-cipitation methods described in PreciPitatlon of the EnzYmes and Their Stability in High Alcohol Concentra-tions by Bauer et al in the Israel J. Chem. 5(3), pages 25 llt-20 (1967) and Enzyme Preparations by Sugiura et al and Yakusaigaku 1967, Volume 27(2), pages 135-9.
Solvent initiated precipitation of a crude commer-cial enzyme solution results in most of the enzymatic activity being precipitated from solution and most of the odor and color impurities remaining in the supernatant liquid. Decantation or centrifugation of the supernatant liquid from the precipitated enzyme results in an enzyme fraction with enriched enzymatic activity/gram and improved odor and color.
~30292S
Various solvents or solvent pair combinatio~s can be used to effect the desired precipitation. For example, methanol, ethanol, acetone, other organic solvents, and combinations of organic solvents with and without water can be used. A highly preferred solvent is a combination of water and 30-70% by weight ethanol. This appears to be optimal to prevent enzyme deactivation and maximum recovery of activity.
Purification of protease enzymes also provide benefits in the area of product color stability.
Boric Acid The compositions of the present invention also contain from about 0.1% to about 10%, more preferably from about 0.25% to about 5%, most preferably from about 0.5% to about 3~, by weight of boric acid or a compound capable of forming boric acid in the composition (calcu-lated on the basis of the boric acid). 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.
Calcium Ion The composition also contains from about 0.01 to about 50, preferably from about 0.1 to about 30, more preferably from about l 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, gener-ally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the ensyme slurry and formula water.
Water Finally, the compositions herein contain from about 10% to about 95~, preferably from about 20~ to about 70~, more preferably from about 30% to about 50%, by weight of S water.
Other Optional Components Other preferred enzyme stabilizers for use in the present compositions are 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 propane diol, which is preferred), ethylene glycol, glycerol, sorbitol, mannitol, and glucose. The polyol generally represents from about 1% to about 15%, preferably from about 1.5% to about 10%, by weight of the composition.
Preferably, the weight ratio of polyol to boric acid is at least 1, more preferably at least about 1.3.
The compositions can 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 prefer-ably from about 0.4% to about 1.5~, by weight of the composition.
The compositions herein preferably have an initial pH of from about 6.5 to about 10.0, preferably from about 7 to about 8.5, most preferably from about 7.2 to about 8.0, at a concentration of 0.2% by weight in distilled water at 20C. Preferred pH buffers include monoethanol-amine and triethanolamine. Monoethanolamine and trieth-anolamine also further enhance enzyme stability, and preferably are included at levels of from about 0.5~ to about 10%, preferably from about 1% to about 4%, by weight of the composition.
Other optional components for use in the liquid detergents herein include soil removal agents, antire-deposition agents, suds regulants, hydrotropes, opaci-fiers, antioxidants, bactericides, dyes, perfumes, and brighteners known in the art. Such optional components generally represent less than about 15%, preferably from about 1% to about 10%, by weight of the composition.
Particularly preferred stable isotropic liquid detergents herein are described in U.S. Patent 4,507,219, Hughes, issued March 26, 1985.
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
The following detergent compositions were prepared.
Component Wt. %
A B C D E
C13 linear alkylbenzene sulfonic acid 7.2 8.0 - _ 8.0 C14-1s alkYl polyethoxyl-ate (2.25) sulfuric acid 10.8 12.0 - - 12.0 C12-14 alkyl polyethoxyl-ate (1) sulfuric acid - - 8.8 (Alkyl sulfuric acid) (2.5) (2.8) (3.9) - (2.8) C12-13 alcohol polyethoxyl_ ate (6.5) 6.5* 5.0* 21.5 - 5.0*
C14_15 alcohol polyethoxyl-ate (7)* - - - 18.0 30 C12 alkyl trimethylammon-ium chloride 1.2 0.6 - - 0.6 Ditallowalkyl dimethyl ammonium chloride - - - 3.6 C12-14 alkyl dimethyl amine oxide - - _ 4.0 .. ~, .
i302g2s C12-14 fatty acid 13.0 10.0 - - 7.7 Palm kernel fatty acid - - - - 3.3 Oleic acid 2.0 0.5 - - 2.0 Citric acid (anhydrous) 4.0 4.0 - - 4.0 Sodium diethylenetri-amine pentaacetate 0.3 0.3 - 0.3 Protease enzyme -- -As indicated ---Amylase enzyme (325 Am. U/g) - - - - 0.16 15-18** 1.5 2.0 - 1.5 2.0 Soil release compound**** - - - - 2.5 Monoethanolamine 2.0 2.0 - - 1.0 Sodium hydroxide 1.7 4.0 - - 2.0 Potassium hydroxide 4.0 1.6 - - 5.4 1,2 Propane diol 7.25 4.0 - - 6.5 Ethanol 7.75 8.5 5.7 7.5 7.0 Boric acid -- As indicated Sodium formate 1.0 1.0 1.6 1.2 1.0 Total calcium ion*** (mm/l) 9.65 9.65 0.25 0.25 9.65 Minors and water Balance to 100 20 Initial pH of 0.2% solution in distilled water at 20C 7.5 7.5 7.2 7.2 7.5 * Alcohol and monoethoxylated alcohol removed.
** Tetraethylene pentaimine ethoxylated with 15-18 moles (avg.) of ethylene oxide at each hydrogen site.
*** Includes estimated 0.25 millimoles of calcium ion per liter from enzyme slurry and formula water.
**** A compound having a range of copolymers of the formula:
CH3 - ~OCH2CH2tl6 O O CH
~0 -- C ~ C - CH2 - CHtU
O O
~O - C ~ C - O t ~CH2CH2O~16 CH3 in which about 20% by weight of the material has a value of u higher tha~ 5 is dissolved at about 15% level in anhydrous ethanol; cooled to about 10C; the insoluble portion (~ 20%) is filtered; and enough ethanol is distilled to reduce the ethanol level to within the level in the formula.
The following proteases were added to the above Compositions B, C and D at a level to provide an initial activity of 0.015 Anson units per gram. Protease sta~
bility, in terms of percent retained activity, was then determined after storage of the compositions for the indicated number of weeks. The results were as follows.
% Retained activity at 37.7C
Composition 1 wk 2 wk 3 wk 4 wk 5 wk 6 wk 8 wk B + Alcalase* 13 0 B + Maxatase** 15 0 B + Protease A 10 0 B + 1.25% boric acid + Alcalase 63 39 25 16 7 5 2 20 B + 1.25% boric acid + Maxatase 67 39 24 13 6 6 2 B + 1.25% boric acid + ProteaseA 98 75 53 50 33 30 18 C + Alcalase 94 88 76 70 60 66 C + Protease A 10091 80 71 61 63 D + Alcalase 93 96 92 82 71 77 D + Protease A 10090 62 64 54 64 *Trademark of Novo Industries A.S.
**Trademark of GistBrocades N.V.
% Retained activity at 21.1~C
Composition 1 wk 2 wk 3 wk 4 wk 5 wk 6 wk . _ . _ B + Alcalase 89 85 85 95 85 89 B + Maxatase 92 94 92 lQ0 100 100 B + Protease A 100 100 100 100 100 100 B + 1.25% boric acid + Alcalase 92 99 96 96 95 100 ,~ , 1~02925 B + 1.25% boric acid + Maxatase98100 100 98 93 100 B + 1.25% boric acid +ProteaseA 100100 100 97 100 100 C + Alcalase 100100100 99 93 100 C + Protease A 100 100 100 100 100 100 D + Alcalase 10095 87 85 88 100 D + Protease A 100 100 100 100 100 100 The above results demonstrate that all three proteases quickly lost activity in Composition B at 37.7C. The addition of 1.25~ boric acid to Composition B improved the stability of all three proteases, but to a much greater degree for Protease A. At 37.7C, the stability of Protease A was comparable to Alcalase in Composition C, and slightly worse in Composition D. All three proteases were stable in Compositions B, C and D at 21.1C.
The stability of Protease A and Maxatase in Composition B with varying levels of boric acid was as ~ollows.
Maxatase - % Retained Activity at 26.6C
Boric acid 0 wk1 wk2 wk3 wk4 wk5 wk 6 wk 0~ 10098 93 92 95 90 83 0.25% 100100 89 90 96 94 87 0.50% 100100 100 99 95 95 88 0.75% 10095 87 85 85 84 87 1.0% 10099 84 84 92 95 88 1.25% 10098 96 96 90 92 82 Protease A - % Retained Activit~ at 26.6C
Boric acid 0 wk1 wk2 wk3 wk4 wkS wk 6 wk 0% 100100 90 87 89 87 82 0.25% 100100 90 89 90 90 89 0.50% 10097 95 95 93 92 92 0.75% 10098 97 100 98 100 90 1.0% 100100 98 100 98 100 93 1.25% 100100 100 100 100 98 97 ~029~S
Maxatase - % Retained Activity at 32.2C
Boric acid 0 wk l wk 2 wk 3 wk 4 wk S wk 6 wk __ _ 0% 100 69 53 40 40 32 20 0.25% 100 84 66 60 46 42 36 0.50% lO0 86 74 69 60 54 45 0.75% 100 87 73 73 67 64 53 1.0% lO0 93 79 80 70 68 61 1.25% 100 94 83 79 77 70 61 Protease A - ~ Retained Activity at 32.2C
Boric acid 0 wk1 wk2 wk 3 wk 4 wk 5 wk 6 wk -0% lO0 67 42 30 22 20 12 0.25% lO0 85 70 72 60 52 45 0.50% 100 86 72 67 68 67 60 0.75% 100 97 79 90* 79 80 75 1.0% 100 97 92 90 92 90 79 1.25% 100100 95 92 85 ~9 80 *Apparently erroneous data.
Maxatase - % Retained ActivitY at 37.7C
Boric acid 0 wk1 wk2 wk 3 wk 4 wk 5 wk 6 wk_ _ _ _ _ _ 0% 1002.4 0.5 0.4 0.4 0.4 0.1 0.25% 100 12 3.6 1.2 0.7 0.8 0.4 0.50% 100 26 11 6 3 1 2 0.75% 100 34 15 8 3 2 1.0% 100 45 24 16 10 6 4 1.25% 100 46 29 20 14 7 5 Protease A - % Retained Activity at 37.7C__ Boric acid 0 wk l wk 2 wk 3 wk 4 wk 5 wk 6 wk . _ 0% 1001.6 0.8 0.3 0.2 0.3 0 0.25% 100 21 8 1.6 1 0.5 0.3 0.50% 100 40 19 11 8 3 2 0.75% 100 56 31 30 18 11 7 1.0% 100 67 48 40 35 17 15 1.25% 100 72 57 48 38 33 21 Protease A and Maxatase had comparable stability in Composition B without boric acid. The addition of boric acid improved the stability of both proteases, but to a much greater degree for Protease A, particularly at longer storage times and higher temperatures.
In Composition C, Protease A, Alcalase and Maxatase had simi~ar stability. The addition of boric acid improved the stability of Protease A, and decreased the stability of Alcalase and Maxatase, as demonstrated by the following results.
_ Retained Activity at 37.7C
Protease A + O wk 1 wk _ 3 wk 4 wk S wk 6 wk 0% boric acid 100 88 63 50 46 41 32 0.5% boric acid 100 90 93 87 80 77 76 1.25% boric acidlOO 97 97 79 89 82 78 Alcalase +
0% boric acid 100 93 6636* 50 41 42 0.5% boric acid 100 81 56 54 30 23 17 1.25% boric acidlOO 73 44 22 19 14 12 Maxatase +
0% boric acid 100 86 7222* 51 47 44 0.5% boric acid 100 83 63 43 35 31 23 1.25% boric acidlOO 86 53 33 27 17 14 *Apparently erroneous data.
In Composition D, Alcalase and Maxatase were sig-nificantly more stable than Protease A. However, theaddition of boric acid directionally improved the stabil-ity of Protease A but decreased the stability of Alcalase and Maxatase, as demonstrated by the following results.
% Retained Activity at 37.7C
Protease A + O wk 1 wk 2 wk 3 wk 4 wk 5 wk 6 wk .
0% boric acid 100 16 3 0.80.5 0.3 0.2 0.5% boric acid 100 37 3 0.6 0.1 0.3 0.1 1.25% boric acidlOO 50 7 1 0.4 0 0.1 Alcalase +
0% boric acid 100 76 S9 43 34 26 24 0.5% boric acid 100 16 7 5 5 4 0.2 1.25% boric acidlOO 22 10 8 7 6 5 130~925 Maxatase +
0% boric acid 100 74 50 35 30 20 16 0.5% boric acid 100 18 7 4 4 2 1.25% boric acidlOO 25 10 6 6 4 2 The above results demonstrate that Protease A has a substantially diferent stability profile in combination with boric acid than does Alcalase or Maxatase.
In Composition B with boric acid, protease A and variants of Protease A in which the Gly at position 166 is replaced with Ser or Asn, the Gly at position 169 is replaced with Ser, or the Met at position 222 is replaced with Phe, also exhibited improved stability versus Alcalase and the variant of Protease A in which the Met at position 222 is replaced with Gln, as demonstrated by the following results.
% Retained activity at 37.7C
0% Boric Acid+ O wk 1 wk 2 wk 3 wk Alcalase100 10 0.9 0.2 Protease A100 5 0.5 0 Asn-166 100 21 9 Gln-222 100 18 2 Ser-169 100 4 0.7 Phe-222 100 6 Ser-16S 100 18 1.25% B.A. +O wk1 wk 2 wk3 wk 4 wk5 wk 6 wk Alcalase100 62 43 29 17 12 10 Protease A100 77 73 53 48 40 35 Asn-166 100 78 70 68 51 46 41 Gln-222 100 93 36 6 3 2 0 Ser-169 100 49 47 37 33 26 21 Phe-222 100 - - 52 40 40 32 Ser-166 100 77 83 77 66 60 54 Compositions A and E of the present invention contain 0.75~ of a slurry of Protease A, providing an activity of 0.015 Anson units per gram of composition, and 1.25% boric acid in place of water.
i30292S
The invention herein can also be utilized in light-duty liquid detergent compositions, such as those described in U.S. Patent 3,634,266, Thiele et al, U~S.
Patent 3,799,879, Francke et al, U.S. Patent 3,707,505, Maeda et al, U.S. Patent 4,316,824, Pancheri, and U.S.
Patent 4,457,856, Mitchell et al, and in hard surface cleaning compositions, such as described in U.S. Patent 3,981,826, Munro, and U.S. Patent 3,985,668, Hartman.
.
Claims (18)
1. A liquid detergent composition comprising, by weight:
(a) from about 7% to about 50% of an anionic synthetic detergent surfactant which comprises a C10-C18 alkyl sulfate, a C10-C18 alkyl ethoxy sulfate containing an average of up to about 4 moles of ethylene oxide per mole of alkyl sulfate, a C11-C13 linear alkylbenzene sulfonate, or mixtures thereof;
(b) from about 0.01% to about 5% of a proteolytic enzyme having the following amino acid sequence:
(c) from about 0.25% to about 5% of boric acid or a boron compound capable of forming boric acid in the composition;
(d) from about 0.1 to about 30 millimoles of calcium ion per liter of composition; and (e) from about 20% to about 70% of water.
(a) from about 7% to about 50% of an anionic synthetic detergent surfactant which comprises a C10-C18 alkyl sulfate, a C10-C18 alkyl ethoxy sulfate containing an average of up to about 4 moles of ethylene oxide per mole of alkyl sulfate, a C11-C13 linear alkylbenzene sulfonate, or mixtures thereof;
(b) from about 0.01% to about 5% of a proteolytic enzyme having the following amino acid sequence:
(c) from about 0.25% to about 5% of boric acid or a boron compound capable of forming boric acid in the composition;
(d) from about 0.1 to about 30 millimoles of calcium ion per liter of composition; and (e) from about 20% to about 70% of water.
2. A composition according to claim 1 comprising from about 15% to about 30% of an anionic surfactant which comprises a C10-C18 alkyl sulfate, a C10-C18 alkyl ethoxy sulfate containing an average of up to about 4 moles of ethylene oxide per mole of alkyl sulfate, a C11-C13 linear alkylbenzene sulfonate, or mixtures thereof.
3. A composition according to Claim 2 comprising from about 30% to about 50% of a mixture of an anionic synthetic surfactant and a detergency builder, said composition having an initial pH of from about 7.0 to about 8.5 at a concentration of 0.2% in water at 20°C.
4. A composition according to Claim 3 comprising from about 5% to about 20% of a saturated fatty acid containing from about 10 to about 14 carbon atoms.
5. A composition according to Claim 3 comprising from about 1% to about 20% of a water-soluble polycarboxylate builder.
6. A composition according to Claim 3 comprising from about 0.5% to about 3% of boric acid.
7. A composition according to Claim 6 further comprising from about 1% to about 15% of a polyol containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups.
8. A composition according to Claim 7 wherein the polyol comprises 1,2 propane diol.
9. A composition according to Claim 6 further comprising from about 0.4% to about 1.5% of a water-soluble formate.
10. A composition according to Claim 1 wherein the proteolytic enzyme has the following amino acid sequence:
11. A composition according to Claim 1 comprising from about 1% to about 5% of an unethoxylated C10-C18 alkyl sulfate surfactant.
12. A composition according to Claim 1 further comprising from about 1% to about 25% of an ethoxylated nonionic surfactant of the formula R1(OC2H4)n OH, wherein R1 is a C10-C16 alkyl group, n is from about 3 to about 9, and said surfactant has an HLB of from about 10 to about 13.
13. A composition according to Claim 12 comprising from about 0.5% to about 3% of boric acid.
14. A composition according to Claim 13 wherein the proteolytic enzyme has the following amino acid sequence
15. A composition according to Claim 14 comprising from about 15% to about 30% of a C10-C18 alkyl sulfate, a C10-C18 alkyl ethoxy sulfate containing an average of up to about 4 moles of ethylene oxide per mole of alkyl sulfate, a C11-C13 linear alkylbenzene sulfonate, or mixtures thereof.
16. A composition according to Claim 14 comprising from about 25% to about 60% of a mixture of anionic synthetic surfactant and detergency builder.
17. A composition according to Claim 16 comprising from about 1% to about 20% of a water-soluble polycarboxylate builder.
18. A composition according to Claim 17 wherein the polycarboxylate builder comprises citrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72310385A | 1985-04-15 | 1985-04-15 | |
| US723,103 | 1985-04-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1302925C true CA1302925C (en) | 1992-06-09 |
Family
ID=24904854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000506568A Expired - Fee Related CA1302925C (en) | 1985-04-15 | 1986-04-14 | Liquid detergents containing surfactant, proteolytic enzyme and boric acid |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0199405B1 (en) |
| JP (1) | JPS62596A (en) |
| AT (1) | ATE77649T1 (en) |
| CA (1) | CA1302925C (en) |
| DE (1) | DE3685769T2 (en) |
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|---|---|---|---|---|
| US4914031A (en) * | 1987-04-10 | 1990-04-03 | Amgen, Inc. | Subtilisin analogs |
| US6287841B1 (en) | 1988-02-11 | 2001-09-11 | Genencor International, Inc. | High alkaline serine protease |
| PT89702B (en) | 1988-02-11 | 1994-04-29 | Gist Brocades Nv | PROCESS FOR PREPARING NEW PROTEOLITIC ENZYMES AND DETERGENTS THAT CONTAINS THEM |
| US5039446A (en) * | 1988-07-01 | 1991-08-13 | Genencor International, Inc. | Liquid detergent with stabilized enzyme |
| NZ237570A (en) * | 1990-04-13 | 1993-09-27 | Colgate Palmolive Co | Enzyme stabilising composition and stabilised enzyme-containing built detergent compositions |
| RU2088645C1 (en) * | 1990-09-28 | 1997-08-27 | Дзе Проктер Энд Гэмбл Компани | Detergent composition and a method of cleansing effect improvement with respect to detergent fabric |
| US5178789A (en) * | 1991-06-27 | 1993-01-12 | Genencor International, Inc. | Liquid detergent with stabilized enzyme |
| JPH0514182U (en) * | 1991-08-08 | 1993-02-23 | 津田駒工業株式会社 | Weft detection device |
| CA2133446A1 (en) * | 1992-04-13 | 1993-10-28 | Janet L. Marshall | Thixotropic liquid automatic dishwashing composition with enzyme |
| EP0693549A1 (en) | 1994-07-19 | 1996-01-24 | The Procter & Gamble Company | Solid bleach activator compositions |
| DE69502097T2 (en) | 1995-07-13 | 1998-11-12 | Procter & Gamble | Packaged foaming composition |
| EP0753567A1 (en) | 1995-07-14 | 1997-01-15 | The Procter & Gamble Company | Softening through the wash compositions |
| EP0778342A1 (en) | 1995-12-06 | 1997-06-11 | The Procter & Gamble Company | Detergent compositions |
| WO1997042282A1 (en) | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Detergent compositions comprising polyamine polymers with improved soil dispersancy |
| GB2367065B (en) | 2000-09-20 | 2002-11-20 | Reckitt Benckiser Inc | Enzyme containing laundry booster compositions |
| GB0104980D0 (en) * | 2001-02-28 | 2001-04-18 | Unilever Plc | Liquid cleaning compositions and their use |
| GB2373254A (en) * | 2001-03-16 | 2002-09-18 | Procter & Gamble | Detergent product |
| GB0207430D0 (en) * | 2002-03-28 | 2002-05-08 | Unilever Plc | Liquid cleaning compositionsand their use |
| US8933131B2 (en) | 2010-01-12 | 2015-01-13 | The Procter & Gamble Company | Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same |
| CN102939367A (en) | 2010-05-14 | 2013-02-20 | 太阳产品公司 | Polymer-containing cleaning compositions and methods of production and use thereof |
| MX2012015174A (en) | 2010-07-02 | 2013-05-09 | Procter & Gamble | Filaments comprising an active agent nonwoven webs and methods for making same. |
| WO2012003300A2 (en) | 2010-07-02 | 2012-01-05 | The Procter & Gamble Company | Filaments comprising a non-perfume active agent nonwoven webs and methods for making same |
| MX2012015187A (en) | 2010-07-02 | 2013-05-09 | Procter & Gamble | Method for delivering an active agent. |
| CA2803636C (en) | 2010-07-02 | 2017-05-16 | The Procter & Gamble Company | Detergent product and method for making same |
| CA2803371C (en) | 2010-07-02 | 2016-04-19 | The Procter & Gamble Company | Process for making films from nonwoven webs |
| US20120172281A1 (en) | 2010-07-15 | 2012-07-05 | Jeffrey John Scheibel | Detergent compositions comprising microbially produced fatty alcohols and derivatives thereof |
| MX2013000592A (en) | 2010-07-15 | 2013-03-05 | Procter & Gamble | A personal care composition comprising a near-terminal branched compound. |
| US20120213726A1 (en) | 2011-02-17 | 2012-08-23 | Phillip Richard Green | Bio-based linear alkylphenyl sulfonates |
| JP5815750B2 (en) | 2011-02-17 | 2015-11-17 | ザ プロクター アンド ギャンブルカンパニー | Composition comprising a mixture of C10 to C13 alkyl phenyl sulfonates |
| EP2725912A4 (en) | 2011-06-29 | 2015-03-04 | Solae Llc | Baked food compositions comprising soy whey proteins that have been isolated from processing streams |
| US20130072414A1 (en) | 2011-09-20 | 2013-03-21 | The Procter & Gamble Company | Detergent compositions comprising sustainable surfactant systems comprising isoprenoid-derived surfactants |
| WO2013043855A2 (en) | 2011-09-20 | 2013-03-28 | The Procter & Gamble Company | High suds detergent compositions comprising isoprenoid-based surfactants |
| AR088758A1 (en) | 2011-09-20 | 2014-07-02 | Procter & Gamble | EASY DETERGENT COMPOSITIONS RINSE THAT UNDERSTAND ISOPRENOID BASED SURFACTANTS |
| US20130072415A1 (en) | 2011-09-20 | 2013-03-21 | The Procter & Gamble Company | DETERGENT COMPOSITIONS COMPRISING SPECIFIC BLEND RATIOS of ISOPRENOID-BASED SURFACTANTS |
| CN103797101A (en) | 2011-09-20 | 2014-05-14 | 宝洁公司 | Detergent compositions comprising primary surfactant systems comprising highly branched surfactants especially isoprenoid-based surfactants |
| MX2014005562A (en) | 2011-11-11 | 2014-05-30 | Procter & Gamble | Surface treatment compositions including shielding salts. |
| CA2860650C (en) | 2012-01-04 | 2016-08-02 | The Procter & Gamble Company | Active containing fibrous structures with multiple regions |
| RU2588573C2 (en) | 2012-01-04 | 2016-07-10 | Дзе Проктер Энд Гэмбл Компани | Active agent-containing fibrous structure with multiple areas with different densities |
| FR2985274B1 (en) | 2012-01-04 | 2021-01-08 | Procter & Gamble | FIBROUS STRUCTURES INCLUDING PARTICLES AND THEIR MANUFACTURING PROCESS |
| DE112014005598B4 (en) | 2013-12-09 | 2022-06-09 | The Procter & Gamble Company | Fibrous structures including an active substance and with graphics printed on it |
| US20150210964A1 (en) | 2014-01-24 | 2015-07-30 | The Procter & Gamble Company | Consumer Product Compositions |
| WO2017192653A1 (en) * | 2016-05-03 | 2017-11-09 | The Procter & Gamble Company | Automatic dishwashing detergent composition |
| US11697905B2 (en) | 2017-01-27 | 2023-07-11 | The Procter & Gamble Company | Active agent-containing articles that exhibit consumer acceptable article in-use properties |
| CN115742472A (en) | 2017-01-27 | 2023-03-07 | 宝洁公司 | Active agent-containing articles exhibiting consumer acceptable article application characteristics |
| US11697904B2 (en) | 2017-01-27 | 2023-07-11 | The Procter & Gamble Company | Active agent-containing articles that exhibit consumer acceptable article in-use properties |
| US11697906B2 (en) | 2017-01-27 | 2023-07-11 | The Procter & Gamble Company | Active agent-containing articles and product-shipping assemblies for containing the same |
| US20200190433A1 (en) | 2018-12-14 | 2020-06-18 | The Procter & Gamble Company | Foaming Fibrous Structures Comprising Particles and Methods for Making Same |
| US11485934B2 (en) | 2019-08-02 | 2022-11-01 | The Procter & Gamble Company | Foaming compositions for producing a stable foam and methods for making same |
| US20210148044A1 (en) | 2019-11-15 | 2021-05-20 | The Procter & Gamble Company | Graphic-Containing Soluble Articles and Methods for Making Same |
| WO2022251838A1 (en) | 2021-05-28 | 2022-12-01 | The Procter & Gamble Company | Natural polymer-based fibrous elements comprising a surfactant and methods for making same |
| WO2023057367A1 (en) | 2021-10-08 | 2023-04-13 | Unilever Ip Holdings B.V. | Laundry composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4529525A (en) * | 1982-08-30 | 1985-07-16 | Colgate-Palmolive Co. | Stabilized enzyme-containing detergent compositions |
| NZ208612A (en) * | 1983-06-24 | 1991-09-25 | Genentech Inc | Method of producing "procaryotic carbonyl hydrolases" containing predetermined, site specific mutations |
| US4507219A (en) * | 1983-08-12 | 1985-03-26 | The Proctor & Gamble Company | Stable liquid detergent compositions |
| DE3574729D1 (en) * | 1984-05-14 | 1990-01-18 | Procter & Gamble | LIQUID CLEANING AGENTS CONTAINING BORIC ACID FOR STABILIZING ENZYMS. |
-
1986
- 1986-04-07 EP EP86200586A patent/EP0199405B1/en not_active Expired
- 1986-04-07 DE DE8686200586T patent/DE3685769T2/en not_active Expired - Fee Related
- 1986-04-07 AT AT86200586T patent/ATE77649T1/en not_active IP Right Cessation
- 1986-04-14 CA CA000506568A patent/CA1302925C/en not_active Expired - Fee Related
- 1986-04-15 JP JP61086963A patent/JPS62596A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3685769D1 (en) | 1992-07-30 |
| EP0199405A2 (en) | 1986-10-29 |
| EP0199405B1 (en) | 1992-06-24 |
| DE3685769T2 (en) | 1993-01-21 |
| EP0199405A3 (en) | 1988-08-31 |
| ATE77649T1 (en) | 1992-07-15 |
| JPS62596A (en) | 1987-01-06 |
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