EP1171562A1 - Compositions de detergents pour le lavage de la vaisselle, contenant des polyamines organiques - Google Patents

Compositions de detergents pour le lavage de la vaisselle, contenant des polyamines organiques

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Publication number
EP1171562A1
EP1171562A1 EP00926085A EP00926085A EP1171562A1 EP 1171562 A1 EP1171562 A1 EP 1171562A1 EP 00926085 A EP00926085 A EP 00926085A EP 00926085 A EP00926085 A EP 00926085A EP 1171562 A1 EP1171562 A1 EP 1171562A1
Authority
EP
European Patent Office
Prior art keywords
diamine
composition
alkyl
dishwashing detergent
detergent composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00926085A
Other languages
German (de)
English (en)
Inventor
Jean-François Bodet
William Michael Scheper
Janice Lee Oglesby
Bruce Prentiss Murch
Mark Leslie Kacher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1171562A1 publication Critical patent/EP1171562A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the present invention relates to hand dishwashing detergent compositions containing polyamines. More particularly, the invention is directed to detergent compositions for hand dishwashing which have improved grease removal performance and benefits in sudsing.
  • the detergents of this invention also have improved low temperature stability properties and superior dissolution, as well as improved tough food stain removal. BACKGROUND OF THE INVENTION
  • Typical commercial hand dishwashing compositions incorporate divalent ions (Mg, Ca) to ensure adequate grease performance in soft water.
  • divalent ions Mg, Ca
  • anionic, nonionic, or additional surfactants e.g., amine oxide, alkyl ethoxylate, alkanoyl glucose amide, al yl betaines
  • amine oxide, alkyl ethoxylate, alkanoyl glucose amide, al yl betaines leads to slower rates of product mixing with water (and hence poor flash foam), poor rinsing, and poor low temperature stability properties.
  • preparation of stable dishwashing detergents containing Ca/Mg is very difficult due to the precipitation issues associated with Ca and Mg as pH increases.
  • hand dishwashing formulations which contain magnesium as well as amine oxide and an anionic surfactant have the added stability problem that at low temperatures, typically about 5°C or less, the product solidifies. This eliminates a potentially useful surfactant system from any possible combinations with magnesium.
  • a hand dishwashing detergent composition comprising: (a) surfactant; (b) polyamine, wherein said polyamine contains at least 3 protonatable nitrogen atoms and at least one pKa above the wash pH (as measured as a 0.2% aqueous solution) and at least two pKa's greater than about 6 and below wash pH (as measured as a 0.2% aqueous solution); wherein the pH (as measured as 10% aqueous solution) is from about 6.0 to about 11.
  • a hand dishwashing detergent composition comprising:
  • a polyamine wherein said polyamine contains at least 3 protonatable nitrogen atoms and has a molecular weight of from about 140 daltons to about 3000 daltons; wherein the pH (as measured as 10% aqueous solution) is from about 6.0 to about 1 1; and the mole ratio of said protonatable nitrogen to moles of anionic surfactant is from about 10: 1 to about 1:15, preferably about 6: 1 to about l:10,more preferably about 3: 1 to about 1 :5.
  • the present detergent compositions comprise an "effective amount” or a "grease removal-improving amount” of individual components defined herein.
  • an “effective amount” of the diamines herein and adjunct ingredients herein is meant an amount which is sufficient to improve, either directionally or significantly at the 90% confidence level, the performance of the cleaning composition against at least some of the target soils and stains.
  • the formulator will use sufficient diamine to at least directionally improve cleaning performance against such stains.
  • the diamine can be used at levels which provide at least a directional improvement in cleaning performance over a wide variety of soils and stains, as will be seen from the examples presented hereinafter.
  • the diamines are used herein in detergent compositions in combination with detersive surfactants at levels which are effective for achieving at least a directional improvement in cleaning performance.
  • usage levels can vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water and the length of time the dishware is contacted with the wash water.
  • the composition will preferably contain at least about 0.1%, more preferably at least about 0.2%, even more preferably, at least about 0.25%, even more preferably still, at least about 0.5% by weight of said composition of diamine.
  • the composition will also preferably contain no more than about 15%, more preferably no more than about 10%, even more preferably, no more than about 6%, even more preferably, no more than about 5%, even more preferably still, no more than about 1.5% by weight of said composition of diamine.
  • this invention provides a means for enhancing the removal of greasy/oily soils by combining the specific diamines of this invention with surfactants.
  • Greasy/oily "everyday”soils are a mixture of triglycerides, lipids, complex polysaccharides, fatty acids, inorganic salts and proteinaceous matter.
  • compositions herein may be formulated at viscosities of over about 50, preferably over about 100 centipoise, and more preferably from about 100 to about 400 centipoise.
  • the compositions may be formulated at viscosites of up to about 1000 centipoise.
  • the superior rate of dissolution achieved by divalent ion elimination even allows the formulator to make hand dishwashing detergents, especially compact formulations, at even significantly higher viscosities (e.g., 1,000 centipoise or higher) than conventional formulations while maintaining excellent dissolution and cleaning performance. This has significant potential advantages for making compact products with a higher viscosity while maintaining acceptable dissolution.
  • Soft water is defined herein as water which has a hardness of less than about 15 gpg, preferably less than about 10 gpg, more preferably, less than about 7 gpg, more preferably less than about 2 gpg, even more preferably about 0 gpg ("gpg” is a measure of water hardness that is well known to those skilled in the art, and it stands for "grains per gallon").
  • Diamines -It is preferred that the diamines used in the present invention are substantially free from impurities. That is, by “substantially free” it is meant that the diamines are over 95% pure, i.e., preferably 97%, more preferably 99%, still more preferably 99.5%, free of impurities.
  • impurities which may be present in commercially supplied diamines include 2-Methyl-l,3-diaminobutane and alkylhydropyrimidine. Further, it is believed that the diamines should be free of oxidation reactants to avoid diamine degradation and ammonia formation.
  • the amine oxide or surfactant should be hydrogen peroxide-free, especially when the compositions contain enzymes.
  • the preferred level of hydrogen peroxide in the amine oxide or surfactant paste of amine oxide is 0-40 ppm, more preferably 0-15 ppm.
  • Amine impurities in amine oxide and betaines, if present, should be minimized to the levels referred above for hydrogen peroxide.
  • conventional amine oxides namely those which are not free of hydrogen peroxide, can be used in the compositions of the present invention. Making the compositions free of hydrogen peroxide is important when the compositions contain an enzyme. The peroxide can react with the enzyme and destroy any performance benefits the enzyme adds to the composition.
  • the diamine can react with any peroxide present and act as an enzyme stabilizer and prevent the hydrogen peroxide from reacting with the enzyme.
  • the only draw back of this stabilization of the enzymes by the diamine is that the nitrogen compounds produced are believed to cause the malodors which can be present in diamine containing compositions. Having the diamine act as an enzyme stabilizer also prevents the diamine from providing the benefits to the composition for which it was originally put in to perform, namely, grease cleaning, sudsing, dissolution and low temperature stability.
  • compositions of the present invention be "malodor" free. That is, that the odor of the headspace does not generate a negative olfactory response from the consumer.
  • One type of preferred organic diamines are those in which pKl and pK2 are in the range of about 8.0 to about 11.5, preferably in the range of about 8.4 to about 11, even more preferably from about 8.6 to about 10.75.
  • Other preferred materials are the primary/primary diamines with alkylene spacers ranging from C4 to C8. In general, it is believed that primary diamines are preferred over secondary and tertiary diamines.
  • pKal and pKa2 are quantities of a type collectively known to those skilled in the art as “pKa” pKa is used herein in the same manner as is commonly known to people skilled in the art of chemistry. Values referenced herein can be obtained from literature, such as from “Critical Stability Constants: Volume 2, Amines” by Smith and Martel, Plenum Press, NY and London, 1975. Additional information on pKa's can be obtained from relevant company literature, such as information supplied by Dupont, a supplier of diamines.
  • the pKa of the diamines is specified in an all- aqueous solution at 25°C and for an ionic strength between 0.1 to 0.5 M.
  • the pKa is an equilibrium constant which can change with temperature and ionic strength; thus, values reported in the literature are sometimes not in agreement depending on the measurement method and conditions.
  • the relevant conditions and/or references used for pKa's of this invention are as defined herein or in "Critical Stability Constants: Volume 2, Amines”.
  • R2.5 are independently selected from H, methyl, -CH3CH2, and ethylene oxides
  • C x and C v are independently selected from methylene groups or branched alkyl groups where x+y is from about 3 to about 6
  • A is optionally present and is selected from electron donating or withdrawing moieties chosen to adjust the diamine pKa's to the desired range. If A is present, then x and y must both be 1 or greater.
  • the diamines can be those organic diamines with a molecular weight less than or equal to 400 g/mol. It is preferred that these diamines have the formula: wherein each R 6 is independently selected from the group consisting of hydrogen, C1-C4 linear or branched alkyl, alkyleneoxy having the formula:
  • R ⁇ is C2-C4 linear or branched alkylene, and mixtures thereof; R ⁇ is hydrogen, C1-C4 alkyl, and mixtures thereof; m is from 1 to about 10;
  • X is a unit selected from: i) 3-C10 linear alkylene, C3-C10 branched alkylene, C3-C10 cyclic alkylene, C3-C10 branched cyclic alkylene, an alkyleneoxyalkylene having the formula: wherein R ⁇ and m are the same as defined herein above; ii) 3-C10 linear, C3-C10 branched linear, C3-C10 cyclic, C3-C10 branched cyclic alkylene, Cg-C ⁇ Q arylene, wherein said unit comprises one or more electron donating or electron withdrawing moieties which provide said diamine with a pK a greater than about 8; and iii) mixtures of (i) and (ii)
  • diamines examples include the following: dimethyl aminopropyl amine, 1,6-hexane diamine, 1,3 propane diamine, 2-methyl 1,5 pentane diamine, 1,3-Pentanediamine (available under the tradename Dytek EP), 1,3- diaminobutane, l,2-bis(2-aminoethoxy)ethane, (available under the tradename Jeffamine EDR 148), Isophorone diamine, l,3-bis(methylamine)-cyclohexane, and mixtures thereof.
  • Polyamines dimethyl aminopropyl amine, 1,6-hexane diamine, 1,3 propane diamine, 2-methyl 1,5 pentane diamine, 1,3-Pentanediamine (available under the tradename Dytek EP), 1,3- diaminobutane, l,2-bis(2-aminoethoxy)ethane, (available under the tradename Jeffamine EDR 148), Isophorone diamine, l,3-bis(methylamine)-cycl
  • compositions of the present invention include a polyamine.
  • the polyamine is a polyalkylamines.
  • the term polyamine used herein does not include alkoxylated polyalkylamines, such as ethoxylated and or propoxylated polyalkylamine. These compounds are unsuitable for use in the compositions of the present invention because such substituient and structural modifications lower pKa below about 7.0 and cause losses in performance.
  • alkoxylated polyalkylamines can interact with any anionic surfactant in a negative fashion as well as unwanted steric effects from the alkoxylated polyalkylamines.
  • Preferred polyamine polymers are the C 2 -C polyalkyleneamines and polyalkyleneimines.
  • Particularly preferred polyalkyleneamines and polyalkyleneimines are the polyethyleneamines (PEAs) and polyethyleneimines (PEIs).
  • Preferred have a molecular weight of from about 140 to about 310, preferably from about 140 to about 200.
  • PEAs can be obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation.
  • the common PEAs obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA), .
  • TETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Pat. No. 2,792,372 to Dickson, issued May 14, 1957, which describes the preparation of PEAs.
  • Preferred PEIs used herein have an average molecular weight of from about 600 to about 2600. Although linear polymer backbones are possible, branched chains can also occur. The relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner of preparation. These PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing PEIs are disclosed in U.S. Pat. No. 2,182,306 to Ulrich et al., issued Dec. 5, 1939; U.S. Pat. No.
  • the polyamines can be included in an amount of from about 0.001% to about 5% by weight of the composition, with the preferred range being from about 0.005% to about 3% by weight, and a more preferred range of about 0.01% to 2%.
  • An example of suitable polyalkylamine has the general formula: E B
  • the units which make up the polyalkyleneimine backbones are derived from primary amine units having the formula:
  • Most preferred polyamines are selected from the group consisting of triethylenetetramine (TETA) tetraethylenepentamine (TEPA), hexaethylhexamine, heptaethylheptamines, octaethyloctamines, nonethylnonamines, and mixtures thereof, more preferably triethylenetetramine (TETA) tetraethylenepentamine (TEPA), and mixtures therof.
  • TETA triethylenetetramine
  • TEPA triethylenetetramine tetraethylenepentamine
  • compositions according to the present invention contain a surfactant, preferably selected from: anionic surfactants, nonionic surfactants; amphoteric surfactants; zwiterionic surfactants and mixtures thereof.
  • a surfactant preferably selected from: anionic surfactants, nonionic surfactants; amphoteric surfactants; zwiterionic surfactants and mixtures thereof.
  • anionic surfactants nonionic surfactants
  • amphoteric surfactants preferably selected from: amphoteric surfactants; amphoteric surfactants; zwiterionic surfactants and mixtures thereof.
  • anionic surfactants preferably selected from: anionic surfactants, nonionic surfactants; amphoteric surfactants; zwiterionic surfactants and mixtures thereof.
  • anionic surfactants preferably selected from: anionic surfactants, nonionic surfactants; amphoteric surfactants; zwiterionic surfactants and mixtures thereof.
  • the composition will preferably contain at least about 0.01%, more preferably at least about 0.1%, even more preferably still, at least about 0.2%, even more preferably still, at least about 0.5% by weight of said composition of surfactant.
  • the composition will also preferably contain no more than about 90%, more preferably no more than about 70%), even more preferably, no more than about 60%, even more preferably, no more than about 35% by weight of said composition of surfactant.
  • anionic surfactants useful in the present invention are preferably selected from the group consisting of, linear alkylbenzene sulfonate, alpha olefm sulfonate, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosinates, taurinates, and mixtures thereof.
  • anionic surfactant When present, anionic surfactant will be present typically in an effective amount. More preferably, the composition may contain at least about 0.5%), more preferably at least about 5%, even more preferably still, at least about 10% by weight of said composition of anionic surfactant. The composition will also preferably contain no more than about 90%, more preferably no more than about 50%, even more preferably, no more than about 30% by weight of said composition of anionic surfactant. Alkyl sulfate surfactants are another type of anionic surfactant of importance for use herein.
  • R preferably is a Ci Q-C 2 4 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C ⁇ Q- C 2 O alkyl component, more preferably a C ⁇ ?-C ⁇ g alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali (Group LA) metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-
  • alkyl chains of C ⁇ _ ⁇ g are preferred for lower wash temperatures (e.g., below about 50°C) and 16-18 a lkyl cnam s are preferred for higher wash temperatures (e.g., above about 50°C).
  • Alkyl alkoxylated sulfate surfactants are another category of useful anionic surfactant.
  • surfactants are water soluble salts or acids typically of the formula RO(A) m SO3M wherein R is an unsubstituted CI Q-C 4 alkyl or hydroxyalkyl group having a C ⁇ )-C 2 4 alkyl component, preferably a C ⁇ -C 2 o alkyl or hydroxyalkyl, more preferably Cj 2 -C ⁇ g alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted CI Q-C 4 alkyl or hydroxyalkyl group having a C ⁇ )-C 2 4 alkyl component, preferably a C ⁇ -C 2 o al
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperidinium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
  • Exemplary surfactants are Cl2* i8 alkyl polyethoxylate (1.0) sulfate, C ⁇ -Ci8 alkyl polyethoxylate (2.25) sulfate, l2" i8 alkyl polyethoxylate (3.0) sulfate, and C ⁇ 2 -C ⁇ g alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium.
  • Surfactants for use herein can be made from natural or synthetic alcohol feedstocks. Chain lengths represent average hydrocarbon distributions, including branching.
  • the anionic surfactant component may comprise alkyl sulfates and alkyl ether sulfates derived from conventional alcohol sources, e.g., natural alcohols, synthetic alcohols such as those sold under the trade name of NEODOLTM, ALFOLTM, LIALTM, LUTENSOLTM and the like.
  • Alkyl ether sulfates are also known as alkyl polyethoxylate sulfates.
  • anionic surfactants examples include "Surface Active Agents and Detergents" (Vol. I and LI by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • One type of anionic surfactant which can be utilized encompasses alkyl ester sulfonates. These are desirable because they can be made with renewable, non-petroleum resources. Preparation of the alkyl ester sulfonate surfactant component can be effected according to known methods disclosed in the technical literature.
  • linear esters of Cg-C 2 Q carboxylic acids can be sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm, and coconut oils, etc.
  • the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprises alkyl ester sulfonate surfactants of the structural formula:
  • R HCOR I SO 3 M wherein R ⁇ is a Cg-C Q hydrocarbyl, preferably an alkyl, or combination thereof, R is a C1 -C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a soluble salt- forming cation.
  • Suitable salts include metal salts such as sodium, potassium, and lithium salts, and substituted or unsubstituted ammonium salts, such as methyl-, dimethyl, - trimethyl, and quaternary ammonium cations, e.g. tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines, e.g.
  • R ⁇ is Cio-Ci g alkyl
  • R ⁇ is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R ⁇ is C 14"C 16 alkyl.
  • anionic surfactants useful for detersive pu ⁇ oses can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cc-C o linear alkylbenzenesulphonates, Cg-C 22 primary or secondary alkanesulphonates, Cg-C 2 4 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • Cc-C o linear alkylbenzenesulphonates Cg-C 22 primary or secondary alkanesulphonates
  • alkyl glycerol sulfonates alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C ⁇ 2 -C ⁇ g monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6- 4 diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglu
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23. Nonionic Detergent Surfactants - Suitable nonionic detergent surfactants are generally disclosed in U.S.
  • Nonionic surfactants include: alkyl ethoxylate, alkanoyl glucose amide, C ⁇ 2 -Ci alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C ⁇ 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), and mixtures thereof.
  • AE C ⁇ 2 -Ci alkyl ethoxylates
  • nonionic surfactant will be present typically in an effective amount.
  • the composition may contain at least about 0.1%, more preferably at least about 0.2%, even more preferably still, at least about 0.5% by weight of said composition of nonionic surfactant.
  • the composition will also preferably contain no more than about 20%, more preferably no more than about 15%, even more preferably, no more than about 10%> by weight of said composition of nonionic surfactant.
  • the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include Igepal® CO-630, marketed by the GAF Co ⁇ oration; and Triton® X-45, X-114, X-100, and X- 102, all marketed by the Rohm & Haas Company. These compounds are commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).
  • alkyl phenol alkoxylates e.g., alkyl phenol ethoxylates.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol are particularly preferred.
  • nonionic surfactants of this type include Tergitol® 15-S-9 (the condensation product of Cl l _ Ci5 linear secondary alcohol with 9 moles ethylene oxide), Tergitol® 24-L-6 NMW (the condensation product of C ⁇ -Ci4 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Co ⁇ oration; Neodol® 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol® 23-6.5 (the condensation product of C ⁇ 2 -Ci 3 linear alcohol with 6.5 moles of ethylene oxide), Neodol® 45-7 (the condensation product of CJ4-C15 linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (the condensation product of C14-C15
  • nonionic surfactants include Dobanol 91-8® marketed by Shell Chemical Co. and Genapol UD-080® marketed by Hoechst. This category of nonionic surfactant is referred to generally as "alkyl ethoxylates.”
  • alkyl ethoxylates The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
  • polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • examples of compounds of this type include certain of the commercially-available Pluronic® surfactants, marketed by BASF.
  • the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenedi amine consist of the reaction product of ethylenedi amine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
  • this type of nonionic surfactant include certain of the commercially available Tetronic® compounds, marketed by BASF.
  • R2 ⁇ (C n H 2n O) t (glycosyl) x wherein R ⁇ is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
  • the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • a polyalkylene-oxide chain joining the hydrophobic moiety and the polysaccharide moiety.
  • the preferred alkyleneoxide is ethylene oxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms.
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, terra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.
  • Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexa-glucosides.
  • Another type of suitable nonionic surfactant comprises the polyhydroxy fatty acid amides. These materials are more fully described in Pan/Gosselink; U.S Patent 5,332,528; Issued July 26, 1994, which is inco ⁇ orated herein by reference. These polyhydroxy fatty acid amides have a general structure of the formula:
  • Rl is H, C1 -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1 -C4 alkyl, more preferably C ⁇ or C alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R ⁇ is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C1 -C15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, marmose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH 2 - (CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n _ ⁇ -CH 2 OH, -CH 2 -(CHOH) 2 (CHOR')- (CHOH)-CH OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH 2 -(CHOH)4-CH 2 OH.
  • R can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2- hydroxy ethyl, or N-2-hydroxy propyl.
  • R2-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1 -deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1- deoxygalactityl, 1 -deoxymannityl, 1-deoxymaltotriotityl, etc.
  • Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product.
  • compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott, each of which is inco ⁇ orated herein by reference.
  • surfactants include the CjQ-Cig N-methyl, or N-hydroxypropyl, glucamides.
  • the N-propyl through N-hexyl C ⁇ 2 -Ci6 glucamides can be used for lower sudsing performance.
  • Preferred amides are Cg-C o ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
  • alkanol amide surfactants including the ammonia, monoethanol, and diethanol amides of fatty acids having an acyl moiety containing from about 8 to about 18 carbon atoms. These materials are represented by the formula:
  • R ⁇ is a saturated or unsaturated, hydroxy-free aliphatic hydrocarbon group having from about 7 to 21, preferably from about 11 to 17 carbon atoms; R represents a methylene or ethylene group; and m is 1, 2, or 3, preferably 1.
  • Specific examples of such amides are monoethanol amine coconut fatty acid amide and diethanolamine dodecyl fatty acid amide.
  • These acyl moieties may be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
  • Amphoteric Surfactants - Amphoteric surfactants may optionally be inco ⁇ orated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate.
  • amphoteric include C ⁇ -Cj betaines and sulfobetaines ("sultaines"), Ci Q-Cjg amine oxides, and mixtures thereof.
  • amphoteric surfactant will be present typically in an effective amount. More preferably, the composition may contain at least about 0.1%, more preferably at least about 0.2%, even more preferably still, at least about 0.5% by weight of said composition of amphoteric surfactant. The composition will also preferably contain no more than about 20%, more preferably no more than about 15%, even more preferably, no more than about 10% by weight of said composition of amphoteric surfactant.
  • Amine oxides are amphoteric surfactants and include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Preferred amine oxide surfactants have the formula
  • R ⁇ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R ⁇ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • These amine oxide surfactants in particular include C o-Cjg alkyl dimethyl amine oxides and Cg-Cj 2 alkoxy ethyl dihydroxy ethyl amine oxides.
  • amine oxide surfactant When present, amine oxide surfactant will be present typically in an effective amount. More preferably, the composition may contain at least about 0.1%, more preferably at least about 0.2%, even more preferably still, at least about 0.5% by weight of said composition of amine oxide surfactant. The composition will also preferably contain no more than about 20%, more preferably no more than about 15%, even more preferably, no more than about 10% by weight of said composition of amine oxide surfactant.
  • Suitable amine oxide surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
  • Suitable betaine surfactants include those of the general formula:
  • R is a hydrophobic group selected from alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amino
  • each R is an alkyl group containing from 1 to about 3 carbon atoms;
  • R is an alkylene group containing from 1 to about 6 carbon atoms.
  • betaines dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamido- propyldimethyl betaine, and dodecyldimethylammonium hexanoate.
  • Other suitable amidoalkylbetaines are disclosed in U.S. Patent Nos. 3,950,417; 4,137,191; and 4,375,421; and British Patent GB No. 2,103,236, all of which are inco ⁇ orated herein by reference.
  • Zwitterionic Surfactants - Zwitterionic surfactants can also be inco ⁇ orated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al, issued December 30, 1975 at column 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants. Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • the surfactant in the compositions of the present invention it is possible for the surfactant to be a combination of different surfactants, such as, different surfactants of the same type, i.e. LAS with PAS, surfactants of different type, an anionic with an nonionic, i.e an alkyl sulfate and an alkyl ethoxylate.
  • different surfactants of the same type i.e. LAS with PAS
  • surfactants of different type an anionic with an nonionic, i.e an alkyl sulfate and an alkyl ethoxylate.
  • One preferred combination is when the surfactant is a mixture of at least one amine oxide and at least one anionic surfactant.
  • Other surfactants may be present along with this combination.
  • the mole ratio of the anionic surfactant: amine oxide: diamine is from about 100:40:1 to about 9:0.5: 1, preferably from about 27:8: 1 to about 11 :3:1. It has been found that detergent compositions containing anionic surfactant, amine oxide and diamine in this specific mole ratio range provide improved low temperature stability, deliver better grease removal and tough food cleaning benefits at pH less than 12.5, and improved hard water cleaning.
  • Magnesium Ions improves the cleaning of greasy soils for various compositions, i.e., compositions containing alkyl ethoxy sulfates and/or polyhydroxy fatty acid amides. This is especially true when the compositions are used in softened water that contains few divalent ions. It is believed, while not wanting to be limited by theory, that, magnesium ions increase the packing of the surfactants at the oil/water interface, thereby reducing interfacial tension and improving grease cleaning. Compositions of the invention herein containing magnesium ions exhibit good grease removal, manifest mildness to the skin, and provide good storage stability.
  • the composition will preferably contain at least about 0.01%, more preferably at least about 0.015%, more preferably at least about 0.02%, even more preferably still, at least about 0.025% by weight of said composition of magnesium ions.
  • the cleaning composition will also preferably contain no more than about 5%, more preferably no more than about 2.5%, more preferably no more than about 1%, even more preferably, no more than about 0.05% by weight of said composition of magnesium ions.
  • the amount of magnesium ions present will always be equimolar or less than the amount of diamine present in the composition.
  • the composition may also be free of magnesium ions, as they are not essential to the invention.
  • the magnesium ions are added as a hydroxide, chloride, acetate, formate, oxide or nitrate salt to the compositions of the present invention.
  • compositions of the present invention are stable at 0°C, where as compositions with greater than equimolar amounts of magnesium than diamine( and outside the scope of the present invention) show no such stability, and fail after a few days at 0°C.
  • OPTIONAL DETERGENT INGREDIENTS
  • compositions herein include, but not limited to, enzymes such as protease, suds stabilizing polymers, builders and a stabilizing system for any enzymes, etc.
  • enzymes such as protease
  • suds stabilizing polymers such as glycerol, glycerol, glycerol, glycerol
  • compositions according to the present invention may further comprise a builder system.
  • a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylene-diamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylene-phosphonic acid.
  • phosphate builders can also be used herein.
  • Suitable polycarboxylates builders for use herein include maleic acid, citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C 10-20 alkyl or alkenyl, preferably C 12- 16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
  • Mixtures of these suitable polycarboxylates builders is also envisioned, such as a mixture of maleic acid and citric acid. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
  • suitable fatty acid builders for use herein are saturated or unsaturated CIO- 18 fatty acids, as well as the corresponding soaps.
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
  • the composition will preferably contain at least about 0.2%>, more preferably at least about 0.5%, more preferably at least about 3%, even more preferably still, at least about 5% by weight of the composition of builder.
  • the cleaning composition will also preferably contain no more than about 50%, more preferably no more than about 40%, more preferably no more than about 30%, even more preferably, no more than about 25% by weight of the composition of builder.
  • Enzymes - Detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance benefits.
  • Suitable enzymes include cellulases, hemicellulases, mannanase, peroxidases, proteases, gluco-amylases, amylases, Upases, cutinases, pectinases, xylanases, xyloglucanase, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases or mixtures thereof.
  • a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase.
  • the composition will preferably contain at least about 0.0001%o, more preferably at least about 0.0005%>, even more preferably still, at least about 0.001% by weight of the composition of enzyme.
  • the cleaning composition will also preferably contain no more than about 5%, more preferably no more than about 2%, even more preferably, no more than about 1% by weight of the composition of enzyme.
  • proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin.
  • the proteases for use in the detergent compositions herein include (but are not limited to) trypsin, subtilisin, chymotrypsin and elastase-type proteases.
  • Preferred for use herein are subtilisin-type proteolytic enzymes. Particularly preferred is bacterial serine proteolytic enzyme obtained from Bacillus subtilis and/or Bacillus licheniformis.
  • Suitable proteolytic enzymes include Novo Industri A/S Alcalase® (preferred), Esperase®' Savinase® (Copenhagen, Denmark), Gist-brocades' Maxatase®, Maxacal® and Maxapem 15® (protein engineered Maxacal®) (Delft, Netherlands), and subtilisin BPN and BPN'(preferred), which are commercially available.
  • Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those made by Genencor International, Inc. (San Francisco, California) which are described in European Patent 251,446B, granted December 28, 1994 (particularly pages 17, 24 and 98) and which are also called herein "Protease B".
  • Protease A a modified bacterial serine proteolytic enzyme
  • BPN modified bacterial serine proteolytic enzyme
  • Preferred proteolytic enzymes are selected from the group consisting of Alcalase ® (Novo Industri A/S), BPN", Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred.
  • proteases described in our co-pending application USSN 08/136,797 can be included in the detergent composition of the invention.
  • protease D is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, + 105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615 published April 20, 1995 by Genencor International (A. Baeck et al. entitled "Protease-Containing Cleaning Com
  • proteases are also described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company.
  • Other particularly useful proteases are multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin in combination with a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160,
  • protease variant includes a substitution set selected from the group consisting of:
  • protease variant includes a substitution set selected from the group consisting of:
  • protease variant includes the substitution set 101/103/104/159/232/236/245/248/252, preferably 101G/103A/104I/159D/232V/ 236H/245R/248D/252K.
  • proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221.
  • protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo.
  • a protease having decreased adso ⁇ tion and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
  • Other suitable proteases are described in EP 516 200 by Unilever.
  • Protease enzyme may be inco ⁇ orated into the compositions in accordance with the invention at a level of from 0.0001%» to 2% active enzyme by weight of the composition.
  • the composition will preferably contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%>, even more preferably still, at least about 0.001% of active enzyme by weight of the composition of protease enzyme.
  • the composition will also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably, no more than about 0.05% of active enzyme by weight of the composition of protease enzyme.
  • Amylase - Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains.
  • Suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN* (Novo Nordisk).
  • the enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • the composition will preferably contain at least about 0.0001%>, more preferably at least about 0.0002%, more preferably at least about 0.0005%, even more preferably still, at least about 0.001% of active enzyme by weight of the composition of amylase enzyme.
  • the composition will also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably, no more than about 0.05% of active enzyme by weight of the composition of amylase enzyme.
  • Amylase enzymes also include those described in WO95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056.
  • Other specific amylase enzymes for use in the detergent compositions of the present invention therefore include :
  • ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay.
  • Phadebas® ⁇ -amylase activity assay is described at pages 9-10, WO95/26397.
  • ⁇ -amylases according (a) comprising the amino sequence shown in the SEQ ID listings in the above cited reference, or an ⁇ -amylase being at least 80%> homologous with the amino acid sequence shown in the SEQ ID listing.
  • ⁇ -amylases according (a) obtained from an alkalophilic Bacillus species, comprising the following amino sequence in the N-terminal : His-His-Asn-Gly-Thr-Asn-Gly-Thr- Met-Me t-Gln-Tyr-Phe-Glu-T ⁇ -Tyr-Leu-Pro- Asn- Asp .
  • a polypeptide is considered to be X% homologous to the parent amylase if a comparison of the respective amino acid sequences, performed via algorithms, such as the one described by Lipman and Pearson in Science 227, 1985, p. 1435, reveals an identity ofX% (d) ⁇ -amylases according (a-c) wherein the ⁇ -amylase is obtainable from an alkalophilic
  • the term "obtainable from” is intended not only to indicate an amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced in an host organism transformed with said DNA sequence.
  • Variants of the following parent ⁇ -amylases which (i) have one of the amino acid sequences shown in corresponding respectively to those ⁇ -amylases in (a-e), or (ii) displays at least 80% homology with one or more of said amino acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an ⁇ -amylase having one of said amino acid sequences, and/or is encoded by a DNA sequence which hybridizes with the same probe as a DNA sequence encoding an ⁇ -amylase having one of said amino acid sequence; in which variants :
  • At least one amino acid residue of said parent ⁇ -amylase has been deleted; and/or 2. at least one amino acid residue of said parent ⁇ -amylase has been replaced by a different amino acid residue; and/or
  • At least one amino acid residue has been inserted relative to said parent ⁇ - amylase; said variant having an ⁇ -amylase activity and exhibiting at least one of the following properties relative to said parent ⁇ -amylase : increased thermostability, increased stability towards oxidation, reduced Ca ion dependency, increased stability and/or ⁇ -amylolytic activity at neutral to relatively high pH values, increased ⁇ -amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for ⁇ - amylase variant to the pH of the medium.
  • amylases suitable herein include, for example, ⁇ -amylases described in GB 1,296,839 to Novo; RAPID ASE®, International Bio-Synthetics, Inc. and TERMAMYL®. Novo. FUNGAMYL® from Novo is especially useful.
  • Engineering of enzymes for improved stability e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521.
  • Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use in 1993.
  • amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide/tetraace-ylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 11, measured versus the above- identified reference-point amylase. Stability can be measured using any of the art- disclosed technical tests. See, for example, references disclosed in WO 9402597.
  • Stability-enhanced amylases can be obtained from Novo or from Genencor International.
  • One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
  • Such preferred amylases include (a) an amylase according to the hereinbefore inco ⁇ orated WO 9402597, Novo, Feb.
  • amylase Stability was measured in CASCADE® and SUNLIGHT®;
  • particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as
  • DURAMYL® oxidative stability enhanced amylase
  • Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
  • carbohydrase enzymes which impart antimicrobial activity may also be included in the present invention.
  • Such enzymes include endoglycosidase, Type II endoglycosidase and glucosidase as disclosed in U.S. Patent Nos. 5,041,236, 5,395,541, 5,238,843 and 5,356,803 the disclosures of which are herein inco ⁇ orated by reference.
  • other enzymes having antimicrobial activity may be employed as well including peroxidases, oxidases and various other enzymes.
  • compositions of the present invention when any enzyme is present in the composition.
  • Cellulases - the cellulases usable in the present invention include both bacterial or fungal cellulase. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids.
  • Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo).
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.
  • Said cellulases and/or peroxidases are normally inco ⁇ orated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • the composition will preferably contain at least about 0.0001%), more preferably at least about 0.0002%), more preferably at least about 0.0005%, even more preferably still, at least about 0.001% of active enzyme by weight of the composition of cellulases and/or peroxidases enzyme.
  • the composition will also preferably contain no more than about 2%, more preferably no more than about 0.5%o, more preferably no more than about 0.1%, even more preferably, no more than about 0.05% of active enzyme by weight of the composition of cellulases and/or peroxidases enzyme.
  • Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable Upases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens LAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • Further suitable Upases are Upases such as Ml
  • Lipase® and Lipomax® are suitable commercial Upases.
  • Other suitable commercial Upases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum Upases from U.S. Biochemical Co ⁇ ., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli.
  • LLPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.
  • Highly preferred Upases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826.
  • D native lipase ex Humicola lanuginosa aspartic acid
  • L Leucine
  • the substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • the Humicola lanuginosa strain DSM 4106 is used.
  • lipase variant (D96L) may be added in an amount corresponding to 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely Upases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
  • the composition will preferably contain at least about 0.0001%>, more preferably at least about 0.0002%, more preferably at least about 0.0005%, even more preferably still, at least about 0.001% of active enzyme by weight of the composition of lipase enzyme.
  • the composition will also preferably contain no more than about 2%, more preferably no more than about 0.5%>, more preferably no more than about 0.1%, even more preferably, no more than about 0.05% of active enzyme by weight of the composition of lipase enzyme.
  • compositions of the present invention may also comprise a mannanase enzyme.
  • the mannanase is selected from the group consisting of: three mannans-degrading enzymes : EC 3.2.1.25 : ⁇ -mannosidase, EC 3.2.1.78 : Endo-l,4- ⁇ - mannosidase, referred therein after as "mannanase” and EC 3.2.1.100 : 1,4- ⁇ - mannobiosidase and mixtures thereof.
  • mannanase is selected from the group consisting of: three mannans-degrading enzymes : EC 3.2.1.25 : ⁇ -mannosidase, EC 3.2.1.78 : Endo-l,4- ⁇ - mannosidase, referred therein after as "mannanase” and EC 3.2.1.100 : 1,4- ⁇ - mannobiosidase and mixtures thereof.
  • the treating compositions of the present invention when a mannanase is present, comprise a ⁇ -l,4-Mannosidase (E.C. 3.2.1.78) referred to as Mannanase.
  • Mannanase or "galactomannanase” denotes a mannanase enzyme defined according to the art as officially being named mannan endo-l,4-beta-mannosidase and having the alternative names beta-mannanase and endo-l,4-mannanase and catalysing the reaction: random hydrolysis of 1,4-beta-D- mannosidic linkages in mannans, galactomannans, glucomannans, and galactoglucomannans.
  • Mannanases (EC 3.2.1.78) constitute a group of polysaccharases which degrade mannans and denote enzymes which are capable of cleaving polyose chains contaning mannose units, i.e. are capable of cleaving glycosidic bonds in mannans, glucomannans, galactomannans and galactogluco-mannans.
  • Mannans are polysaccharides having a backbone composed of ⁇ -1,4- linked mannose; glucomannans are polysaccharides having a backbone or more or less regularly alternating ⁇ -1,4 linked mannose and glucose; galactomannans and galactoglucomannans are mannans and glucomannans with ⁇ -1,6 linked galactose sidebranches. These compounds may be acetylated.
  • the degradation of galactomannans and galactoglucomannans is facilitated by full or partial removal of the galactose sidebranches. Further the degradation of the acetylated mannans, glucomannans, galactomannans and galactogluco-mannans is facilitated by full or partial deacetylation. Acetyl groups can be removed by alkali or by mannan acetylesterases.
  • the oligomers which are released from the mannanases or by a combination of mannanases and ⁇ -galactosidase and/or mannan acetyl esterases can be further degraded to release free maltose by ⁇ -mannosidase and/or ⁇ -glucosidase.
  • Mannanases have been identified in several Bacillus organisms. For example, Talbot et al, Appl. Environ. Microbiol, Vol.56, No. 11, pp. 3505-3510 (1990) describes a beta-mannanase derived from Bacillus stearothermophilus in dimer form having molecular weight of 162 kDa and an optimum pH of 5.5-7.5. Mendoza et al, World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551-555 (1994) describes a beta-mannanase derived from Bacillus subtilis having a molecular weight of 38 kDa, an optimum activity at pH 5.0 and 55C and a pi of 4.8.
  • JP-03047076 discloses a beta-mannanase derived from Bacillus sp., having a molecular weight of 373 kDa measured by gel filtration, an optimum pH of 8-10 and a pi of 5.3-5.4.
  • JP-63056289 describes the production of an alkaline, thermostable beta-mannanase which hydrolyses beta-l,4-D-mannopyranoside bonds of e.g. mannans and produces manno-oligosaccharides.
  • JP-63036774 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta- mannosidase at an alkaline pH.
  • JP-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001.
  • a purified mannanase from Bacillus amyloliquefaciens useful in the bleaching of pulp and paper and a method of preparation thereof is disclosed in WO 97/11164.
  • WO 91/18974 describes a hemicellulase such as a glucanase, xylanase or mannanase active at an extreme pH and temperature.
  • WO 94/25576 discloses an enzyme from AspergiUus aculeatus, CBS 101.43, exhibiting mannanase activity which may be useful for degradation or modification of plant or algae cell wall material.
  • WO 93/24622 discloses a mannanase isolated from Trichoderma reseei useful for bleaching lignocellulosic pulps.
  • An hemicellulase capable of degrading mannan-containing hemicellulose is described in WO91/18974 and a purified mannanase from Bacillus amyloliquefaciens is described in WO97/11164.
  • the mannanase enzyme will be an alkaline mannanase as defined below, more preferably, a mannanase originating from a bacterial source.
  • the laundry detergent composition of the present invention will comprise an alkaline mannanase selected from the mannanase from the strain Bacillus agaradhaerens NICMB 40482; the mannanase from Bacillus subtilis strain 168, gene yght; the mannanase from Bacillus sp. 1633 and/or the mannanase from Bacillus sp. AAI12.
  • Most preferred mannanase for the inclusion in the detergent compositions of the present invention is the mannanase enzyme originating from Bacillus sp. 1633 as described in the co-pending Danish patent application No. PA 1998 01340.
  • alkaline mannanase enzyme is meant to encompass an enzyme having an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to 10.5.
  • the alkaline mannanase from Bacillus agaradhaerens NICMB 40482 is described in the co-pending U.S. patent application serial No. 09/111,256. More specifically, this mannanase is: i) a polypeptide produced by Bacillus agaradhaerens, NCEVIB 40482; or ii) a polypeptide comprising an amino acid sequence as shown in positions
  • isolated polypeptide having mannanase activity selected from the group consisting of: (a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 97 to nucleotide 1029 as shown in U.S. patent application serial No. 09/111,256; (b) species homo logs of (a); (c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70%> identical to the amino acid sequence of SEQ LD NO: 2 from amino acid residue 32 to amino acid residue 343 as shown in U.S. patent application serial No. 09/111,256; (d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d).
  • the plasmid pSJ1678 comprising the polynucleotide molecule (the DNA sequence) encoding said mannanase has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the
  • a second more preferred enzyme is the mannanase from the Bacillus subtilis strain 168, which is described in the co-pending U.S. patent application serial No. 09/095,163. More specifically, this mannanase is: i) is encoded by the coding part of the DNA sequence shown in SED LD No. 5 shown in the U.S. patent application serial No. 09/095,163 or an analogue of said sequence; and/or ii) a polypeptide comprising an amino acid sequence as shown SEQ ID NO:6 shown in the U.S. patent application serial No.
  • an analogue of the polypeptide defined in ii) which is at least 70% homologous with said polypeptide, or is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form.
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70% identical to the amino acid sequence of SEQ LD NO: 6 as shown in the U.S. patent application serial No. 09/095,163; (d) molecules complementary to (a), (b) or (c); and
  • mannanase degenerate nucleotide sequences of (a), (b), (c) or (d).
  • a third more preferred mannanase is described in the co-pending Danish patent application No. PA 1998 01340. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. 1633; ii) a polypeptide comprising an amino acid sequence as shown in positions 33-340 of SEQ ID NO:2 as shown in the Danish application No.
  • PA 1998 01340 or iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous with said polypeptide, is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form.
  • an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous with said polypeptide is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form.
  • the corresponding isolated polynucleotide molecule selected from the group consisting of:
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 33 to amino acid residue 340 the Danish application No. PA 1998 01340; (d) molecules complementary to (a), (b) or (c); and
  • the plasmid pBXM3 comprising the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Pu ⁇ oses of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 29 May 1998 under the deposition number DSM 12197.
  • mannanase A fourth more prefe ⁇ ed mannanase is described in the Danish co-pending patent application No. PA 1998 01341. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. AAI 12; ii) a polypeptide comprising an amino acid sequence as shown in positions 25-362 of SEQ LD NO:2as shown in the Danish application No.
  • PA 1998 01341 or iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous with said polypeptide, is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form. Also encompassed is the corresponding isolated polynucleotide molecule selected from the group consisting of
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ LD NO: 2 from amino acid residue 25 to amino acid residue 362 as shown in the Danish application No. PA 1998 01341; (d) molecules complementary to (a), (b) or (c); and
  • the plasmid pBXMl comprising the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Pu ⁇ oses of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 7 October 1998 under the deposition number DSM 12433.
  • the mannanase when present, is inco ⁇ orated into the treating compositions of the present invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, most preferred from 0.001% to 0.02% pure enzyme by weight of the composition.
  • compositions of the present invention may also comprise a xyloglucanase enzyme.
  • Suitable xyloglucanases for the pu ⁇ ose of the present invention are enzymes exhibiting endoglucanase activity specific for xyloglucan, preferably at a level of from about 0.001% to about 1%, more preferably from about 0.01% to about 0.5%, by weight of the composition.
  • the term "endoglucanase activity” means the capability of the enzyme to hydrolyze 1,4- ⁇ -D-glycosidic linkages present in any cellulosic material, such as cellulose, cellulose derivatives, lichenin, ⁇ -D-glucan, or xyloglucan.
  • the endoglucanase activity may be determined in accordance with methods known in the art, examples of which are described in WO 94/14953 and hereinafter.
  • One unit of endoglucanase activity e.g. CMCU, AVIU, XGU or BGU
  • CMCU CMC
  • AVIU acid swollen Avicell
  • XGU xyloglucan
  • BGU cereal ⁇ - glucan
  • the reducing sugars are determined as described in WO 94/14953 and hereinafter.
  • the specific activity of an endoglucanase towards a substrate is defined as units/mg of protein.
  • AACCAACCCC AGCCGACCGA TTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTTTCAC CATGAAGCTT
  • AAAA SEQ LD NO: 18 or a sequence homologous thereto encoding a polypeptide specific for xyloglucan with endoglucanase activity, ii) is immunologically reactive with an antibody raised against a highly purified endoglucanase encoded by the DNA sequence defined in i) and derived from AspergiUus aculeatus, CBS 101.43, and is specific for xyloglucan.
  • the term "specific for xyloglucan” means that the endoglucanse enzyme exhibits its highest endoglucanase activity on a xyloglucan substrate, and preferably less than 75% activity, more preferably less than 50% activity, most preferably less than about 25% activity, on other cellulose-containing substrates such as carboxymethyl cellulose, cellulose, or other glucans.
  • the specificity of an endoglucanase towards xyloglucan is further defined as a relative activity determined as the release of reducing sugars at optimal conditions obtained by incubation of the enzyme with xyloglucan and the other substrate to be tested, respectively.
  • the specificity may be defined as the xyloglucan to ⁇ -glucan activity (XGU/BGU), xyloglucan to carboxy methyl cellulose activity (XGU/CMCU), or xyloglucan to acid swollen Avicell activity (XGU/ AVIU), which is preferably greater than about 50, such as 75, 90 or 100.
  • the term "derived from” as used herein refers not only to an endoglucanase produced by strain CBS 101.43, but also an endoglucanase encoded by a DNA sequence isolated from strain CBS 101.43 and produced in a host organism transformed with said DNA sequence.
  • homologue indicates a polypeptide encoded by DNA which hybridizes to the same probe as the DNA coding for an endoglucanase enzyme specific for xyloglucan under certain specified conditions (such as presoaking in 5xSSC and prehybridizing for 1 h at -40°C in a solution of 5xSSC, 5xDenhardt's solution, and 50 ⁇ g of denatured sonicated calf thymus DNA, followed by hybridization in the same solution supplemented with 50 ⁇ Ci 32-P-dCTP labelled probe for 18 h at -40°C and washing three times in 2xSSC, 0.2% SDS at 40°C for 30 minutes).
  • the term is intended to refer to a DNA sequence which is at least 70% homologous to any of the sequences shown above encoding an endoglucanase specific for xyloglucan, including at least 75%, at least 80%, at least 85%, at least 90% or even at least 95% with any of the sequences shown above.
  • the term is intended to include modifications of any of the DNA sequences shown above, such as nucleotide substitutions which do not give rise to another amino acid sequence of the polypeptide encoded by the sequence, but which co ⁇ espond to the codon usage of the host organism into which a DNA construct comprising any of the DNA sequences is introduced or nucleotide substitutions which do give rise to a different amino acid sequence and therefore, possibly, a different amino acid sequence and therefore, possibly, a different protein structure which might give rise to an endoglucanase mutant with different properties than the native enzyme.
  • Other examples of possible modifications are insertion of one or more nucleotides into the sequence, addition of one or more nucleotides at either end of the sequence, or deletion of one or more nucleotides at either end or within the sequence.
  • Endoglucanase specific for xyloglucan useful in the present invention preferably is one which has a XGU/BGU, XGU/CMU and/or XGU/AVLU ratio (as defined above) of more than 50, such as 75, 90 or 100.
  • endoglucanase specific for xyloglucan is preferably substantially devoid of activity towards ⁇ -glucan and/or exhibits at the most 25% such as at the most 10% or about 5%, activity towards carboxymethyl cellulose and/or Avicell when the activity towards xyloglucan is 100%>.
  • endoglucanase specific for xyloglucan of the invention is preferably substantially devoid of transferase activity, an activity which has been observed for most endoglucanases specific for xyloglucan of plant origin.
  • Endoglucanase specific for xyloglucan may be obtained from the fungal species A. aculeatus, as described in WO 94/14953. Microbial endoglucanases specific for xyloglucan has also been described in WO 94/14953. Endoglucanases specific for xyloglucan from plants have been described, but these enzymes have transferase activity and therefore must be considered inferior to microbial endoglucanses specific for xyloglucan whenever extensive degradation of xyloglucan is desirable.
  • An additional advantage of a microbial enzyme is that it, in general, may be produced in higher amounts in a microbial host, than enzymes of other origins.
  • the xyloglucanase when present, is inco ⁇ orated into the treating compositions of the invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, most prefe ⁇ ed from 0.001% to 0.02% pure enzyme by weight of the composition.
  • Enzyme Stabilizing System The preferred compositions herein may additionally comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the protease or other enzymes used in the compositions herein.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, polyhydroxyl compounds and mixtures thereof such as are described in U.S. Patents 4,261,868, Hora et al, issued April 14, 1981; 4,404,115, Tai, issued September 13, 1983; 4,318,818, Letton et al; 4,243,543, Guildert et al issued January 6, 1981; 4,462,922, Boskamp, issued July 31, 1984; 4,532,064, Boskamp, issued July 30, 1985; and 4,537,707, Severson Jr., issued August 27, 1985, all of which are inco ⁇ orated herein by reference.
  • the composition will preferably contain at least about 0.001%>, more preferably at least about 0.005%, even more preferably still, at least about 0.01%> by weight of the composition of enzyme stabilizing system.
  • the composition will also preferably contain no more than about 10%, more preferably no more than about 8%, no more than about 6% of active enzyme by weight of the composition of enzyme stabilizing system.
  • One stabilizing approach is the use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes.
  • Calcium ions are generally more effective than magnesium ions and are prefe ⁇ ed herein if only one type of cation is being used.
  • Typical detergent compositions, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes inco ⁇ orated.
  • Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts co ⁇ esponding to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant. However, it is especially prefe ⁇ ed that the composition contain no added calcium ions, and even more prefe ⁇ ed that the composition be free of calcium ions.
  • Borate stabilizers when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use.
  • Substituted boric acids such as phenylboronic acid, butaneboronic acid, p- bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.
  • chlorine bleach or oxygen bleach scavengers can be added to compositions of the present invention to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
  • Suitable chlorine scavenger anions are salts containing ammonium cations. These can be selected from the group consisting of reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc., antioxidants like carbonate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
  • reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • antioxidants like carbonate, ascorbate, etc.
  • organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
  • EDTA ethylenediaminetetracetic acid
  • MEA monoethanolamine
  • compositions of the present invention may optionally contain a polymeric suds stabilizer.
  • These polymeric suds stabilizers provide extended suds volume and suds duration without sacrificing the grease cutting ability of the liquid detergent compositions.
  • These polymeric suds stabilizers are selected from: homopolymers of (N,N-dialkylamino)alkyl acrylate esters having the formula:
  • each R is independently hydrogen, Cj-Cg alkyl, and mixtures thereof, R 1 is hydrogen, Cj-C6 alkyl, and mixtures thereof, n is from 2 to about 6; and ii) copolymers of (i) and
  • R 1 is hydrogen, C1-C6 alkyl, and mixtures thereof, provided that the ratio of (ii) to (i) is from about 2 to 1 to about 1 to 2;
  • the molecular weight of the polymeric suds boosters, determined via conventional gel permeation chromatography, is from about 1.000 to about 2,000,000, preferably from about 5,000 to about 1,000,000, more preferably from about 10,000 to about 750.000, more preferably from about 20,000 to about 500.000, even more preferably from about 35.000 to about 200,000.
  • the polymeric suds stabilizer can optionally be present in the form of a salt, either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
  • a salt either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
  • One prefe ⁇ ed polymeric suds stabilizer is (N.N-dimethylamino)alkyl acrylate esters, namelv
  • the composition will preferably contain at least about 0.01%, more preferably at least about 0.05%, even more preferably still, at least about 0.1% by weight of the composition of polymeric suds booster.
  • the cleaning composition will also preferably contain no more than about 15%, more preferably no more than about 10%, even more preferably, no more than about 5% by weight of the composition of polymeric suds booster.
  • suitable polymeric include: Lysozyme, a Polypeptide comprising Lys, Ala, Glu, Tyr (5:6:2: 1) having a molecular weight of approximately 52,000 daltons, LX1279 available from Baker Petrolite.
  • the dishwashing detergent compositions herein can also contain from about 0.2% to 5% of a thickening agent. More preferably, such a thickener will comprise from about 0.5% to 2.5% of the compositions herein.
  • Thickeners are typically selected from the class of cellulose derivatives. Suitable thickeners include hydroxy ethyl cellulose, hydroxyethyl methyl cellulose, carboxy methyl cellulose, Quatrisoft LM200, and the like.
  • a prefe ⁇ ed thickening agent is hydroxypropyl methylcellulose.
  • the composition will preferably contain at least about 0.1%, more preferably at least about 0.2%, even more preferably still, at least about 5% by weight of the composition of thickener.
  • the composition will also preferably contain no more than about 5%, more preferably no more than about 3%, even more preferably, no more than about 2.5% by weight of the composition of thickener.
  • the hydroxypropyl methylcellulose polymer has a number average molecular weight of about 50,000 to 125,000 and a viscosity of a 2 wt.% aqueous solution at 25°C. (ADTMD2363) of about 50,000 to about 100,000 cps.
  • An especially prefe ⁇ ed hydroxypropyl cellulose polymer is Methocel® J75MS-N wherein a 2.0 wt.% aqueous solution at 25°C. has a viscosity of about 75,000 cps.
  • hydroxypropyl cellulose polymers are surface treated such that the hydroxypropyl cellulose polymer will ready disperse at 25°C. into an aqueous solution having a pH of at least about 8.5.
  • the hydroxypropyl methylcellulose polymer should impart to the detergent composition a Brookfield viscosity of from about 500 to 3500 cps at 25°C. More preferably, the hydroxypropyl methylcellulose material will impart a viscosity of from about 1000 to 3000 cps at 25°C. For pu ⁇ oses of this invention, viscosity is measured with a Brookfield LVTDV-11 viscometer apparatus using an RV #2 spindle at 12 ⁇ m. Solvents.
  • a variety of water-miscible liquids such as lower alkanols, diols, other polyols, ethers, amines, and the like may be used Particularly prefe ⁇ ed are the C1-C4 alkanols.
  • Such solvents can be present in the compositions herein to the extent of from about 1% to 8%.
  • the composition will preferably contain at least about 0.01%, more preferably at least about 0.5%, even more preferably still, at least about 1% by weight of the composition of solvent.
  • the composition will also preferably contain no more than about 20%, more preferably no more than about 10%>, even more preferably, no more than about 8%> by weight of the composition of solvent.
  • solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present.
  • Solvents are broadly defined as compounds that are liquid at temperatures of 20°C-25°C and which are not considered to be surfactants. One of the distinguishing features is that solvents tend to exist as discrete entities rather than as broad mixtures of compounds. Examples of suitable solvents for the present invention include, methanol, ethanol, propanol, isopropanol, 2-methyl py ⁇ olidinone, benzyl alcohol and mo ⁇ holine n-oxide. Prefe ⁇ ed among these solvents are methanol and isopropanol.
  • Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms.
  • suitable solvents are glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons.
  • Suitable glycols which can be used herein are according to the formula HO- CR1 2-OH wherein Rl and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic.
  • Suitable glycols to be used herein are dodecaneglycol and/or propanediol.
  • polypropylene glycols such as those with a molecular weigh in the range of about 100 to 1000.
  • Suitable alkoxylated glycols which can be used herein are according to the formula R-(A)n-Rl-OH wherein R is H, OH, a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein Rl is H or a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated glycols to be used herein are methoxy octadecanol and/or ethoxyethoxyethanol .
  • Suitable alkoxylated aromatic alcohols which can be used herein are according to the formula R (A) n -OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10. wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated aromatic alcohols are benzoxyethanol and/or benzoxypropanol.
  • Suitable aromatic alcohols which can be used herein are according to the formula R-OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
  • R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
  • a suitable aromatic alcohol to be used herein is benzyl alcohol.
  • Suitable aliphatic branched alcohols which can be used herein are according to the formula R-OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12.
  • Particularly suitable aliphatic branched alcohols to be used herein include 2-ethylbutanol and/or 2- methylbutanol.
  • Suitable alkoxylated aliphatic branched alcohols which can be used herein are according to the formula R (A) n -OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and/or 2-methylbutoxyethanol.
  • Suitable alkoxylated linear C1-C5 alcohols which can be used herein are according to the formula R (A) n -OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated aliphatic linear C1-C5 alcohols are butoxy propoxy propanol (n-BPP), butoxyethanol, butoxypropanol, ethoxvethanol or mixtures thereof. Butoxy propoxy propanol is commercially available under the trade name n-BPP® from Dow chemical.
  • Suitable linear C1-C5 alcohols which can be used herein are according to the formula R-OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4.
  • Suitable linear C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof.
  • Suitable solvents include, but are not limited to, butyl diglycol ether (BDGE), butyltriglycol ether, ter amilic alcohol and the like. Particularly prefe ⁇ ed solvents which can be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
  • BDGE butyl diglycol ether
  • ter amilic alcohol ter amilic alcohol
  • Particularly prefe ⁇ ed solvents which can be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
  • Suitable solvents for use herein include propylene glycol derivatives such as n-butoxypropanol or n- butoxypropoxypropanol, water-soluble CARBITOL R solvents or water-soluble CELLOSOLVE R solvents; water-soluble CARBITOL R solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a prefe ⁇ ed water-soluble carbitol is 2-(2- butoxyethoxy)ethanol also known as butyl carbitol.
  • Water-soluble CELLOSOLVE R solvents are compounds of the 2-alkoxyethoxy ethanol class, with 2-butoxyethoxyethanol being prefe ⁇ ed.
  • Other suitable solvents include benzyl alcohol, and diols such as 2-ethyl- 1, 3-hexanediol and 2,2,4- -rimethyl-l,3-pentanediol and mixtures thereof.
  • Some prefe ⁇ ed solvents for use herein are n-butoxypropoxypropanol, BUTYL CARBITOL ® and mixtures thereof.
  • the solvents can also be selected from the group of compounds comprising ether derivatives of mono-, di- and tri-ethylene glycol, propylene glycol, butylene glycol ethers, and mixtures thereof.
  • the molecular weights of these solvents are preferably less than 350, more preferably between 100 and 300, even more preferably between 115 and 250.
  • Examples of prefe ⁇ ed solvents include, for example, mono-ethylene glycol n-hexyl ether, mono-propylene glycol n-butyl ether, and tri-propylene glycol methyl ether.
  • Ethylene glycol and propylene glycol ethers are commercially available from the Dow Chemical Company under the tradename "Dowanol” and from the Arco Chemical Company under the tradename “Arcosolv”.
  • Other prefe ⁇ ed solvents including mono- and di-ethylene glycol n-hexyl ether are available from the Union Carbide company.
  • Perfumes - Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished perfumes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from about 0.01 %> to about 2%>, by weight, of the detergent compositions herein, and individual perfumery ingredients can comprise from about 0.0001%> to about 90% of a finished perfume composition.
  • Non-limiting examples of perfume ingredients useful herein include: 7-acetyl- l,2,3,4,5,6,7,8-octahydro-l,l,6,7-tetramethyl naphthalene; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl l,6,10-trimethyl-2,5,9- cyclododecatrien-1-yl ketone; 7-acetyl-l,l,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert- butyl- 1 , 1 -dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta- naphthyl ketone; 6-acetyl-l,l,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-l,l,2,6- tetramethyl in
  • perfume materials are those that provide the largest odor improvements in finished product compositions containing cellulases.
  • These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(para-tert- butylphenyl)-propionaldehyde; 7-acetyl-l,2,3,4,5,6,7,8-octahydro-l,l,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-l,l,3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta- naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8- hexahydro-4,6,6,6,
  • perfume materials include essential oils, resinoids, and resins from a variety of sources including, but not limited to: Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin.
  • perfume chemicals include phenyl ethyl alcohol, te ⁇ ineol, linalool, linalyl acetate, geraniol, nerol, 2-(l,l-dimethylethyl)-cyclohexanol acetate, benzyl acetate, and eugenol.
  • Carriers such as diethylphthalate can be used in the finished perfume compositions.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates. polvfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetrace-tates, N-hydroxyethylethylenediaminetriacetates, nitrilo-tri- acetates, ethylenediamine tetrapro-prionates, triethylenetetraaminehexacetates. diethylenetriaminepentaacetates, and ethanoldi-glycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methyl enephosphonates) as DEQUEST. Prefe ⁇ ed, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Prefe ⁇ ed compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2- dihydroxy-3,5-disulfobenzene.
  • a prefe ⁇ ed biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • EDDS ethylenediamine disuccinate
  • the compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder.
  • MGDA water-soluble methyl glycine diacetic acid
  • the so called "weak” builders such as citrate can also be used as chelating agents.
  • these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if utilized. the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
  • composition will preferably contain at least about 0.01%, more preferably at least about 0.1% by weight of the composition of chelating agent.
  • the composition will also preferably contain no more than about 15%, more preferably no more than about 3% by weight of the composition of chelating agent.
  • Composition pH Dishwashing compositions of the invention will be subjected to acidic stresses created by food soils when put to use, i.e., diluted and applied to soiled dishes. If a composition with a pH greater than 7 is to be more effective, it may optionally contain a buffering agent capable of providing a generally more alkaline pH in the composition and in dilute solutions, i.e., about 0.1% to 0.4% by weight aqueous solution, of the composition.
  • the pKa value of this buffering agent should be about 0.5 to 1.0 pH units below the desired pH value of the composition (determined as described above).
  • the pKa of the buffering agent should be from about 7 to about 10. Under these conditions the buffering agent most effectively controls the pH while using the least amount thereof.
  • the buffering agent may be an active detergent in its own right, or it may be a low molecular weight, organic or inorganic material that is used in this composition solely for maintaining an alkaline pH.
  • Prefe ⁇ ed buffering agents for compositions of this invention are nitrogen-containing materials. Some examples are amino acids such as lysine or lower alcohol amines like mono-, di-, and tri-ethanolamine.
  • Tri(hydroxymethyl)amino methane (HOCH2)3CNH3 Tri(hydroxymethyl)amino methane (HOCH2)3CNH3
  • 2-amino-2-ethyl-l,3-propanediol 2-amino-2-methyl-propanol
  • 2-amino-2- methyl-l,3-propanol disodium glutamate
  • N-methyl diethanolamide 1,3-diamino- propanol N,N'-tetra-methyl-l ,3-diamino-2-propanol
  • Useful inorganic buffers/alkalinity sources include the alkali metal carbonates and alkali metal phosphates, e.g., sodium carbonate, sodium polyphosphate.
  • alkali metal carbonates and alkali metal phosphates e.g., sodium carbonate, sodium polyphosphate.
  • alkali metal carbonates and alkali metal phosphates e.g., sodium carbonate, sodium polyphosphate.
  • McCutcheon's EMULSLFLERS AND DETERGENTS North American Edition, 1997, McCutcheon Division, MC Publishing Company Kirk and WO 95/07971 both of which are inco ⁇ orated herein by reference.
  • the composition will preferably contain at least about 0.1%, more preferably at least about 1%, even more preferably still, at least about 2% by weight of the composition of buffering agent.
  • the composition will also preferably contain no more than about 15%. more preferably no more than about 10%. even more preferably, no more than about 8% by weight of the composition of buffering agent.
  • Hydrotropes -
  • the aqueous liquid carrier may comprise one or more materials which are hydrotropes.
  • Hydrotropes suitable for use in the compositions herein include the C1-C3 alkyl aryl sulfonates, C6-C12 alkanols, C1-C6 carboxylic sulfates and sulfonates, urea, Ci -Cg hydrocarboxylates, C1-C4 carboxylates, C2-C4 organic diacids and mixtures of these hydrotrope materials.
  • the liquid detergent composition of the present invention preferably comprises from about 0.5% to 8%, by weight of the liquid detergent composition of a hydrotrope selected from alkali metal and calcium xylene and toluene sulfonates.
  • Suitable C1 -C3 alkyl aryl sulfonates include sodium, potassium, calcium and ammonium xylene sulfonates; sodium, potassium, calcium and ammonium toluene sulfonates; sodium, potassium, calcium and ammonium cumene sulfonates; and sodium, potassium, calcium and ammonium substituted or unsubstituted naphthalene sulfonates and mixtures thereof.
  • Ci -Cg carboxylic sulfate or sulfonate salts are any water soluble salts or organic compounds comprising 1 to 8 carbon atoms (exclusive of substituent groups), which are substituted with sulfate or sulfonate and have at least one carboxylic group.
  • the substituted organic compound may be cyclic, acylic or aromatic, i.e. benzene derivatives.
  • Prefe ⁇ ed alkyl compounds have from 1 to 4 carbon atoms substituted with sulfate or sulfonate and have from 1 to 2 carboxylic groups.
  • hydrotrope examples include sulfosuccinate salts, sulfophthalic salts, sulfoacetic salts, m- sulfobenzoic acid salts and diester sulfosuccinates, preferably the sodium or potassium salts as disclosed in U.S. 3,915,903.
  • Suitable C1 -C4 hydrocarboxylates and -C4 carboxylates for use herein include acetates and propionates and citrates.
  • Suitable C2-C4 diacids for use herein include succinic, glutaric and adipic acids.
  • hydrotrope examples include C6-Cj2 alkanols and urea.
  • Prefe ⁇ ed hydrotropes for use herein are sodium, potassium, calcium and ammonium cumene sulfonate; sodium, potassium, calcium and ammonium xylene sulfonate; sodium, potassium, calcium and ammonium toluene sulfonate and mixtures thereof. Most prefe ⁇ ed are sodium cumene sulfonate and calcium xylene sulfonate and mixtures thereof. These prefe ⁇ ed hydrotrope materials can be present in the composition to the extent of from about 0.5% to 8% by weight.
  • the composition will preferably contain at least about 0.1%, more preferably at least about 0.2%, even more preferably still, at least about 0.5% by weight of the composition of hydrotrope.
  • the composition will also preferably contain no more than about 15%, more preferably no more than about 10%, even more preferably, no more than about 8% by weight of the composition of hydrotrope.
  • the detergent compositions will further preferably comprise one or more detersive adjuncts selected from the following: soil release polymers, polymeric dispersants, polysaccharides, abrasives, bactericides, tarnish inhibitors, dyes, antifungal or mildew control agents, insect repellents, hydrotropes, processing aids, suds boosters, brighteners, anti-co ⁇ osive aids and stabilizers antioxidants.
  • detersive adjuncts selected from the following: soil release polymers, polymeric dispersants, polysaccharides, abrasives, bactericides, tarnish inhibitors, dyes, antifungal or mildew control agents, insect repellents, hydrotropes, processing aids, suds boosters, brighteners, anti-co ⁇ osive aids and stabilizers antioxidants.
  • detersive adjuncts selected from the following: soil release polymers, polymeric dispersants, polysaccharides, abrasives, bactericides, tarnish inhibitors
  • suds boosters such as the C ⁇ O' l ⁇ alkanolamides can be inco ⁇ orated into the compositions, typically at 1 %- 10% levels.
  • the C10- 4 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • An antioxidant can be optionally added to the detergent compositions of the present invention. They can be any conventional antioxidant used in detergent compositions, such as 2.6-di-tert-butyl-4-methylphenol (BHT), carbamate, ascorbate. thiosulfate, monoethanolamine(MEA), diethanolamine, triethanolamine, etc. It is prefe ⁇ ed that the antioxidant, when present, be present in the composition from about 0.001% to about 5% by weight.
  • BHT 2.6-di-tert-butyl-4-methylphenol
  • MEA monoethanolamine
  • diethanolamine diethanolamine
  • triethanolamine triethanolamine
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function
  • a porous hydrophobic silica (trademark SLPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C]_3_i5 ethoxylated alcohol (EO 7) nonionic surfactant Typically, the enzyme/surfactant solution is 2 5 X the weight of silica
  • the resulting powder is dispersed with stirring in sihcone oil (va ⁇ ous silicone oil viscosities in the range of 500- 12,500 can be used)
  • the resulting si cone oil dispersion is emulsified or otherwise added to the final detergent mat ⁇ x
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, faboc conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions Form of the composition
  • compositions herein can be in any of the conventional forms for hand dishwashing compositions, such as, paste, liquid, granule, powder, gel, and mixtures thereof Highly prefe ⁇ ed embodiments are in liquid or gel form
  • the liquid compositions can be either aqueous or nonaqueous When the composition is a aqueous liquid the composition will preferably further contain an aqueous liquid earner in which the other essential and optional compositions components are dissolved, dispersed or suspended
  • composition When the composition is an aqueous liquid the composition will preferably contain at least about 5%, more preferably at least about 10%, even more preferably still at least about 30% by weight of the composition of aqueous liquid earner The composition will also preferably contain no more than about 95%, more preferably no more than about 60%, even more preferably, no more than about 50% by weight of the composition of aqueous liquid earner
  • the aqueous liquid earner may contain other matenals which are liquid, or which dissolve in the liquid earner, at room temperature and which may also serve some other function besides that of a simple filler
  • matenals can include, for example hydrotropes and solvents Low molecular weight pnmary or secondary alcohols exemplified by methanol, ethanol. propanol, and isopropanol are suitable.
  • Monohydric alcohols are prefe ⁇ ed for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3- propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • An example of the procedure for making granules of the detergent compositions herein is as follows: - Linear aklylbenzenesulfonate, citric acid, sodium silicate, sodium sulfate perfume, diamine and water are added to, heated and mixed via a crutcher. The resulting slurry is spray dried into a granular form.
  • Non-Aqueous Liquid Detergents The manufacture of liquid detergent compositions which comprise a non-aqueous carrier medium can be prepared according to the disclosures of U.S. Patents 4,753,570; 4.767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2,158,838; GB-A-2,195.125; GB-A- 2.195,649; U.S. 4,988,462; U.S. 5,266,233; EP-A-225,654 (6/16/87); EP-A-510,762 ( 10/28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); U.S.
  • compositions can contain various particulate detersive ingredients stably suspended therein.
  • non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references.
  • compositions of this invention can be used to form aqueous washing solutions for use hand dishwashing.
  • an effective amount of such compositions is added to water to form such aqueous cleaning or soaking solutions.
  • the aqueous solution so formed is then contacted with the dishware. tableware, and cooking utensils.
  • An effective amount of the detergent compositions herein added to water to form aqueous cleaning solutions can comprise amounts sufficient to form from about 500 to 20,000 ppm of composition in aqueous solution. More preferably, from about 800 to 5,000 ppm of the detergent compositions herein will be provided in aqueous cleaning liquor.
  • Example 1 Example 2 Example 3 Example 4 Example 5
  • Viscosity (cps 150 330 650 330
  • Example EExxaammppllee 11 Example 12
  • Example 13 Example 13
  • Viscosity (cps 330 330 330 330 330 330 330 330 330 330 330 330 330
  • Polyamine is a tetraethylenepentamine with a molecular weight of about 175
  • Polyamine is triaminoethyl amine with a molecular weight of about 132

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Abstract

Cette invention se rapporte à des compositions de détergents pour le lavage de la vaisselle à la main, contenant des polyamines et, plus particulièrement, à des compositions de détergents pour le lavage de la vaisselle à la main qui possèdent une action dégraissante améliorée et offrent des bénéfices du point de vue du savonnage dans l'eau douce. Ces détergents possèdent en outre des propriétés améliorées de stabilité à basse température et de dissolution.
EP00926085A 1999-04-19 2000-04-18 Compositions de detergents pour le lavage de la vaisselle, contenant des polyamines organiques Withdrawn EP1171562A1 (fr)

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US12995199P 1999-04-19 1999-04-19
US129951P 1999-04-19
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