USH1776H - Enzyme-containing heavy duty liquid detergent - Google Patents

Enzyme-containing heavy duty liquid detergent Download PDF

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Publication number
USH1776H
USH1776H US08/470,643 US47064395A USH1776H US H1776 H USH1776 H US H1776H US 47064395 A US47064395 A US 47064395A US H1776 H USH1776 H US H1776H
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composition
weight
enzyme
heavy duty
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Jack E. Linard
Daniel J. Fox
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Lever Brothers Co
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Lever Brothers Co
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • C11D3/2044Dihydric alcohols linear
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2065Polyhydric alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663Stabilised liquid enzyme compositions

Definitions

  • Liquid laundry detergents provide the same performance benefits as powdered detergents such as whole wash cleaning, whitening, antiredeposition and odor removal, while providing additional benefits such as convenient dispensing, complete solubility and improved stain removal on localized stains.
  • the improved localized cleaning is accomplished by pretreating the stain directly without the need to make a paste as with powder detergents.
  • Liquid laundry detergents have become increasingly popular in recent years due in large part to these advantages over powders.
  • Liquid detergents encounter formulation difficulties over and above those seen in powders largely due to the desire to keep a wide variety of surfactants, builders and other cleaning agents solubilized for long periods in a homogeneous free flowing form. Many of the chemicals available and desirable for use in liquids are physically as well as chemically incompatible. Much of the skill utilized in formulating liquid detergents goes into keeping these chemicals stable for long periods in intimate contact with incompatible materials.
  • wash solution pH's of 9.0 or greater are desirable because alkaline liquids give improved performance on fatty soils, both in concentrated form during pretreatment with the neat liquid, and in the wash solution where it is used at a concentration of about 0.2%. Wash solution pH's of 8.5 or greater permit improved whole wash detergency on fatty soils by saponifying the fatty materials to form an easily removed soap. Improved performance on both proteinaceous and fatty soils would result from an enzyme-containing, high pH liquid. Furthermore, because fatty soils lower wash solution pH, liquid detergents which resist drops in wash solution pH are preferred. This resistance to lowering of wash solution pH in the presence of fatty soils results from the buffering capacity provided by the detergent.
  • Hora et al. U.S. Pat. No. 4,261,868 discloses the use of an enzyme in a high pH (7.5 to 11.0) liquid laundry detergent with a stabilizing system including a polyfunctional amino compound (such as triethanolamine) and borax.
  • a polyfunctional amino compound such as triethanolamine
  • borax anionic to nonionic surfactant ratios of 1:1 to 1:10 are disclosed.
  • Example 1 includes sodium tripolyphosphate, dimethyl glycine and Alcalase® enzyme and is said to have a pH of 10.0.
  • Boskamp U.S. Pat. No. 4,462,922 discloses the use of a high alkaline enzyme in a liquid laundry detergent along with a stabilizing system including borax, a reducing alkali metal salt and a polyol and/or a polyfunctional amino compound.
  • the pH of the '922 composition is said to be near neutral, preferably from 8.0 to 10.0.
  • the composition can be buffered to a value within that range by addition of a suitable buffer system.
  • the pH of the wash liquor is said preferably to be 1 pH unit higher at an in-use concentration of 1%.
  • Boskamp uses the reducing alkali metal salt to provide effective enzyme stabilization.
  • Boskamp U.S. Pat. No. 4,532,064 teaches the use of a high alkaline enzyme having a maximum activity at pH 8-12 in a liquid laundry detergent along with a stabilizing system including borax, a reducing metal salt, an optional buffer, and the use of a dicarboxylic acid as replacement for the polyol or polyfunctional amino compound.
  • the pH of the final composition is near neutral, preferably 7.5 or higher and may be buffered to a value in that region by addition of a suitable buffer system.
  • the pH of the wash water is about 1 pH unit higher at an in-use concentration of 1%.
  • the pH of Example 1 is 7.5.
  • Letton et al. U.S. Pat. No. 4,318,818 discloses the use of an enzyme in a liquid laundry detergent with a stabilizing system comprising a polyol, calcium and a short chain carboxylic acid. Mono-, di-, and triethanol amines may be used as pH buffers. While Letton et al. disclose a potential product pH range of from 6.5 to 10, they prefer a range of from 7 to about 8.5 to obtain a combination of enzyme stability and detergency.
  • Example XIII E of Letton et al. includes Maxatase, surfactant, ethanol, sodium formate and triethanolamine, and is said to have a pH of 9.6.
  • Example XIII P includes surfactant, ethanol, Maxatase, sodium carbonate, and sodium formate and is said to have a pH of 10.0.
  • Tai U.S. Pat. No. 4,404,115 teaches the use of an enzyme in a liquid laundry detergent with a stabilizing system including a polyol (optional), an alkali metal sulphite and an alkaline metal pentaborate.
  • the pentaborate is said to provide a buffering effect on its own at the optimal pH condition to the liquid composition which on dilution in use gives a sufficiently alkaline pH for optimal detergency.
  • the pH of the Tai wash liquor on use of the composition is said to be in the alkaline range of well above 8 at an in-use concentration of about 1%.
  • Example III(6) discloses a metaborate and enzyme-including composition which has a pH of 11.36 and a 1% solution pH of 9.26 but an enzyme stability after 2 weeks of 10% or less.
  • Other ingredients include surfactants + triphosphate builder.
  • Our invention involves the stable incorporation of enzymes in a high pH liquid laundry detergent and the resultant improvements in detergency on both enzyme-susceptible and fatty soils. It is the stable inclusion of the specified levels of titratable alkalinity in conjunction with an enzyme stabilization system utilizing glycols, calcium and/or borax resulting in improved proteolytic enzyme performance and excellent fatty soil removal (both in the whole wash and in pretreat usage) that forms the basis of our invention.
  • Our invention includes a liquid laundry detergent comprising: 1) a neat liquid pH of 9.5 or greater to provide good pretreat fatty soil removal, 2) a solution pH of 8.5 or greater at a 0.2% wt. use level to provide good whole wash detergency on fatty soils, 3) titratable alkalinity of at least 0.5% wt.
  • preferred systems encompassing all of the above named features comprise an active system at a level of from about 5% to about 40% wt. comprising principally anionic and nonionic surfactants, a soluble builder (such as citrate) from about 5 to about 20% wt., an alkalinity system that includes the use of one or more alkanolamines from about 1 to about 6% wt., an enzyme system containing at least one alkaline protease such as Alcalase®, Savinase®, Maxacal® or Esperase®, an enzyme stabilizing system containing a glycol at from 1 to about 8%, a boron compound, preferably borax at from about 1 to about 8% by weight and a source of alkaline earth cation provided by an alkaline earth salt (such as CaCl 2 ) at between 0.001 and 0.1% wt.
  • an alkaline earth salt such as CaCl 2
  • compositions of the invention may be substantially or essentially phosphate-free.
  • essentially phosphate free it is meant that there is 0.5% or less phosphorous (as phosphorous) present.
  • the compositions of the invention exhibit at least 25% of initial enzyme activity after 2 weeks at 105° F.
  • the preferred liquid detergent of this invention would additionally include hydrotrope for product stability, one or more fluorescent dyes and/or bluing agents for brightening garments, colorants and/or opacifiers for product appearance, and a fragrance to provide acceptable product odor.
  • the detergent of the invention can be an isotropic, i.e., single phase, liquid. It is the stable inclusion of the aforementioned components in a liquid laundry detergent that provides both effective enzyme stain removal along with excellent fatty soil removal, both in whole wash and pretreat usage, that provides the basis for our invention.
  • pH when used herein means the pH measured at 25° C.
  • the liquid laundry detergents described in this invention contain the following components either as essential components or as optional ingredients: surfactants (either anionic, nonionic, cationic, zwitterionic or amphoteric or mixtures thereof) for detergency, both whole wash and pretreatment, builders for hardness ion sequestration, alkalinity/buffering agents for pH maintenance both in the neat liquid and upon dilution in the whole wash, solubilizers or hydrotropes for phase stability of the active in solution, enzymes (protease, and optionally amylase, cellulase, lipase or mixtures thereof) for stain removal, polyhydric alcohols and/or boron compounds to preserve enzyme activity upon storage, fluorescent whitening agents for whitening and brightening of clothing, softeners, foam control agents, appearance modifiers such as thickeners or opacifiers, bluing agents and colorants, germicides, perfumes and preservatives. Additional performance agents such as bleaching agents (either chlorine or oxygen bleaching), soil release
  • anionic or nonionic surfactants are acceptable for use and may be considered within the scope of this invention
  • anionic or nonionic surfactants and mixtures thereof are more commonly used in formulating liquid laundry detergents.
  • a ternary surfactant system of linear alkyl benzene sulfonate, linear ether sulfate and ethoxylated alcohol nonionic is especially preferred.
  • the ratio of anionic to nonionic surfactants is preferably 1:1 to 10:1.
  • Suitable zwitterionics and amphoteric surfactants are described in U.S. Pat. No. 4,528,039 while suitable cationic surfactants are described in U.S. Pat. No. 4,497,718, which patents are hereby incorporated by reference.
  • the compositions of the invention may include from 1-60% by weight of one or more surfactants.
  • the preferred anionic and nonionic surfactants are described in more detail as follows:
  • Anionic surfactants comprise both soap-based and synthetic detergents.
  • the synthetic anionic detergents can be broadly described as the water-soluble salts of organic sulfur reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • Such surfactants are well known in the detergent art and are described in "Surface Active Agents and Detergents", Vol. II, by Schwartz, Perry and Berch.
  • the more useful synthetic anionics are the alkyl, alkylaryl or alkenyl sulfonates and the alkyl and alkylene ethoxy sulfates.
  • Suitable alkylaryl sulfonates include the alkali metal or the ammonium or alkanol ammonium salts of the alkyl aromatic sulfonates such as the higher alkylbenzene sulfonates containing from 10 to 16 carbon atoms in the alkyl groups and a straight or branched chain. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 10 to about 14 carbon atoms.
  • olefin sulfonates including long chain alkane sulfonates, long chain hydroxyalkane sulfonates or mixtures thereof, paraffin sulfonates, alkyl glyceryl sulfonates or mixtures of these sulfonates particularly with the linear alkyl benzene sulfonates.
  • Suitable alkyl sulfates include those in which the alkyl chain contains from about 10 to about 18 carbon atoms and the sulfate salt is formed by a solubilizing salt forming cation such as an alkali metal (such as sodium or potassium) or ammonium or alkanolammonium compounds such as the mono, di, or triethanol ammonium salt.
  • Suitable alkyl ethoxy sulfates include those of the formula RP(C 2 H 4 O) n SO 3 M where R is an alkyl preferably from C 10 to C 16 chain length, n averages from 0.5 to about 10, and M is a solubilizing salt forming cation as described above for the alkyl sulfates.
  • anionic surfactant useful by itself or in combination with other surfactants for practice of this invention comprises the soaps.
  • Sodium or potassium soaps are generally used with the fatty acid component or the soap derived from mixtures of saturated and partially unsaturated fatty acids in the C 8 to C 26 chain length region.
  • the source of the fatty acid is traditionally a blend of coconut oil and tallow but may come from other sources such as palm oil, peanut oil or sunflower seed oil.
  • the liquid detergents of the invention need not include soap.
  • anionic surfactants as described above are employed in amounts from about 1% to about 30% by weight of the total formulation.
  • Preferred anionic surfactant use levels are from about 2 to about 20% and may include either a single anionic surfactant or a mixture of the anionics described above. Most preferred are a mixture of anionics, each at a level of from about 4 to about 15% with a total anionic surfactant level from about 8 to about 30%.
  • Suitable nonionic surfactants are those of the formula RO(C 2 H 4 O) n OH where R is a C 8 to C 18 carbon chain or a C 8 to C 12 alkyl phenyl group, and n is from about 2 to about 12.
  • suitable linear, straight chain alkyl nonionics are those sold under various Neodol names (ex Shell Chemical), those sold under various Alfonic names (ex Vista) and those sold under various Tergitol names (ex Union Carbide).
  • the nonionic surfactants as described above are employed in amounts from about 1% to about 20% by weight of the total formula.
  • Preferred nonionic surfactant use levels are from about 3% to about 12% and may consist of either a single nonionic surfactant or may be a mixture of the nonionics described above.
  • composition of the invention may optionally include builders.
  • Suitable builders useful in this invention include organic and inorganic builders.
  • suitable inorganic builders are the alkali metal salts of ortho-, pyro- or tripolyphosphate, silicates or crystalline or amorphous zeolites.
  • suitable organic builders include the alkali salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid and polycarboxylic acids such as citric acid.
  • suitable organic builders include carbonates succinates and polymers and copolymers of maleic and acrylic acids.
  • the builders described above are employed in amounts from about 0.5 to 25% by weight of the total formula.
  • Preferred builder use levels are from about 3% to about 25% especially about 5% to about 20% and may include either a single builder or may be a mixture of the builders described above.
  • alkalinity agents are often used in addition to the builders to provide an alkalinity reservoir to maintain a high pH and saponify the acidic constituent of soil.
  • Suitable alkalinity sources that may be used within the scope of this invention include alkali metal hydroxides, silicates, carbonates and alkanolamines from the group consisting of monoethanolamine, diethanolamine, triethanolamine and mixtures thereof.
  • the alkalinity agents as described above are used in amounts from 0.1% to about 10% by weight of the total formula.
  • Preferred alkalinity agent use levels are from about 0.5% to about 8% and may consist of either a single alkalinity source or may be a mixture of the alkalinity agents described above. Most preferred alkalinity agents are the preferred alkanolamines, either individually or in mixtures, with the total alkanolamine level being from about 1% to about 6% by weight of the total formula. Monoethanolamine is particularly preferred. Levels of polyfunctional amino compounds may be from 0.5 to 10%. While the alkanolamines are preferred ingredients, the liquid detergents of the invention may be amine-free.
  • the total titratable alkalinity from all sources in the present compositions equals at least 0.5% wt. per gram of product when expressed as % Na 2 O as measured to pH 7.
  • Boron compounds useful in this invention include boric acid, boric oxide and alkali metal borates.
  • alkali metal borates are sodium and potassium, ortho, pyro and meta borates, polyborates and borax.
  • Borax is the preferred alkali metal borate and is a tetraborate that is sold commercially in either the pentahydrate or decahydrate form.
  • the boron compounds are used in amounts of from 0.1% to 10% by weight of the total formula with the borax pentahydrate being the preferred compound with a use level of from about 1% to 8% by weight. It is not necessary that pentaborates be included in the compositions of the invention.
  • the enzymes to be incorporated in this compound can be proteolytic, amylolytic, lipolytic and cellulolytic enzymes as well as mixtures thereof.
  • Particularly suitable enzymes are alkaline proteases obtained from strains of Bacillus, having maximum activity throughout the pH range from 7.0 to 12.0.
  • the enzymes can be incorporated in any suitable form, i.e., as granulates, marunes, prills, etc., but are more conveniently added to liquid detergents in a fluid form such as in a liquid or slurry.
  • Examples of proteolytic enzymes suitable for use in this invention are sold under the names Alcalase®, Savinase® and Esperase® by Novo Industries, Copenhagen, Denmark and Maxatase® and Maxacal® by International Biosynthetics, Rijswijk, Netherlands. Savinase®, Maxacal®, and Alcalase® are particularly preferred.
  • amylase enzymes suitable for use in this invention are Termamyl sold by Novo and Maxamyl sold by International Biosynthetics, Rijswijk, Netherlands.
  • the amount of enzyme present in the liquid composition will depend on the concentration of active enzyme in the specific product but will in general be at a level from about 0.001 to about 10% by weight.
  • a preferred system would employ an alkaline protease, possibly in combination with an ⁇ -amylase at a total enzyme level from about 0.05 to about 5% by weight of total formula.
  • the activity of the enzyme in the present liquid composition is preferably from 0.001 kilo Novo Protease Units (KNPU) to 1 KNPU per gram of product.
  • One Novo Protease Unit is the amount of enzyme which hydrolyzes dimethyl casein to peptides (as determined by reaction of primary amino groups with trinitrobenzene sulfonic acid at an initial rate that corresponds to 1 micromole of glycine/minute at 50° C. and a pH of 8.3).
  • 3 KNPU are roughly equal to 1 Anson unit.
  • One KNPU roughly corresponds to 80,000 Alkaline Delft Units.
  • a protease as used herein will have a minimum of 0.001 KNPU.
  • Polyols useful within the scope of this invention include those polyols containing from two to six hydroxyl groups. Preferably the polyols include from one to six carbon atoms.
  • Typical examples include the polyhydric alcohols ethylene glycol, propylene glycol, dipropylene glycol, and glycerol.
  • Preferred polyol use levels are from about 0.1 to about 20% of the total formula weight with most preferred levels being from about 1 to about 8% of the formula either as a single polyol or as a mixture of polyols.
  • polyols can likewise be used within the range of from about 0.1 to about 8% of the formula.
  • Preferable alkaline earth salts include calcium and magnesium salts such as chlorides, sulfates and acetates.
  • Calcium salts are the most preferred alkaline earth salts and are used at levels of from about 0.0001% to about 1%, with a preferred range of about 0.001 to about 0.1% by weight based on the weight of the Ca ++ ion. The levels are over and above any metal iron present in the enzyme.
  • hydrotrope as used herein means an agent which will water-solubilize the main surface active agents used in the composition.
  • Suitable hydrotropes for use in this invention include the ammonium or alkali metal salts of benzene sulfonate and mono- or dialkyl substituted benzene sulfonates wherein the alkyl chains contain 1 to 3 carbon atoms.
  • the alkyl benzene sulfonates include such compounds as toluene, ethyl benzene, isopropyl benzene and o-, m- and p-xylene sulfonates and mixtures thereof.
  • Hydrotropes suitable for use in this invention may also include short chain alcohols containing from two to six carbon atoms and mixtures thereof. The hydrotropes described above are used in amounts from 1% to 15% by weight of the total formula. Preferred hydrotrope use levels are from about 2% to 10% and may include either a single hydrotrope or a mixture of the hydrotropes described above.
  • fluorescent whitening agents suitable for use within the scope of this invention are the diaminostilbene disulfonate cyanuric chloride derivatives (DAS/CC).
  • the main constituents of the DAS/CC type fluorescent dyes are the 4,4'bis 4-anilo-6-substituted-1,3,5 triazin-2-yl)amino! stilbene-2,2' disulfonic acids, or their alkali metal or alkanolamino salts, in which the substituted group is either morpholino, hydroxyethyl, methylamino, dihydroxyethylamino or methylamino.
  • the structure of the acid form is shown in FIG. 1. ##
  • the fluorescent whitening agents most preferably used are those in which R 1 and R 2 are morpholino as in Tinopal AMS (ex Ciba-Geigy), R 1 and R 2 are hydroxyethylmethylamino as in Tinopal 5BM (ex Ciba-Geigy), or R 1 and R 2 are dihydroxyethylamino as in Tinopal UNPA (ex Ciba-Geigy).
  • fluorescent whitening agents suitable for use in this invention include the naphthotriazolylstilbene type sold under the trade name Tinopal RBS (ex Ciba-Geigy) or the diphenyl-triazolylstilbene- (Phorwite BHC (ex Mobay)) or distyrylbiphenyl-type (Tinopal CBS-X (ex Ciba-Geigy)) florescent whiteners.
  • the fluorescent whitening agents described above are used in amounts of from about 0.001% to about 2% by weight of the total formula.
  • Preferred fluorescent whitening agent use levels are from about 0.01% to about 0.5% and may include either a single fluorescent whitener or a mixture of the fluorescent whiteners described above.
  • Suitable for use within the scope of this invention are a number of heavy duty detergent additives, collectively referred to as "minor additives.” These are ingredients that, while present in minor amounts, can contribute significantly to the performance and marketability of detergent products.
  • minor components that can be used in this invention are foam control agents, thickeners (such as cellulose ethers), opacifiers (such as polystyrene latices), bluing agents, colorants, preservatives, processing aids, and perfumes.
  • optional performance enhancement components may be included, often in larger amounts. These include bleaching agents, such as inorganic peroxy compounds and activators, soil shield agents, antiredeposition or soil suspending materials and other optional performance components.
  • the preparation method for these liquid laundry detergent systems comprises a two mix process involving a main mix and a premix.
  • the main mix includes the batch water plus all or part of the hydrotrope, builder, anionic active(s), enzyme stabilizing system and minor ingredients such as colorants, etc. These components are stirred and heated (either directly or through the heat of neutralization of the anionic active) to a temperature not to exceed about 140° F. Part of the alkalinity/buffering agents may optionally be added to the main batch.
  • the premix comprises the nonionic active plus the fluorescent dyes and may optionally contain part or all of the hydrotrope and some minor components such as the foam control agents. In its preferred form the premix contains part or all of the alkalinity agents.
  • the premix is heated to a temperature between about 140° to 160° F. with stirring to disperse the fluorescent dyes. The premix is then added to the main batch mix with sufficient stirring to ensure that a uniform mixture is achieved. The main batch mix thus prepared is then cooled to 100° F. or below before addition of enzyme(s) and fragrance(s).
  • compositions are used to illustrate the invention. All components are given in terms of weight percent of 100% active material unless specified otherwise.
  • Comparative Compositions 1 and 2 are enzyme-containing, commercially available liquid laundry detergents believed to have the components and levels indicated.
  • Comparative Composition 3 is a commercially available, built liquid detergent which does not incorporate enzymes.
  • Enzyme efficacy and stability can also be evaluated by washing protease-sensitive test cloths.
  • the results below were obtained by washing test cloths containing casein (dry milk) in a Terg-o-tometer® (U.S. Testing) at 60 ppm hardness (2 Ca:1 Mg) at 100° F.
  • the detergencies were obtained from reflectance, R, measurements done on the unsoiled cloth, soiled cloth, and washed cloth:
  • Comparative Composition 1 was equal to or poorer than comparative Composition 3, which did not include enzymes.
  • a product which gives higher pH washing conditions and greater alkaline buffer capacity is desirable for two reasons: the alkaline proteases currently available perform better in alkaline wash pH's, and alkaline wash conditions help to deterge fatty soils from the substrates. Consequently, formulations which have a buffer capacity yielding pH's at and above 8.5 at a dilution of 0.2% (wt.) product in water are desirable. This dilution is typical of wash doses for most liquid laundry detergents.
  • Compositions II--VII further illustrate the invention. All have active and builder systems equal to that of Composition I, although other ratios and levels can provide similar results. To compare the formulations, all miscellaneous ingredients were the same as for Composition I. Comparative Composition 4, not in accordance with the invention, is also given.
  • compositions I-VII and comparative Compositions 1-4 are given in Table 4.
  • the alkalinity reserve is most important on soils which contain natural oils and fatty acids. They are hydrolyzed at high pH's, but this causes the wash pH to drop. High levels of alkalinity reserve, such as those in the compositions of the invention (I-VII) and the non-enzymatic liquid (3), provide significant benefits on such soils. Evaluations of these detergents on fatty acid/vacuum cleaner dust shown in Table 5 demonstrate this trend.
  • compositions I-V according to the invention are significantly superior to the commercial products on at least one of the test cloths and equal on the other.
  • These formulas represent the preferred compositions of this invention.
  • Compositions VI-VII show performance equal to or better than the commercial products, it is the high pH of these neat enzyme containing liquids that distinguishes them from the less desirable liquids with lower, near-neutral pH's. The higher neat pH is important for removing fatty soils in a pretreat situation.
  • Comparative Composition 3 does have substantial alkalinity reserve, but its lack of an enzyme prevents significant casein test cloth cleaning.
  • Comparison formula 4 does not have the reserve alkalinity of the compositions of the invention. While it does show modest enzyme cleaning performance, its fatty acid/vacuum cleaner dust test cloth results are poor. While markedly inferior to the compositions described by this invention, even Composition 4 is in many respects superior to Composition 2, one of the commercial enzyme products.
  • compositions I-VII and comparison Composition 3 have neat liquid pH's of above 9.5 or greater, 0.2% aqueous solution pH's of at least 8.5, and alkalinity reserves at pH 7.0 above 0.5% Na 2 O. Composition 3 has no enzyme; if enzyme were added its activity would fall to near zero after only a few days storage. Compositions I-VII have the unique combination of high alkalinity, high alkalinity reserve, and enzyme effectiveness that this invention describes.
  • compositions VIII and IX using sodium carbonate as alkalinity source were prepared having the following formulas:
  • Enzyme stability testing shows both Compositions VIII and IX to have good stability after storage at elevated temperatures (105° F. for 4 weeks).

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US08/470,643 1988-06-23 1995-06-06 Enzyme-containing heavy duty liquid detergent Abandoned USH1776H (en)

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US08/470,643 USH1776H (en) 1988-06-23 1995-06-06 Enzyme-containing heavy duty liquid detergent

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US21047488A 1988-06-23 1988-06-23
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US24137894A 1994-05-10 1994-05-10
US08/470,643 USH1776H (en) 1988-06-23 1995-06-06 Enzyme-containing heavy duty liquid detergent

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US6180585B1 (en) 1999-04-16 2001-01-30 Spartan Chemical Company, Inc. Aqueous disinfectant and hard surface cleaning composition and method of use
US20030087787A1 (en) * 2000-06-29 2003-05-08 Ecolab Inc. Stable liquid enzyme compositions with enhanced activity
US20050020466A1 (en) * 2000-06-29 2005-01-27 Man Victor F. Stable liquid enzyme compositions
US20050164902A1 (en) * 2003-10-24 2005-07-28 Ecolab Inc. Stable compositions of spores, bacteria, and/or fungi
US20060247150A1 (en) * 2000-06-29 2006-11-02 Molinaro Katherine J Stable antimicrobial compositions including spore, bacteria, fungi, and/or enzyme
US7211552B1 (en) 2002-11-13 2007-05-01 Melton Sherwood Thoele Enzymatic detergent
US20080274936A1 (en) * 2007-04-27 2008-11-06 Adamy Steven T High ash liquid laundry detergents
US7723281B1 (en) 2009-01-20 2010-05-25 Ecolab Inc. Stable aqueous antimicrobial enzyme compositions comprising a tertiary amine antimicrobial
US20110053824A1 (en) * 2001-02-28 2011-03-03 Chandrika Kasturi Liquid detergent composition exhibiting enhanced alpha-amylase enzyme stability
US7964548B2 (en) 2009-01-20 2011-06-21 Ecolab Usa Inc. Stable aqueous antimicrobial enzyme compositions
US8420584B2 (en) 2007-03-30 2013-04-16 Melton Sherwood Thoele Enzymatic detergent
US9353334B2 (en) 2010-12-28 2016-05-31 Kao Corporation Method for cleaning medical instrument
US10011808B2 (en) 2013-11-11 2018-07-03 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US11434454B2 (en) 2017-12-22 2022-09-06 Church & Dwight Co., Inc. Laundry detergent composition

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JPH0775620B2 (ja) * 1991-04-08 1995-08-16 トーメー産業株式会社 含水性コンタクトレンズ用液剤組成物及び含水性コンタクトレンズの洗浄方法
BR9702049B1 (pt) * 1996-01-31 2010-08-10 sistema distribuidor contendo dois compartimentos para a dosagem simultánea de duas composições aquosas.
CN1238002A (zh) * 1996-09-24 1999-12-08 普罗格特-甘布尔公司 含有蛋白水解酶、肽醛和硼酸源的液体洗涤剂
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ATE262026T1 (de) * 1999-09-02 2004-04-15 Weigert Chem Fab Enzymkonzentrat und verfahren zum reinigen von oberflächen
MXPA02003744A (es) * 1999-10-15 2002-08-30 Procter & Gamble Composicion enzimatica liquida para limpieza.
JP2009507085A (ja) * 2005-09-02 2009-02-19 ノボザイムス アクティーゼルスカブ 濃縮された液体酵素添加剤の安定化
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JP2021080378A (ja) * 2019-11-20 2021-05-27 花王株式会社 デンプン汚れ固着防止剤

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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6165965A (en) * 1999-04-16 2000-12-26 Spartan Chemical Company, Inc. Aqueous disinfectant and hard surface cleaning composition and method of use
US6180585B1 (en) 1999-04-16 2001-01-30 Spartan Chemical Company, Inc. Aqueous disinfectant and hard surface cleaning composition and method of use
US7795199B2 (en) 2000-06-29 2010-09-14 Ecolab Inc. Stable antimicrobial compositions including spore, bacteria, fungi, and/or enzyme
US6624132B1 (en) * 2000-06-29 2003-09-23 Ecolab Inc. Stable liquid enzyme compositions with enhanced activity
US20050020466A1 (en) * 2000-06-29 2005-01-27 Man Victor F. Stable liquid enzyme compositions
US8211849B2 (en) 2000-06-29 2012-07-03 Ecolabb USA Inc. Stable antimicrobial compositions including spore, bacteria, fungi and/or enzyme
US20060247150A1 (en) * 2000-06-29 2006-11-02 Molinaro Katherine J Stable antimicrobial compositions including spore, bacteria, fungi, and/or enzyme
US20110207649A1 (en) * 2000-06-29 2011-08-25 Ecolab Usa Inc. Stable antimicrobial compositions including spore, bacteria, fungi and/or enzyme
US7951767B2 (en) 2000-06-29 2011-05-31 Ecolab Usa Inc. Stable antimicrobial compositions including spore, bacteria, fungi and/or enzyme
US7553806B2 (en) * 2000-06-29 2009-06-30 Ecolab Inc. Stable liquid enzyme compositions with enhanced activity
US7569532B2 (en) * 2000-06-29 2009-08-04 Ecolab Inc. Stable liquid enzyme compositions
US20030087787A1 (en) * 2000-06-29 2003-05-08 Ecolab Inc. Stable liquid enzyme compositions with enhanced activity
US20110053824A1 (en) * 2001-02-28 2011-03-03 Chandrika Kasturi Liquid detergent composition exhibiting enhanced alpha-amylase enzyme stability
US7211552B1 (en) 2002-11-13 2007-05-01 Melton Sherwood Thoele Enzymatic detergent
US20050164902A1 (en) * 2003-10-24 2005-07-28 Ecolab Inc. Stable compositions of spores, bacteria, and/or fungi
US8420584B2 (en) 2007-03-30 2013-04-16 Melton Sherwood Thoele Enzymatic detergent
US7915213B2 (en) * 2007-04-27 2011-03-29 Church & Dwight Co., Inc. High ash liquid laundry detergents comprising a urea and/or glycerine hygroscopic agent
US20080274936A1 (en) * 2007-04-27 2008-11-06 Adamy Steven T High ash liquid laundry detergents
US7723281B1 (en) 2009-01-20 2010-05-25 Ecolab Inc. Stable aqueous antimicrobial enzyme compositions comprising a tertiary amine antimicrobial
US7964548B2 (en) 2009-01-20 2011-06-21 Ecolab Usa Inc. Stable aqueous antimicrobial enzyme compositions
US8227397B2 (en) 2009-01-20 2012-07-24 Ecolab Usa Inc. Stable aqueous antimicrobial lipase enzyme compositions
US9353334B2 (en) 2010-12-28 2016-05-31 Kao Corporation Method for cleaning medical instrument
US10011808B2 (en) 2013-11-11 2018-07-03 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US11434454B2 (en) 2017-12-22 2022-09-06 Church & Dwight Co., Inc. Laundry detergent composition

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BR8903088A (pt) 1990-02-06
JPH0245599A (ja) 1990-02-15
EP0348183A2 (en) 1989-12-27
ZA894785B (en) 1991-02-27
EP0348183A3 (en) 1991-05-29
AU3667189A (en) 1990-01-04

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