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WO2000000580A1 - Laundry compositions comprising ethoxylated polyalkyleneimines which enhance the beta-keto ester fragrance delivery system - Google Patents

Laundry compositions comprising ethoxylated polyalkyleneimines which enhance the beta-keto ester fragrance delivery system Download PDF

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Publication number
WO2000000580A1
WO2000000580A1 PCT/US1999/014831 US9914831W WO0000580A1 WO 2000000580 A1 WO2000000580 A1 WO 2000000580A1 US 9914831 W US9914831 W US 9914831W WO 0000580 A1 WO0000580 A1 WO 0000580A1
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Prior art keywords
substituted
unsubstituted
oxo
formula
dimethyl
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PCT/US1999/014831
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French (fr)
Inventor
Amy Lynn Japikse
Joseph Paul Morelli
Eugene Steven Sadlowski
John Cort Severns
Mark Robert Sivik
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP99932107A priority Critical patent/EP1092008A1/en
Publication of WO2000000580A1 publication Critical patent/WO2000000580A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/507—Compounds releasing perfumes by thermal or chemical activation

Definitions

  • the present invention relates to a fragrance delivery system useful in laundry detergent compositions, preferably liquid laundry detergent compositions.
  • the fragrance delivery system comprises one or more ⁇ -ketoester pro-fragrance compounds which release fragrance raw material alcohols, ketones, and mixtures thereof, thereby providing a "freshness” or “clean” scent to fabric and one or more alkoxylated polyalkyleneimines.
  • the present invention also relates to a method for providing a fragrance benefit to laundered fabric by contacting soiled fabric with a laundry detergent composition described herein.
  • laundry detergent formulators In addition to the removal of stains, dirt, soil, grime, and grease from fabric, laundry detergent formulators have attempted to deliver a "fresh” or “clean” odor to washed clothing to provide an olfactory aesthetic benefit and to serve as a signal that the product is effective.
  • Laundry detergent compositions including rinse-added fabric softeners and dryer-added substrates, are currently formulated with perfume and fragrance ingredients which are aesthetically pleasing to the consumer and which attempt to deliver a prolonged "fragrance” or “pleasurable smell” to fabric which has been laundered via automatic appliance.
  • Liquid laundry detergent compositions are typically formulated with adjunct materials which are designed and formulated to work in high or low density liquid laundry detergent compositions.
  • adjunct materials which are designed and formulated to work in high or low density liquid laundry detergent compositions.
  • certain enzymes, bleaches, soil release agents, and dispersants which comprise granular laundry detergent compositions may not be compatible with liquid laundry detergent formulations. Therefore, liquid laundry detergents comprise adjunct materials which are especially designed to fit the special needs of liquid compositions.
  • fragrance raw materials are delivered to fabric by way of a liquid laundry detergent composition comprising one or more pro-fragrance or pro-accord compounds having high substantivity and water dispersing properties which provides the cleaned clothing or fabric with a "fresh" or “clean” smell for a protracted period after washing.
  • the present invention meets the aforementioned needs in that it has been surprisingly discovered that fragrance raw materials can be delivered onto fabric "through the wash" by way of a ⁇ -ketoester pro-fragrance delivery system which enhances the duration of the released fragrance.
  • a ⁇ -ketoester pro-fragrance delivery system which enhances the duration of the released fragrance.
  • an ethoxylated polyethyleneimine having a backbone molecular weight of 600 daltons and an average of 20 ethoxylations per nitrogen (PEI 600 E20) enhanced fragrance longevity is achieved.
  • this fragrance delivery system comprising ⁇ -ketoester pro- fragrances/PEI 600 E20 is combined with at least one hydrophilic (clay soil) dispersant inter o// ⁇ PEI 189 E15-18.
  • a first aspect of the present invention relates to a fragrance delivery system comprising: a) from about 0.01% by weight, of a ⁇ -ketoester pro-fragrance having the formula:
  • R is alkoxy derived from a fragrance raw material alcohol
  • R*, R and R-* are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C3Q substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2- C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl, C6-C30 substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C
  • R ⁇ , R ⁇ ; and R" are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1-C30 substituted or unsubstituted linear alkoxy, C3-C3 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsub
  • E NCH 2 CH 2 ]w[NCH 2 CH 2 ] x [NCH 2 CH 2 ] y NE 2 wherein B is a continuation by branching; E is an ethyleneoxy unit having the formula:
  • m has an average value of about 20; the values of w, x, and y are such that when taken together the polyalkyleneimine backbone has a molecular weight prior to ethoxylation of about 600 daltons.
  • a further aspect of the present invention relates to laundry detergent compositions comprising: a) from about 0.01% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01%, preferably from about 0.01% to about 15%, more preferably from about 1% to about 5%, most preferably from about 0.1% to about 1% by weight, of a ⁇ -ketoester having the formula:
  • R is alkoxy derived from a fragrance raw material alcohol
  • R ⁇ R ⁇ , and R3 are each independently hydrogen, C1 -C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2- C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl, C6-C30 substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C
  • R ⁇ , R ⁇ , and R" are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1-C30 substituted or unsubstituted linear alkoxy, C3-C30 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, Cg-C3 Q substituted or unsubsti
  • m has an average value of about 20; the values of w, x, and y are such that when taken together the polyalkyleneimine backbone has a molecular weight prior to ethoxylation of about 600 daltons; and d) the balance carriers and adjunct ingredients.
  • laundry detergent compositions which comprise: a) from about 0.01 % by weight, of a detersive surfactant; b) from about 0.01 % by weight, of a ⁇ -ketoester pro-fragrance; c) from about 0.01 % by weight, of PEI 600 E20; d) from about 0.01% by weight, of an ethoxylated polyamine dispersant, preferably PEI 189 E15-18; and e) the balance carriers and adjunct ingredients.
  • a further aspect of the present invention relates to laundry detergent compositions and laundry pre-soak compositions which comprise one or more enzymes and the herein described pro-fragrance/PEI 600 E20 fragrance delivery system.
  • the present invention relates to a novel fragrance delivery system and liquid laundry detergent compositions comprising said fragrance delivery system, said system comprising one or more ⁇ -ketoester pro-fragrances or pro-accords suitable for use in providing an extended fragrance benefit to fabric and an ethoxylated polyethyleneimine having an average backbone molecular weight prior to ethoxylation of about 600 daltons and an average of 20 ethoxylation per N-H unit.
  • the fragrance delivery system further comprises one or more hydrophilic dispersants inter alia PEI 189 E15-18.
  • the liquid laundry detergent compositions may optionally comprise bleaching materials or the compositions may be non- aqueous liquid detergents.
  • the liquid laundry detergent compositions of the present invention also preferably comprise one or more enzymes.
  • the laundry detergent compositions of the present invention comprise a fragrance delivery system which lays down one or more "pro-fragrance” compounds onto the fabric surface during the laundry wash cycle which are capable of releasing a fragrance raw material alcohol or in the case of "pro-accords” the compounds are capable of releasing a mixture of fragrance raw materials.
  • the key advantages provided by the ⁇ -ketoester pro- fragrances or pro-accords of the present invention include chemical stability in the final product matrix, ease of formulation into the product matrix, and a highly desirable rate of fragrance raw material alcohol release.
  • the ⁇ -ketoester pro-fragrances and pro-accords of the present invention begin delivering the fragrance raw materials to the fabric surface once the fabric is exposed to the laundry liquor.
  • pro-fragrance is defined as "a ⁇ -ketoester which releases a fragrance raw material alcohol”
  • pro-accord is defined as " ⁇ -ketoester which release two or more fragrance raw materials”.
  • pro-fragrance is used interchangeably with the term “pro-accord” and either term may be used to stand equally well for either ⁇ -ketoester pro-fragrance molecules, ⁇ -ketoester pro-accord molecules, or both collectively.
  • pro-fragrance compounds are rapidly deposited onto the fabric surface due to the high fabric substantivity of the compounds and once deposited, begin to release the fragrance raw material alcohols during the wash and drying cycles.
  • the "pro-fragrances" of the present invention are a means for effectively delivering fragrance raw materials to the fabric surface even upon exposure to prolonged heating which occurs during automatic dryer usage. Once the laundry cycle is complete, that is the clothing or fabric is dry and ready for use, the "pro-fragrance” continues to release the fragrance raw material alcohol and because this release of material is protracted, the fabric remains “fresh” and “clean” smelling longer.
  • fragment raw materials are herein defined as alcohols and ketones having a molecular weight of at least about 100 g/mol and which are useful in imparting an odor, fragrance, essence, or scent either alone or in combination with other "fragrance raw material alcohols and ketones”.
  • fragrance raw material alcohols which comprise the ⁇ -ketoester "pro- fragrances" of the present invention are not deliverable as individual compounds to fabric via the laundry cycle either due to solubility factors (not sufficiently soluble in the liquid laundry liquor), substantivity factors (do not sufficiently adhere to fabric surface), or volatility factors (evaporation during storage). Therefore, the pro-fragrances described herein are a means for delivering certain fragrance raw materials to fabric which could not have previously been effectively or efficiently delivered.
  • ⁇ -Ketoester Pro-fragrances are a means for delivering certain fragrance raw materials to fabric which could not have previously been effectively or efficiently delivered.
  • compositions according to the present invention comprise one or more ⁇ - ketoesters having the formula:
  • R is alkoxy derived from a fragrance raw material alcohol.
  • preferred fragrance raw material alcohols include 2,4-dimethyl-3-cyclohexene-l-methanol (Floralol), 2,4-dimethyl cyclohexane methanol (Dihydro floralol), 5,6-dimethyl-l- methylethenylbicyclo[2.2.
  • the fragrance raw material alcohol is selected from the group consisting of cw-3-hexen-l-ol, hawthanol [admixture of 2-(o-methylphenyl)-ethanol, 2-(m- methylphenyl)ethanol, and 2-(p-methylphenyl)ethanol], heptan-1-ol, decan-1-ol, 2,4-dimethyl cyclohexane methanol, 4-methylbutan-l-ol, 2,4,6-trimethyl-3-cyclohexene-l-methanol, 4-(l- methylethyl)cyclohexane methanol, 3-(hydroxy-methyl)-2-nonanone, octan-1-ol, 3- phenylpropanol, Rhodinol 70 [3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octenol admixture], 9- decen-1-ol, a-3,3-trimethyl-2-nor
  • R1, R ⁇ , and R ⁇ are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or unsubstituted alkyleneoxyalkyl, C7-C20 substituted or unsubstituted alky
  • R ⁇ , R5 ? and R ⁇ are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1-C30 substituted or unsubstituted linear alkoxy, C3-C30 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsub
  • pro-fragrance 3,7-dimethyl-l,6-octadien-3-yl 3-( ⁇ - naphthyl)-3-oxo-propionate having the formula:
  • fragrance delivery systems of the present invention include 3,7-dimethyl-l,6-octadien-3-yl 3- (a-naphthyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate, 2,6-dimethyl- 7-octen-2-yl 3-(4-nitrophenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-( ⁇ -naphthyl)- 3-oxo-propionate, 3,7-dimethyl-l,6-octadien-3-yl 3-(4-methoxyphenyl)-3-oxo-propionate, 9- de
  • the fragrance delivery system of the present invention further comprises a polyethyleneimine, PEI 600 E20, having the general formula:
  • E NCH2CH 2 ]w [NCH 2 CH2] x [NCH 2 CH 2 ] y NE 2
  • B is a continuation by branching of the polyethyleneimine backbone.
  • E is an ethyleneoxy unit having the formula:
  • m has an average value of about 20.
  • an average value of 20 is that sufficient ethylene oxide or other suitable reagent is reacted with the polyethyleneimine starting material to fully ethoxylate each N-H unit to a degree of 20 ethoxylations.
  • N-H unit hydrogen atoms will be replaced by less than 20 ethoxy units and some will be replaced by more than 20 ethoxy units, therefore, the average of the number of ethoxylations is 20.
  • the units which make up the polyalkyleneimine backbones are primary amine units having the formula:
  • B [N-CH 2 CH 2 ]— which are the branching points of the main and secondary backbone chains, B representing a continuation of the chain structure by branching.
  • the tertiary units have no replaceable hydrogen atom and are therefore not modified by substitution with ethyleneoxy units.
  • an amount of cyclic polyamine can be present in the parent polyalkyleneimine backbone mixture.
  • Each primary and secondary amine unit of the cyclic alkyleneimines undergoes modification by the addition of alkyleneoxy units in the same manner as linear and branched polyalkyleneimines.
  • the indices w, x, and y have values such that the average molecular weight of the polyethyleneimine backbone prior to modification is about 600 daltons.
  • each branch chain must terminate in a primary amine unit, therefore the value of the index w is y + 1 in the case where no cyclic amine backbones are present.
  • the average molecular weight for each ethylene backbone unit, -NCH 2 CH 2 -, is approximately 43 daltons.
  • the polyamines of the present invention 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.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21, 1951; all herein incorporated by reference.
  • Preferred Polyamine Dispersants are disclosed in U.S. Patent 2,182,
  • compositions of the present invention may also comprise at least about 0.1% by weight, preferably from about 0.1%, more preferably from about 0.5% to about 10%, preferably to about 5% by weight, of a water-soluble or water dispersible polyalkyleneimine dispersant, said dispersant comprises a polyamine backbone, preferably said backbone having a molecular weight of about 189 daltons having the formula: E R'
  • the laundry detergent compositions of the present invention in their most basic form comprise: a) from about 0.01 % by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01 % by weight, of a ⁇ -ketoester pro-fragrance as described herein; c) from about 0.01% by weight, of an ethoxylated polyalkyleneimine having the formula:
  • E is an ethyleneoxy unit having the formula: -(CH 2 CH 2 0) m H wherein m has an average value of about 20; the values of w, x, and y are such that when taken together the polyalkyleneimine backbone has a molecular weight prior to ethoxylation of about 600 daltons; and d) the balance carriers and adjunct ingredients, said adjunct ingredients are selected from the group consisting of builders, optical brighteners, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti- wrinkle agents, germicides, fungicide
  • the laundry detergent compositions of the present invention comprise at least about 0.01% by weight, preferably from about 0.1% to about 60%, more preferably from about 0.1% to about 30% by weight, of a detersive surfactant system, said system is comprised of one or more category of surfactants depending upon the embodiment, said categories of surfactants are selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof. Within each category of surfactant, more than one type of surfactant of surfactant can be selected. For example, preferably the solid (i.e. granular) and viscous semi-solid (i.e. gelatinous, pastes, etc.) systems of the present invention, surfactant is preferably present to the extent of from about 0.1% to 60 %, more preferably 0.1% to about 30% by weight of the composition.
  • Nonlimiting examples of surfactants useful herein include: a) Cn-Cjg alkyl benzene sulfonates (LAS); b) C ⁇ o-C 2 o primary, branched-chain and random alkyl sulfates (AS); c) Cio-Cis secondary (2,3) alkyl sulfates having the formula:
  • x and (y + 1) are integers of at least about 7, preferably at least about 9; said surfactants disclosed in U.S. 3,234,258 Morris, issued February 8, 1966; U.S. 5,075,041 Lutz, issued December 24, 1991; U.S. 5,349,101 Lutz et al., issued September 20, 1994; and U.S.
  • Cio-Cig alkyl alkoxy sulfates (AE ⁇ S) wherein preferably x is from 1-7; e) C 1 0-C 1 8 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) C 12 -C 1 8 alkyl ethoxylates, C ⁇ -C ⁇ 2 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units, C ⁇ 2 -C ⁇ 8 alcohol and C ⁇ - C ⁇ 2 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers inter alia Pluronic ® ex BASF which are disclosed in U.S.
  • R ⁇ is C5-C31 alkyl
  • R is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl
  • Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof; preferred Q is derived from a reducing sugar in a reductive amination reaction, more preferably Q is a glycityl moiety; Q is more preferably selected from the group consisting of -CH 2 (CHOH) n CH 2 OH, -CH(CH 2 OH)(CHOH) n .
  • n is an integer from 3 to 5, inclusive
  • R 1 is hydrogen or a cyclic or aliphatic monosaccharide, which are described in U.S. 5,489,393 Connor et al., issued February 6, 1996; and U.S. 5,45,982 Murch et al., issued October 3, 1995, both incorporated herein by reference.
  • adjunct ingredients useful in the laundry compositions of the present invention
  • said adjunct ingredients include builders, optical brighteners, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti corrosion agents, and mixtures thereof.
  • the laundry detergent compositions of the present invention preferably comprise one or more detergent builders or builder systems.
  • the compositions will typically comprise at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%, preferably to about 50%, more preferably to about 30% by weight, of detergent builder.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. 4,664,839 Rieck, issued May 12, 1987.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si ⁇ 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 x + ⁇ yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na2Si ⁇ 5-(NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. 3,985,669, Krummel et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in U.S. 3,128,287 Berg, issued April 7, 1964, and U.S. 3,635,830 Lamberti et al., issued January 18, 1972. See also "TMS/TDS" builders of U.S. 4,663,071 Bush et al., issued May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. 3,923,679 Rapko, issued December 2, 1975; U.S.
  • ether hydroxypolycarboxylates include the ether hydroxypolycarboxylates, copoly- mers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxy- disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxy- disuccinic acid
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is do- decenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsucci- nate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C ⁇ -C j g monocarboxylic acids
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium ortho- phosphate can be used.
  • Phosphonate builders such as ethane- l-hydroxy-l,l-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from surfaces such as textiles, for the prevention of refugee dye transfer, for example in laundering, and for fabric restoration.
  • Suitable enzymes include proteases, amylases, Upases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Detersive enzyme means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition.
  • Preferred detersive enzymes are hydrolases such as proteases, amylases and Upases.
  • Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, Upases and peroxidases.
  • Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount".
  • cleaning effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics.
  • typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.
  • the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • detergents it may be desirable to increase the active enzyme content of the commercial preparation in order to minimize the total amount of non-catalytically active materials and thereby improve spotting/filming or other end-results. Higher active levels may also be desirable in highly concentrated detergent formulations.
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo.
  • proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
  • proteases include those of WO 9510591 A to Procter & Gamble .
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
  • an especially preferred protease 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.
  • Amylases suitable herein include, for example, ⁇ -amylases described in GB 1,296,839 to Novo; RAPIDASE®, 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.
  • compositions can make use of amylases having improved stability in detergents, 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 / tetraacetylethylenediamine 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 Baccillus 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 incorporated WO 9402597, Novo, Feb.
  • 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.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5.
  • U.S. 4,435,307, Barbesgoard et al, March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also Upases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” or "Amano-P.” 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 Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli.
  • Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution.
  • oxygen sources e.g., percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1 89 to Novo and WO 8909813 A to Novo.
  • a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques.
  • Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
  • a further preferred enzyme according to the present invention are mannanase enzymes.
  • present mannanase enzymes comprise from about 0.0001%, preferably from 0.0005%, more preferably from about 0.001% to about 2%, preferably to about 0.1% more preferably to about 0.02% by weight, of said composition.
  • 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 (IUPAC Classification- Enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic Press) are useful in the compositions of the present invention.
  • the detergent compositions of the present invention comprise a ⁇ - 1,4-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 sideb ranches. 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.
  • 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 Aspergillus 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 W091/18974 and a purified mannanase from Bacillus amyloliquefaciens is described in W097/11164.
  • 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 agaradherens NICMB 40482; the mannanase from Bacillus 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 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 agaradherens 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 agaradherens, NCIMB 40482; or ii) a polypeptide comprising an amino acid sequence as shown in positions 32-
  • 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 homologs 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 ID 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 International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 18 May 1998 under the deposition number DSM 12180.
  • 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 ID 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.
  • 09/095,163 b) species homologs 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 ID NO: 6 as shown in the U.S. patent application serial No. 09/095,163; d) molecules complementary to (a), (b) or (c); and e) 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-
  • 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 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 Purposes 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.
  • a fourth more preferred 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 ID 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.
  • 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 Purposes 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. Soil Release Agents
  • compositions according to the present invention may optionally comprise one or more soil release agents.
  • soil release agents will generally comprise from about 0.01%, preferably from about 0.1%, more preferably from about 0.2% to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of the laundry cycle and , thus, serve as an anchor for the hydrophilic segments. This can enable stains occuring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the present invention also relates to a method for using the laundry detergent or pre- soak compositions to suitably clean fabric.
  • the methods of the present invention include a method for cleaning fabric comprising the step of contacting fabric in need of cleaning with an aqueous solution containing a least 50 ppm, preferably at least about 100 ppm, more preferably at least about 200 ppm, of a laundry detergent composition which comprises: a) from about 0.01% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01% by weight, of a soil dispersant as described herein above; and c) the balance carriers and adjunct ingredients.
  • a laundry detergent composition which comprises: a) from about 0.01% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01% by weight, of a soil dispersant as described herein above; and
  • the detergent compositions according to the present invention can be in liquid, paste, laundry bar, or granular form, preferably liquid.
  • Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means.
  • Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations.
  • Liquid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • Addition of the polyalkyleneimine dispersant to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the polyalkyleneimine dispersant.
  • Lithium diisopropylamide (101.0 mL of a 2.0 M solution, 0.202 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is placed in a dry ice-acetone bath. 3,7-Dimethyl-l,6-octadien-3-yl acetate (linalyl acetate) in the amount of (18.66 g, 0.095 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min.
  • the mixture is stirred for an additional 15 min before being treated with a solution of 2-naphthoyl chloride in the amount of (17.43 g, 0.090 mol) dissolved in THF (25 mL) over 30 min.
  • the mixture is warmed to -20 °C and stirred at that temperature for 18 h.
  • the mixture is quenched with 20% HC1 (53 mL).
  • the mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL).
  • Step 1 linalyl acetoacetate.
  • Step 2 3.7-dimethyl-l,6-octadien-3-yl 3-( ⁇ -naphthyl)-3-oxo-propionate.
  • Crude linalyl acetoacetate (154.51, 0.648 mol) from above is placed in a 3000 mL three- necked round-bottomed flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal thermometer. The contents are dissolved in 350 mL of dichloromethane and treated with powdered calcium hydroxide (50.44 g, 0.681 mol). The mixture is stirred at 30 °C for 30 min and then heated to 40 °C.
  • the ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
  • a ⁇ 20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
  • PEI polyethyleneimine
  • Nippon Shokubai having a listed average molecular weight of 600 equating to about 0.417 moles of polymer and 6.25 moles of nitrogen functions
  • the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
  • the autoclave contents are heated to 130 °C while applying vacuum. After about one hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
  • Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
  • the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
  • the temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction.
  • the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
  • Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure.
  • the autoclave is charged to 200 psia with nitrogen.
  • Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm. After the addition of approximately 5225 g of ethylene oxide (resulting in a total of 20 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.
  • reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
  • the strong alkali catalyst is neutralized by adding 60 g methanesulfonic acid (0.625 moles).
  • the reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
  • inert gas argon or nitrogen
  • the final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
  • Ci2-Cj4 alkyl ethoxylate as sold by Shell Oil Co.

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Abstract

The present invention relates to a fragrance delivery system which provides enhanced fragrance endurance. The fragrance delivery system is suitable for use in preferably liquid laundry detergent compositions which comprise a β-ketoester pro-fragrance, an ethoxylated polyethyleneimine, PEI 600 E20, and preferably a hydrophilic soil dispersant inter alia PEI 189 E15-E18. The fragrance delivery system of the present invention is suitable for use in laundry pre-soaks and detergent compositions which comprise one or more enzymes.

Description

LAUNDRY COMPOSITIONS COMPRISING
ETHOXYLATED POLYALKYLENEIMINES
WHICH ENHANCE THE BETA-KETO ESTER
FRAGRANCE DELIVERY SYSTEM
FIELD OF THE INVENTION The present invention relates to a fragrance delivery system useful in laundry detergent compositions, preferably liquid laundry detergent compositions. The fragrance delivery system comprises one or more β-ketoester pro-fragrance compounds which release fragrance raw material alcohols, ketones, and mixtures thereof, thereby providing a "freshness" or "clean" scent to fabric and one or more alkoxylated polyalkyleneimines. The present invention also relates to a method for providing a fragrance benefit to laundered fabric by contacting soiled fabric with a laundry detergent composition described herein.
BACKGROUND OF THE INVENTION
In addition to the removal of stains, dirt, soil, grime, and grease from fabric, laundry detergent formulators have attempted to deliver a "fresh" or "clean" odor to washed clothing to provide an olfactory aesthetic benefit and to serve as a signal that the product is effective. Laundry detergent compositions, including rinse-added fabric softeners and dryer-added substrates, are currently formulated with perfume and fragrance ingredients which are aesthetically pleasing to the consumer and which attempt to deliver a prolonged "fragrance" or "pleasurable smell" to fabric which has been laundered via automatic appliance.
Liquid laundry detergent compositions are typically formulated with adjunct materials which are designed and formulated to work in high or low density liquid laundry detergent compositions. For example, certain enzymes, bleaches, soil release agents, and dispersants which comprise granular laundry detergent compositions may not be compatible with liquid laundry detergent formulations. Therefore, liquid laundry detergents comprise adjunct materials which are especially designed to fit the special needs of liquid compositions.
Attempts have been made to deliver perfume ingredients, especially fragrance raw material alcohols and ketones, which have an enduring fragrance benefit, from liquid laundry detergent compositions. The admixture of fragrance and perfume raw materials into a perfume component, which is subsequently added to the liquid laundry composition, may provide a short-term fragrance benefit, however, these materials have, in general, failed to provide a lasting fragrance benefit to fabric. Accordingly, there remains a need in the art for a fragrance delivery system wherein fragrance raw materials are delivered to fabric by way of a liquid laundry detergent composition comprising one or more pro-fragrance or pro-accord compounds having high substantivity and water dispersing properties which provides the cleaned clothing or fabric with a "fresh" or "clean" smell for a protracted period after washing.
SUMMARY OF THE INVENTION
The present invention meets the aforementioned needs in that it has been surprisingly discovered that fragrance raw materials can be delivered onto fabric "through the wash" by way of a β-ketoester pro-fragrance delivery system which enhances the duration of the released fragrance. When one or more of the pro-fragrances of the present invention are combined with an ethoxylated polyethyleneimine having a backbone molecular weight of 600 daltons and an average of 20 ethoxylations per nitrogen (PEI 600 E20), enhanced fragrance longevity is achieved. Preferably this fragrance delivery system comprising β-ketoester pro- fragrances/PEI 600 E20 is combined with at least one hydrophilic (clay soil) dispersant inter o//α PEI 189 E15-18.
A first aspect of the present invention relates to a fragrance delivery system comprising: a) from about 0.01% by weight, of a β-ketoester pro-fragrance having the formula:
Figure imgf000004_0001
wherein R is alkoxy derived from a fragrance raw material alcohol; R*, R and R-* are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C3Q substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2- C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl, C6-C30 substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or unsubstituted alkyleneoxyalkyl, C7-C20 substituted or unsubstituted alkylenearyl, Cg-C20 substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof; provided at least one R*, R^, or R- is a unit having the formula:
Figure imgf000005_0001
wherein R^, R^; and R" are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1-C30 substituted or unsubstituted linear alkoxy, C3-C3 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl; or R^, R5, and R > can be taken together to form C6-C30 substituted or unsubstituted aryl; and mixtures thereof; and b) from about 0.01 % by weight, of an ethoxylated polyalkyleneimine having the formula:
E B
I I
[E2NCH2CH2]w[NCH2CH2]x[NCH2CH2]yNE2 wherein B is a continuation by branching; E is an ethyleneoxy unit having the formula:
-(CH2CH20)mH wherein m has an average value of about 20; the values of w, x, and y are such that when taken together the polyalkyleneimine backbone has a molecular weight prior to ethoxylation of about 600 daltons. A further aspect of the present invention relates to laundry detergent compositions comprising: a) from about 0.01% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01%, preferably from about 0.01% to about 15%, more preferably from about 1% to about 5%, most preferably from about 0.1% to about 1% by weight, of a β-ketoester having the formula:
Figure imgf000006_0001
wherein R is alkoxy derived from a fragrance raw material alcohol; R\ R^, and R3 are each independently hydrogen, C1 -C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2- C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl, C6-C30 substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or unsubstituted alkyleneoxyalkyl, C7-C20 substituted or unsubstituted alkylenearyl, Cg-C20 substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof; provided at least one R*, R^, or R^ is a unit having the formula:
Figure imgf000006_0002
wherein R^, R^, and R" are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1-C30 substituted or unsubstituted linear alkoxy, C3-C30 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, Cg-C3Q substituted or unsubstituted alkylenearyl; or R^, R^, and R^ can be taken together to form C6-C30 substituted or unsubstituted aryl; and mixtures thereof; c) from about 0.01% by weight, of an ethoxylated polyalkyleneimine having the formula:
E B
I I
[E2NCH2CH2]w[NCH2CH2]χ[NCH2CH2]yNE2 wherein B is a continuation by branching; E is an ethyleneoxy unit having the formula:
-(CH2CH20)mH wherein m has an average value of about 20; the values of w, x, and y are such that when taken together the polyalkyleneimine backbone has a molecular weight prior to ethoxylation of about 600 daltons; and d) the balance carriers and adjunct ingredients.
Another aspect of the present invention relates to laundry detergent compositions which comprise: a) from about 0.01 % by weight, of a detersive surfactant; b) from about 0.01 % by weight, of a β-ketoester pro-fragrance; c) from about 0.01 % by weight, of PEI 600 E20; d) from about 0.01% by weight, of an ethoxylated polyamine dispersant, preferably PEI 189 E15-18; and e) the balance carriers and adjunct ingredients.
A further aspect of the present invention relates to laundry detergent compositions and laundry pre-soak compositions which comprise one or more enzymes and the herein described pro-fragrance/PEI 600 E20 fragrance delivery system. These and other objects, features, and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims.
All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a novel fragrance delivery system and liquid laundry detergent compositions comprising said fragrance delivery system, said system comprising one or more β-ketoester pro-fragrances or pro-accords suitable for use in providing an extended fragrance benefit to fabric and an ethoxylated polyethyleneimine having an average backbone molecular weight prior to ethoxylation of about 600 daltons and an average of 20 ethoxylation per N-H unit. Preferably the fragrance delivery system further comprises one or more hydrophilic dispersants inter alia PEI 189 E15-18. The liquid laundry detergent compositions may optionally comprise bleaching materials or the compositions may be non- aqueous liquid detergents. The liquid laundry detergent compositions of the present invention also preferably comprise one or more enzymes.
The following is a detailed description of the elements of the present invention. FRAGRANCE DELIVERY SYSTEM
The laundry detergent compositions of the present invention comprise a fragrance delivery system which lays down one or more "pro-fragrance" compounds onto the fabric surface during the laundry wash cycle which are capable of releasing a fragrance raw material alcohol or in the case of "pro-accords" the compounds are capable of releasing a mixture of fragrance raw materials. The key advantages provided by the β-ketoester pro- fragrances or pro-accords of the present invention include chemical stability in the final product matrix, ease of formulation into the product matrix, and a highly desirable rate of fragrance raw material alcohol release.
The β-ketoester pro-fragrances and pro-accords of the present invention begin delivering the fragrance raw materials to the fabric surface once the fabric is exposed to the laundry liquor. For the purposes of the present invention the term "pro-fragrance" is defined as "a β-ketoester which releases a fragrance raw material alcohol" whereas a "pro-accord" is defined as "β-ketoester which release two or more fragrance raw materials". For the purposes of the present invention, however, since a material that is a "pro-fragrance" in one embodiment can serve as a "pro-accord" in a different embodiment, the term "pro-fragrance" is used interchangeably with the term "pro-accord" and either term may be used to stand equally well for either β-ketoester pro-fragrance molecules, β-ketoester pro-accord molecules, or both collectively. These "pro-fragrance" compounds are rapidly deposited onto the fabric surface due to the high fabric substantivity of the compounds and once deposited, begin to release the fragrance raw material alcohols during the wash and drying cycles. Because the β-ketoester "pro-fragrances" of the present invention generally have a higher molecular weight than uncombined fragrance raw material alcohols are therefore less volatile, the "pro-fragrances" of the present invention are a means for effectively delivering fragrance raw materials to the fabric surface even upon exposure to prolonged heating which occurs during automatic dryer usage. Once the laundry cycle is complete, that is the clothing or fabric is dry and ready for use, the "pro-fragrance" continues to release the fragrance raw material alcohol and because this release of material is protracted, the fabric remains "fresh" and "clean" smelling longer.
For the purposes of the present invention "fragrance raw materials" are herein defined as alcohols and ketones having a molecular weight of at least about 100 g/mol and which are useful in imparting an odor, fragrance, essence, or scent either alone or in combination with other "fragrance raw material alcohols and ketones".
Most of the fragrance raw material alcohols which comprise the β-ketoester "pro- fragrances" of the present invention are not deliverable as individual compounds to fabric via the laundry cycle either due to solubility factors (not sufficiently soluble in the liquid laundry liquor), substantivity factors (do not sufficiently adhere to fabric surface), or volatility factors (evaporation during storage). Therefore, the pro-fragrances described herein are a means for delivering certain fragrance raw materials to fabric which could not have previously been effectively or efficiently delivered. β-Ketoester Pro-fragrances
The compositions according to the present invention comprise one or more β- ketoesters having the formula:
Figure imgf000009_0001
wherein R is alkoxy derived from a fragrance raw material alcohol. Non-limiting examples of preferred fragrance raw material alcohols include 2,4-dimethyl-3-cyclohexene-l-methanol (Floralol), 2,4-dimethyl cyclohexane methanol (Dihydro floralol), 5,6-dimethyl-l- methylethenylbicyclo[2.2. l]hept-5-ene-2-methanol (Arbozol), a,a,-4-trimethyl-3-cyclohexen- 1-methanol (a-te ineol), 2,4,6-trimethyl-3-cyclohexene-l -methanol (Isocyclo geraniol), 4-(l- methylethyl)cyclohexane methanol (Mayol), a-3,3-trimethyl-2-norborane methanol, 1,1- dimethyl-l-(4-methylcyclohex-3-enyl)methanol, 2-phenylethanol, 2-cyclohexyl ethanol, 2-(o- methylphenyl)-ethanol, 2-(m-methylphenyl)ethanol, 2-(p-methylphenyl)ethanol, 6,6- dimethylbicyclo-[3.1.1]hept-2-ene-2-ethanoI (nopol), 2-(4-methylphenoxy)-ethanol, 3,3- dimethyl-D^-β-norbornane ethanol (patchomint), 2-methyl-2-cyclohexylethanol, l-(4- isopropylcyclohexyl)-ethanol, 1-phenylethanol, l,l-dimethyl-2-phenylethanol, l,l-dimethyl-2- (4-methyl-phenyl)ethanol, 1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (Hydrotropic Alcohol), 2-(cyclododecyl)propan-l-ol (Hydroxy-ambran), 2,2-dimethyl-3-(3- methylphenyl)-propan-l-ol (Majantol), 2-methyl-3-phenylpropanol, 3-phenyl-2-propen-l-ol (cinnamyl alcohol), 2-methyl-3-phenyl-2-propen-l-ol (methylcinnamyl alcohol), a-n-pentyl-3- phenyl-2-propen-l-ol (a-amyl-cinnamyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2-(4- methylphenyl)-2-propanol, 3-(4-methylcyclohex-3-ene)butanol, 2-methyl-4-(2,2,3-trimethyl- 3-cyclopenten-l-yl)butanol, 2-ethyl-4-(2,2,3-trimethyl-cyclopent-3-enyl)-2-buten-l-ol, 3- methyl-2-buten- 1 -ol (prenol), 2-methyl-4-(2,2,3 -trimethyl-3 -cyclopenten- 1 -yl)-2-buten- 1 -ol, ethyl 3-hydroxybutyrate, 4-phenyl-3-buten-2-ol, 2-methyl-4-phenylbutan-2-ol, 4-(4- hydroxyphenyl)butan-2-one, 4-(4-hydroxy-3-methoxyphenyl)-butan-2-one, 3-methyl- pentanol, 3-methyl-3-penten-l-ol, l-(2-propenyl)cyclopentan-l-ol (plinol), 2-methyl-4- phenylpentanol (Pamplefleur), 3-methyl-5-phenylpentanol (Phenoxanol), 2-methyl-5- phenylpentanol, 2-methyl-5-(2,3-dimethyltricyclo[2.2.1.θ(2,6)]hept.3.yi).2-penten- l-ol (santalol), 4-methy 1- 1 -phenyl-2-pentanol, 5 -(2,2,3-trimethyl-3 -cyclopentenyl)-3 - methylpentan-2-ol (sandalore), ( 1 -methyl-bicyclo[2.1.1 ]hepten-2-yl)-2-methylpent- 1 -en-3-ol, 3-methyl- 1 -phenylpentan-3-ol, 1 ,2-dimethyl-3-( 1 -methylethenyl)cyclopentan- 1 -ol, 2- isopropyl-5-methyl-2-hexenol, cw-3-hexen-l-ol, trα«5-2-hexen-l-ol, 2-isoproenyl-4-methyl-4- hexen-1-ol (Lavandulol), 2-ethyl-2-prenyl-3-hexenol, l-hydroxymethyl-4-iso-propenyl-l- cyclohexene (Dihydrocuminyl alcohol), l-methyl-4-isopropenylcyclohex-6-en-2-ol (carvenol), 6-methyl-3-isopropenylcyclohexan-l-ol (dihydrocarveol), l-methyl-4-iso- propenylcyclohexan-3-ol, 4-isopropyl-l-methylcyclohexan-3-ol, 4-tert-butylcyclo-hexanol, 2- tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol (rootanol), 4-isopropyl- cyclohexanol, 4-methyl- 1 -( 1 -methylethyl)-3 -cyclohexen- 1 -ol, 2-(5 ,6,6-trimethyl-2- norbornyl)cyclohexanol, isobornylcyclohexanol, 3,3,5-trimethylcyclohexanol, l-methyl-4- isopropylcyclohexan-3-ol, l-methyl-4-isopropylcyclohexan-8-ol (dihydroterpineol), 1,2- dimethyl-3-(l-methylethyl)cyclohexan-l-ol, heptanol, 2,4-dimethylheptan-l-ol, 6-heptyl-5- hepten-2-ol (isolinalool), 2,4-dimethyl-2,6-heptandienol, 6,6-dimethyl-2-oxymethyl- bicyclo[3.1.1]hept-2-ene (myrtenol), 4-methyl-2,4-heptadien-l-ol, 3,4,5,6,6-pentamethyl-2- heptanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, 6,6-dimethyl-3-hydroxy-2- methylenebicyclo[3.1.1]heptane, l,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, 2,6- dimethylheptan-2-ol (dimetol), 2,6,6-trimethylbicyclo[1.3.3]heptan-2-ol, octanol, 2-octenol, 2-methyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-ol (myrcenol), 7-methyloctan-l-ol, 3,7- dimethyl-6-octenol, 3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octen-l-ol (citronellol), 3,7- dimethyl-2,6-octadien-l-ol (geraniol), 3,7-dimethyl-2,6-octadien-l-ol (nerol), 3,7-dimethyl-7- methoxyoctan-2-ol (osyrol), 3,7-dimethyl-l,6-octadien-3-ol (linalool), 3,7-dimethyloctan-l-ol (pelargol), 3,7-dimethyloctan-3-ol (tetrahydrolinalool), 2,4-octadien-l-ol, 3,7-dimethyl-6- octen-3-ol (dihydrolinalool), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol), 2,6-dimethyl-5,7- octadien-2-ol, 4,7-dimethyl-4-vinyl-6-octen-3-ol, 3-methyloctan-3-ol, 2,6-dimethyloctan-2-ol, 2,6-dimethyloctan-3-ol, 3,6-dimethyloctan-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-3,5- octadien-2-ol (muguol), 3-methyl-l-octen-3-oI, 7-hydroxy-3,7-dimethyloctanal, 3-nonanol, 2,6-nonadien-l-ol, cis-6-nonen-l-ol, 6,8-dimethylnonan-2-ol, 3-(hydroxymethyl)-2-nonanone, 2-nonen-l-ol, 2,4-nonadien-l-ol, 3,7-dimethyl-l,6-nonadien-3-ol, decanol, 9-decenol, 2- benzyl-M-dioxa-5-ol, 2-decen-l-ol, 2,4-decadien-l-ol, 4-methyl-3-decen-5-ol, 3,7,9- trimethyl-l,6-decadien-3-ol (isobutyl linalool), undecanol, 2-undecen-l-ol, 10-undecen-l-ol, 2-dodecen-l-ol, 2,4-dodecadien-l-ol, 2,7,1 l-trimethyl-2,6,10-dodecatrien-l-ol (farnesol), 3,7,1 l-trimethyl-l,6,10,-dodecatrien-3-ol (nerolidol), 3,7,1 l,15-tetramethylhexadec-2-en-l-ol (phytol), 3,7,1 l,15-tetramethylhexadec-l-en-3-ol (iso phytol), benzyl alcohol, p-methoxy benzyl alcohol (anisyl alcohol), /rørø-cymen-7-ol (cuminyl alcohol), 4-methyl benzyl alcohol, 3,4-methylenedioxy benzyl alcohol, methyl salicylate, benzyl salicylate, cw-3-hexenyl salicylate, n-pentyl salicylate, 2-phenylethyl salicylate, n-hexyl salicylate, 2-methyl-5- isopropylphenol, 4-ethyl-2-methoxyphenol, 4-allyl-2-methoxyphenol (eugenol), 2-methoxy-4- (l-propenyl)phenol (isoeugenol), 4-allyl-2,6-dimethoxy-phenol, 4-tert-butylphenol, 2-ethoxy- 4-methylphenol, 2-methyl-4-vinylphenoI, 2-isopropyl-5-methylphenol (thymol), pentyl-ortΛo- hydroxy benzoate, ethyl 2-hydroxy-benzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3- hydroxy-5-methoxy-l-methylbenzene, 2-tert-butyl-4-methyl-l-hydroxybenzene, l-ethoxy-2- hydroxy-4-propenylbenzene, 4-hydroxytoluene, 4-hydroxy-3-methoxybenzaldehyde, 2- ethoxy-4-hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5 -trimethyl-octahydro-2-naphthol, l,3,3-trimethyl-2-norbornanol (fenchol), 3a,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano- lH-inden-5-ol, 3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano- lH-inden-5-ol, 2-methyl- 2-vinyl-5-(l-hydroxy-l-methylethyl)tetra-hydrofuran, β-caryophyllene alcohol, vanillin, ethyl vanillin, and mixtures thereof.
More preferably, the fragrance raw material alcohol is selected from the group consisting of cw-3-hexen-l-ol, hawthanol [admixture of 2-(o-methylphenyl)-ethanol, 2-(m- methylphenyl)ethanol, and 2-(p-methylphenyl)ethanol], heptan-1-ol, decan-1-ol, 2,4-dimethyl cyclohexane methanol, 4-methylbutan-l-ol, 2,4,6-trimethyl-3-cyclohexene-l-methanol, 4-(l- methylethyl)cyclohexane methanol, 3-(hydroxy-methyl)-2-nonanone, octan-1-ol, 3- phenylpropanol, Rhodinol 70 [3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octenol admixture], 9- decen-1-ol, a-3,3-trimethyl-2-norborane methanol, 3-cyclohexylpropan-l-ol, 4-methyl-l- phenyl-2-pentanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, phenyl ethyl methanol; propyl benzyl methanol, 1 -methyl-4-isopropenylcyclohexan-3-ol, 4-isopropyl- 1 -methylcyclohexan-3-ol (menthol), 4-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol, 4-isopropylcyclo- hexanol, tra/w-decahydro-β-naphthol, 2-tert-butylcyclohexanol, 3-phenyl-2-propen-l-ol, 2,7,1 l-trimethyl-2,6,10-dodecatrien-l-ol, 3,7-dimethyl-2,6-octadien-l-ol (geraniol), 3,7- dimethyl-2,6-octadien-l-ol (nerol), 4-methoxybenzyl alcohol, benzyl alcohol, 4-allyl-2- methoxyphenol, 2-methoxy-4-(l-propenyl)phenol, vanillin, and mixtures thereof.
R1, R^, and R^ are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or unsubstituted alkyleneoxyalkyl, C7-C20 substituted or unsubstituted alkylenearyl, Cg-C20 substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof; provided at least one R^, R^, or R^ is a unit having the formula:
Figure imgf000012_0001
wherein R^, R5? and R^ are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1-C30 substituted or unsubstituted linear alkoxy, C3-C30 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl, C6-C30 substituted or unsubstituted aryl; or R^, R$, and R^ can be taken together to form C6-C30 substituted or unsubstituted aryl; and mixtures thereof.
An example of a preferred pro-fragrance is 3,7-dimethyl-l,6-octadien-3-yl 3-(β- naphthyl)-3-oxo-propionate having the formula:
Figure imgf000013_0001
which releases at least the fragrance raw material alcohol, linalool, having the formula:
Figure imgf000013_0002
and the fragrance raw material ketone, methyl naphthyl ketone, having the formula:
Figure imgf000013_0003
Additional non-limiting examples of preferred pro-fragrances which comprise the fragrance delivery systems of the present invention include 3,7-dimethyl-l,6-octadien-3-yl 3- (a-naphthyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo- propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate, 2,6-dimethyl- 7-octen-2-yl 3-(4-nitrophenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)- 3-oxo-propionate, 3,7-dimethyl-l,6-octadien-3-yl 3-(4-methoxyphenyl)-3-oxo-propionate, 9- decen-1-yl 3-(β-naphthyl)-3-oxo-propionate, 3,7-dimethyl-l,6-octadien-3-yl 3-(nonanyl)-3- oxo-propionate, (a,a-4-trimethyl-3-cyclohexenyl)methyl 3-(β-naphthyl)-3-oxo-propionate, cis 3-hexen-l-yl 3-(β-naphthyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(nonanyl)-3- oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate, 3,7-dimethyl-l,6-octadien-3-yl 3- oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7- dimethyl- 1 ,6-octadien-3 -yl 3 -(β-naphthyl)-3 -oxo-2,2-dimethylpropionate, 3 ,7-dimethyl- 1 ,6- octadien-3-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3-(β- naphthyl)-3 -oxo-propionate, 3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-propionate, and mixtures thereof. PEI 600 E20
The fragrance delivery system of the present invention further comprises a polyethyleneimine, PEI 600 E20, having the general formula:
E B
I I
[E2NCH2CH2]w [NCH2CH2]x[NCH2CH2]y NE2 wherein B is a continuation by branching of the polyethyleneimine backbone. E is an ethyleneoxy unit having the formula:
-(CH2CH20)mH wherein m has an average value of about 20. What is meant herein by an average value of 20 is that sufficient ethylene oxide or other suitable reagent is reacted with the polyethyleneimine starting material to fully ethoxylate each N-H unit to a degree of 20 ethoxylations. However, those skilled in the art will realize that some N-H unit hydrogen atoms will be replaced by less than 20 ethoxy units and some will be replaced by more than 20 ethoxy units, therefore, the average of the number of ethoxylations is 20.
The units which make up the polyalkyleneimine backbones are primary amine units having the formula:
H2N-CH2CH2]- and -NH which terminate the main backbone and any branching chains, secondary amine units having the formula:
H [N~CH2CH2]- and which, after modification, have their hydrogen atom substituted by an average of 20 ethyleneoxy units, and tertiary amine units having the formula:
B — [N-CH2CH2]— which are the branching points of the main and secondary backbone chains, B representing a continuation of the chain structure by branching. The tertiary units have no replaceable hydrogen atom and are therefore not modified by substitution with ethyleneoxy units. During the formation of the polyamine backbones cyclization may occur, therefore, an amount of cyclic polyamine can be present in the parent polyalkyleneimine backbone mixture. Each primary and secondary amine unit of the cyclic alkyleneimines undergoes modification by the addition of alkyleneoxy units in the same manner as linear and branched polyalkyleneimines.
The indices w, x, and y have values such that the average molecular weight of the polyethyleneimine backbone prior to modification is about 600 daltons. In addition, those skilled in the art will recognize that each branch chain must terminate in a primary amine unit, therefore the value of the index w is y + 1 in the case where no cyclic amine backbones are present. The average molecular weight for each ethylene backbone unit, -NCH2CH2-, is approximately 43 daltons.
The polyamines of the present invention 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 these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21, 1951; all herein incorporated by reference. Preferred Polyamine Dispersants
Preferably the compositions of the present invention may also comprise at least about 0.1% by weight, preferably from about 0.1%, more preferably from about 0.5% to about 10%, preferably to about 5% by weight, of a water-soluble or water dispersible polyalkyleneimine dispersant, said dispersant comprises a polyamine backbone, preferably said backbone having a molecular weight of about 189 daltons having the formula: E R'
I I
[E2N-R] [N-R]x[N-R]yNE2
wherein R is ethylene; R' is -RNE2; E is an ethyleneoxy unit having the formula:
-(CH2CH20)mH wherein m has an average value of from about 15 to about 18; x is 2 or 3; y is 0 or 1; and x + y = 3.
A further description of polyamine dispersants suitable for use in the present invention is found in U.S. 4,891,160 Vander Meer, issued January 2, 1990; U.S.4,597,898, Vander Meer, issued July 1, 1986; European Patent Application 111,965, Oh and Gosselink, published June 27, 1984; European Patent Application 111,984, Gosselink, published June 27, 1984; European Patent Application 112,592, Gosselink, published July 4, 1984; U.S. 4,548,744, Connor, issued October 22, 1985; and U.S. 5,565,145 Watson et al., issued October 15, 1996; all of which are included herein by reference. However, any suitable clay/soil dispersent or anti-redeposition agent can be used in the laundry compositions of the present invention.
LAUNDRY DETERGENT COMPOSITIONS
The laundry detergent compositions of the present invention in their most basic form comprise: a) from about 0.01 % by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01 % by weight, of a β-ketoester pro-fragrance as described herein; c) from about 0.01% by weight, of an ethoxylated polyalkyleneimine having the formula:
E B
I I
[E2NCH2CH2]w [NCH2CH2]x[NCH2CH2]y NE2 wherein B is a continuation by branching; E is an ethyleneoxy unit having the formula: -(CH2CH20)mH wherein m has an average value of about 20; the values of w, x, and y are such that when taken together the polyalkyleneimine backbone has a molecular weight prior to ethoxylation of about 600 daltons; and d) the balance carriers and adjunct ingredients, said adjunct ingredients are selected from the group consisting of builders, optical brighteners, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti- wrinkle agents, germicides, fungicides, anti corrosion agents, and mixtures thereof.
The following is a description of the laundry compositions of the present invention.
SURFACTANT SYSTEM
The laundry detergent compositions of the present invention comprise at least about 0.01% by weight, preferably from about 0.1% to about 60%, more preferably from about 0.1% to about 30% by weight, of a detersive surfactant system, said system is comprised of one or more category of surfactants depending upon the embodiment, said categories of surfactants are selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof. Within each category of surfactant, more than one type of surfactant of surfactant can be selected. For example, preferably the solid (i.e. granular) and viscous semi-solid (i.e. gelatinous, pastes, etc.) systems of the present invention, surfactant is preferably present to the extent of from about 0.1% to 60 %, more preferably 0.1% to about 30% by weight of the composition.
Nonlimiting examples of surfactants useful herein include: a) Cn-Cjg alkyl benzene sulfonates (LAS); b) Cιo-C2o primary, branched-chain and random alkyl sulfates (AS); c) Cio-Cis secondary (2,3) alkyl sulfates having the formula:
OSO3 " Iv OSO3 " M*
I I
CH3(CH2)X(CH)CH3 or CH3(CH )y(CH)CH CH3
wherein x and (y + 1) are integers of at least about 7, preferably at least about 9; said surfactants disclosed in U.S. 3,234,258 Morris, issued February 8, 1966; U.S. 5,075,041 Lutz, issued December 24, 1991; U.S. 5,349,101 Lutz et al., issued September 20, 1994; and U.S. 5,389,277 Prieto, issued February 14, 1995 each incorporated herein by reference; d) Cio-Cig alkyl alkoxy sulfates (AEχS) wherein preferably x is from 1-7; e) C10-C18 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) C12-C18 alkyl ethoxylates, Cβ-Cι2 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units, Cι2-Cι8 alcohol and Cβ- Cι2 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers inter alia Pluronic® ex BASF which are disclosed in U.S. 3,929,678 Laughlin et al., issued December 30, 1975, incorporated herein by reference; g) Alkylpolysaccharides as disclosed in U.S. 4,565,647 Llenado, issued January 26, 1986, incorporated herein by reference; h) Polyhydroxy fatty acid amides having the formula:
O R8 R7— C-N-Q wherein R^ is C5-C31 alkyl; R is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof; preferred Q is derived from a reducing sugar in a reductive amination reaction, more preferably Q is a glycityl moiety; Q is more preferably selected from the group consisting of -CH2(CHOH)nCH2OH, -CH(CH2OH)(CHOH)n. ]CH2OH, -CH2(CHOH)2-(CHOR')(CHOH)CH2θH, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R1 is hydrogen or a cyclic or aliphatic monosaccharide, which are described in U.S. 5,489,393 Connor et al., issued February 6, 1996; and U.S. 5,45,982 Murch et al., issued October 3, 1995, both incorporated herein by reference.
ADJUNCT INGREDIENTS The following are non-limiting examples of adjunct ingredients useful in the laundry compositions of the present invention, said adjunct ingredients include builders, optical brighteners, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti corrosion agents, and mixtures thereof.
Builders - The laundry detergent compositions of the present invention preferably comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%, preferably to about 50%, more preferably to about 30% by weight, of detergent builder.
The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly those having a Siθ2:Na2θ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. 4,664,839 Rieck, issued May 12, 1987. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Siθ5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A- 3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSixθ2x+ι yH2θ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2Siθ5-(NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
[Mz(zA102)y] xH20 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. 3,985,669, Krummel et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Na12[(Alθ2)i2(Siθ2)i2] xH20 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in U.S. 3,128,287 Berg, issued April 7, 1964, and U.S. 3,635,830 Lamberti et al., issued January 18, 1972. See also "TMS/TDS" builders of U.S. 4,663,071 Bush et al., issued May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. 3,923,679 Rapko, issued December 2, 1975; U.S. 4,158,635 Crutchfield et al., issued June 19, 1979; U.S. 4,120,874 Crutchfield et al., issued October 17, 1978; and U.S. 4,102,903 Crutchfield et al., issued July 25, 1978.
Other useful detergency builders include the ether hydroxypolycarboxylates, copoly- mers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxy- disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the 3,3-dicar- boxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is do- decenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsucci- nate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. 4,144,226, Crutchfield et al., issued March 13, 1979 and in U.S. 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C^-Cjg monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium ortho- phosphate can be used. Phosphonate builders such as ethane- l-hydroxy-l,l-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used. Enzymes
Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from surfaces such as textiles, for the prevention of refugee dye transfer, for example in laundering, and for fabric restoration. Suitable enzymes include proteases, amylases, Upases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and Upases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, Upases and peroxidases.
Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, it may be desirable to increase the active enzyme content of the commercial preparation in order to minimize the total amount of non-catalytically active materials and thereby improve spotting/filming or other end-results. Higher active levels may also be desirable in highly concentrated detergent formulations.
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis. One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other preferred proteases include those of WO 9510591 A to Procter & Gamble . When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
In more detail, an especially preferred protease, referred to as "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.
Useful proteases are also described in PCT publications: WO 95/30010 published Novenber 9, 1995 by The Procter & Gamble Company; WO 95/30011 published Novenber 9, 1995 by The Procter & Gamble Company; WO 95/29979 published Novenber 9, 1995 by The Procter & Gamble Company. Amylases suitable herein include, for example, α-amylases described in GB 1,296,839 to Novo; RAPIDASE®, 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, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use in 1993. These preferred 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 / tetraacetylethylenediamine 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 Baccillus amylases, especially the Bacillus α-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 incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b) stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant; (c) 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®. 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.
Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6, 1984, discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
CAREZYME® (Novo) is especially useful. See also WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also Upases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P." 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 Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli. LIPOLASE® 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.
Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1 89 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
A further preferred enzyme according to the present invention are mannanase enzymes. When present mannanase enzymes comprise from about 0.0001%, preferably from 0.0005%, more preferably from about 0.001% to about 2%, preferably to about 0.1% more preferably to about 0.02% by weight, of said composition.
Preferably, the following three mannans-degrading enzymes : EC 3.2.1.25 : β-mannosidase, EC 3.2.1.78 : Endo-l,4-β-mannosidase, referred therein after as "mannanase" and EC 3.2.1.100 : 1,4-β-mannobiosidase (IUPAC Classification- Enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic Press) are useful in the compositions of the present invention.
More preferably, the detergent compositions of the present invention comprise a β- 1,4-Mannosidase (E.C. 3.2.1.78) referred to as Mannanase. The term "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 .
In particular, 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 β- 1,4- linked mannose; glucomannans are polysaccharides having a backbone or more or less regularly alternating β-1,4 linked mannose and glucose; galactomannans and galactoglucomannans are mannans and glucomannans with α-1,6 linked galactose sideb ranches. 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 α-galactosidase and/or mannan acetyl esterases can be further degraded to release free maltose by β-mannosidase and/or β-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 Aspergillus 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 W091/18974 and a purified mannanase from Bacillus amyloliquefaciens is described in W097/11164. Preferably, the mannanase enzyme will be an alkaline mannanase as defined below, more preferably, a mannanase originating from a bacterial source. Especially, the laundry detergent composition of the present invention will comprise an alkaline mannanase selected from the mannanase from the strain Bacillus agaradherens NICMB 40482; the mannanase from Bacillus 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 application No. PA 1998 01340.
The terms "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 agaradherens 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 agaradherens, NCIMB 40482; or ii) a polypeptide comprising an amino acid sequence as shown in positions 32-
343 of SEQ ID NO:2 as shown in U.S. patent application serial No. 09/111,256; or iii) an analogue of the polypeptide defined in i) or 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. Also encompassed is the corresponding 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 homologs 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 ID 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 International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 18 May 1998 under the deposition number DSM 12180.
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 ID 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. 09/095,163; or iii) 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. Also encompassed in the corresponding 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:5 as shown in the U.S. patent application serial No. 09/095,163 b) species homologs 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 ID NO: 6 as shown in the U.S. patent application serial No. 09/095,163; d) molecules complementary to (a), (b) or (c); and e) 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. Also encompassed is the corresponding isolated polynucleotide molecule 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 317 to nucleotide 1243 the Danish application No. PA 1998 01340; b) species homologs of (a); c) 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 e) degenerate nucleotide sequences of (a), (b), (c) or (d).
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 Purposes 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.
A fourth more preferred 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 ID 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 a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 225 to nucleotide 1236 as shown in the Danish application No. PA 1998 01341; b) species homologs of (a); c) 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 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 e) degenerate nucleotide sequences of (a), (b), (c) or (d).
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 Purposes 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. Soil Release Agents
The compositions according to the present invention may optionally comprise one or more soil release agents. If utilized, soil release agents will generally comprise from about 0.01%, preferably from about 0.1%, more preferably from about 0.2% to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of the laundry cycle and , thus, serve as an anchor for the hydrophilic segments. This can enable stains occuring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
The following, all included herein by reference, describe soil release polymers suitable for us in the present invention. U.S. 5,691,298 Gosselink et al, issued November 25, 1997; U.S. 5,599,782 Pan etal, issued February 4, 1997; U.S. 5,415,807 Gosselink et al, issued May 16, 1995; U.S. 5,182,043 Morrall et al, issued January 26, 1993; U.S. 4,956,447 Gosselink etal, issued September 11, 1990; U.S. 4,976,879 Maldonado etal. issued December 11, 1990; U.S. 4,968,451 Scheibel etal, issued November 6, 1990; U.S. 4,925,577 Borcher, Sr. et al, issued May 15, 1990; U.S. 4,861,512 Gosselink, issued August 29, 1989; U.S. 4,877,896 Maldonado et al, issued October 31, 1989; U.S. 4,771,730 Gosselink et al, issued October 27, 1987; U.S. 711,730 Gosselink et al, issued December 8, 1987; U.S. 4,721,580 Gosselink issued January 26, 1988; U.S. 4,000,093 Nicol etal, issued December 28, 1976; U.S. 3,959,230 Hayes, issued May 25, 1976; U.S. 3,893,929 Basadur, issued July 8, 1975; and European Patent Application 0219048, published April 22, 1987 by Kud et al.
Further suitable soil release agents are described in U.S. 4,201,824 Voilland et al; U.S. 4,240,918 Lagasse et al; U.S. 4,525,524 Tung et al; U.S. 4,579,681 Ruppert et al; U.S. 4,220,918; U.S. 4,787,989; EP 279,134 A, 1988 to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 to Unilever N.V., 1974; all incorporated herein by reference.
METHOD OF USE
The present invention also relates to a method for using the laundry detergent or pre- soak compositions to suitably clean fabric.
The methods of the present invention include a method for cleaning fabric comprising the step of contacting fabric in need of cleaning with an aqueous solution containing a least 50 ppm, preferably at least about 100 ppm, more preferably at least about 200 ppm, of a laundry detergent composition which comprises: a) from about 0.01% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01% by weight, of a soil dispersant as described herein above; and c) the balance carriers and adjunct ingredients.
The detergent compositions according to the present invention can be in liquid, paste, laundry bar, or granular form, preferably liquid. Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means.
Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. Addition of the polyalkyleneimine dispersant to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the polyalkyleneimine dispersant.
The following examples illustrate the β-ketoesters and compositions of this invention, but are not intended to be limiting thereof.
EXAMPLE 1 Preparation of 3,7-dimethyl-l ,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate
Lithium diisopropylamide (101.0 mL of a 2.0 M solution, 0.202 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is placed in a dry ice-acetone bath. 3,7-Dimethyl-l,6-octadien-3-yl acetate (linalyl acetate) in the amount of (18.66 g, 0.095 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of 2-naphthoyl chloride in the amount of (17.43 g, 0.090 mol) dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20 °C and stirred at that temperature for 18 h. After warming to 0 °C, the mixture is quenched with 20% HC1 (53 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHC03 solution (2 x 100 mL), water (2 x 150 mL) and brine (150 mL), dried over MgS04 and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 5% ethyl acetate dissolved in petroleum ether) to give an oil. Purity of the product is determined by thin layer chromatography and GC analysis and the structure confirmed by mass spectrometry, 1H and 13C NMR.
EXAMPLE 2
The following is a further illustration of a preparation of a β-ketoesters of this invention, but is not intended to be limiting thereof.
Step 1: linalyl acetoacetate.
A mixture of linalool (100.00 g, 0.648 mol) and 4-dimethylamino-pyridine (0.40 g, 3.20 mmol, Aldrich, DMAP) in a 500 mL three-necked round-bottomed flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal thermometer is heated to 55 °C. Diketene (54.50 g, 0.648 mol) is added dropwise in the course of 30 min. The mixture has a slight exotherm and turns from yellow to red during this time. After stirring an additional hour at 50 °C, the mixture is cooled to room temperature. At this point, NMR analysis indicates the reaction is complete. The material from this lot is carried onto the next step. Purification of an earlier sample from this route by flash chromtography (elution with dichloromethane) yields linalyl acetoacetate of 92% yield and nearly colorless.
Step 2: 3.7-dimethyl-l,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate. Crude linalyl acetoacetate (154.51, 0.648 mol) from above is placed in a 3000 mL three- necked round-bottomed flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal thermometer. The contents are dissolved in 350 mL of dichloromethane and treated with powdered calcium hydroxide (50.44 g, 0.681 mol). The mixture is stirred at 30 °C for 30 min and then heated to 40 °C. 2-Naphthoyl chloride (142.12 g, 0.746 mol) dissolved in 20 mL of dichloromethane is added dropwise over 15 min. The mixture continues to be heated at this temperature for 1 h. Ammonium chloride (36.41 g, 0.681 mol) dissolved in 250 mL of water is added to the reaction mixture and the pH adjusted to ~9 with 28% ammonium hydroxide. After stirring 30 min at 35 °C the pH is adjusted to ~1 with 20% HCl. The mixture is transferred to a separatory funnel containing diethyl ether (500 mL) and water (500 mL). The layers are separated and the organic phase is washed with saturated NaHC03 solution (2 x 500 mL), dried over MgSθ4, filtered and concentrated by rotary evaporation to give a yellow red oil. At this point a light yellow solid precipitates from the mixture. An equal volume of hexane is added and the solids is collected by filtration and dried. NMR analysis indicates the solid is 2-naphthoic acid. The eluent is concentrated again by rotary evaporation to give a red oil. The oil is taken up in an equal volume of dichloromethane, passed through a plug of silica gel (400 g) and eluted with dichloromethane. The mixture is concentrated by rotary evaporation and stripped by Kugelrohr distillation (40 °C, 0.10 mm Hg, 30 min) to yield 173.26 g (76.3%) of the product as a red oil; this product is a mixture of a 1:10 molar ratio of linalyl acetoacetate to linalyl (2-naphthoyl)acetate. A portion of this material is purified by column chromatography (elution with 2.5% ethyl acetate in hexanes) to give 3,7-dimethyl-l,6-octadien-3-yl 3 -(β-naphthyl)-3 -oxo-propionate as a light yellow oil.
EXAMPLE 3 Preparation of PEI 600 E20
The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid. A ~20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
A 250 g portion of polyethyleneimine (PEI) (Nippon Shokubai, having a listed average molecular weight of 600 equating to about 0.417 moles of polymer and 6.25 moles of nitrogen functions) is added to the autoclave. The autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure). The autoclave contents are heated to 130 °C while applying vacuum. After about one hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C. Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate. The ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm. The temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 275 grams of ethylene oxide has been charged to the autoclave (roughly equivalent to one mole ethylene oxide per PEI nitrogen function), the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
Next, vacuum is continuously applied while the autoclave is cooled to about 50 °C while introducing 135 g of a 25% sodium methoxide in methanol solution (0.625 moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions). The methoxide solution is sucked into the autoclave under vacuum and then the autoclave temperature controller setpoint is increased to 130 °C. A device is used to monitor the power consumed by the agitator. The agitator power is monitored along with the temperature and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1 hour indicating that most of the methanol has been removed. The mixture is further heated and agitated under vacuum for an additional 30 minutes.
Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 °C and limiting any temperature increases due to reaction exotherm. After the addition of approximately 5225 g of ethylene oxide (resulting in a total of 20 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.
The reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation. The strong alkali catalyst is neutralized by adding 60 g methanesulfonic acid (0.625 moles). The reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
The final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
In other preparations the neutralization and deodorization is accomplished in the reactor before discharging the product.
The following illustrate the laundry detergent compositions of the present invention.
TABLE I weight %
Figure imgf000036_0001
Figure imgf000037_0001
1. C i2"C 14 alkyl ethoxylate as sold by Shell Oil Co.
2. C12-C13 alkyl ethoxylate as sold by Shell Oil Co.
3. Protease B variant of BPN' wherein Tyr 17 is replaced with Leu.
4. Derived from Humicola lanugmosa and commercially available from Novo.
5. Disclosed in WO 9510603 A and available from Novo.
6. PEI 189 E,5-E,8.
7. Polyalkyleneimine dispersant according to Example 2.
8. Pro-fragrance according to Example 1 or 3. TABLE II weight %
Figure imgf000038_0001
Figure imgf000039_0002
1. Ci2-Cj4 alkyl ethoxylate as sold by Shell Oil Co.
2. C]2"Ci3 alkyl ethoxylate as sold by Shell Oil Co.
3. 5,12-dimethyl-l,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane manganese (II) chloride.
4. Enzyme stabilizer.
5. Protease B variant of BPN' wherein Tyr 17 is replaced with Leu.
6. Derived from Humicola lanuginosa and commercially available from Novo.
7. Disclosed in WO 9510603 A and available ex Novo.
8. Disclosed in WO 9909128 A 1 and available ex Novo.
Figure imgf000039_0001
10. Polyalkyleneimine dispersant according to Example 2.
11. Pro-fragrance according to Example 1 or 3.

Claims

WHAT IS CLAIMED IS:
1. A fragrance delivery system comprising: a) from about 0.01% by weight, of a β-ketoester pro-fragrance having the formula:
Figure imgf000040_0001
wherein R is alkoxy derived from a fragrance raw material alcohol; R*, R and R3 are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2- C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl, C6-C30 substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or unsubstituted alkyleneoxyalkyl, C7-C20 substituted or unsubstituted alkylenearyl, Cg-C20 substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof; provided at least one R^, R^, or R-> is a unit having the formula:
Figure imgf000040_0002
wherein R , R*5 and R" are each independently hydrogen, C 1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1-C30 substituted or unsubstituted linear alkoxy, C3-C30 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C3 substituted or unsubstituted alkylenearyl; or R , R*5 and R" can be taken together to form C6-C30 substituted or unsubstituted aryl; and mixtures thereof; and b) from about 0.01% by weight, of an ethoxylated polyalkyleneimine having the formula:
E B
I I
[E2NCH2CH2]w[NCH2CH2]x[NCH2CH2]yNE2 wherein B is a continuation by branching; E is an ethyleneoxy unit having the formula:
-(CH2CH20)mH wherein m has an average value of about 20; the values of w, x, and y are such that when taken together the polyalkyleneimine backbone has a molecular weight prior to ethoxylation of about 600 daltons.
2. A laundry detergent composition comprising: a) from about 0.01% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01 % by weight, of a β-ketoester having the formula:
Figure imgf000041_0001
wherein R is alkoxy derived from a fragrance raw material alcohol; R , R2, and R-* are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2- C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C5-C30 substituted or unsubstituted alkylenearyl, C6-C30 substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or unsubstituted alkyleneoxyalkyl, C7-C20 substituted or unsubstituted alkylenearyl, Cg-C2o substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof; provided at least one R R^, or R3 is a unit having the formula:
Figure imgf000042_0001
wherein R , R*5 and R" are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1-C30 substituted or unsubstituted linear alkoxy, C3-C30 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cy ic alkoxy, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl; or R , R$, and R° can be taken together to form C6-C30 substituted or unsubstituted aryl; and mixtures thereof; c) from about 0.01 % by weight, of an ethoxylated polyall yleneimine having the formula:
E B
I I
[E2NCH2CH2]w[NCH2CH2]x[NCH2CH2]yNE2 wherein B is a continuation by branching; E is an ethyleneoxy unit having the formula:
-(CH2CH20)mH wherein m has an average value of about 20; the values of w, x, and y are such that when taken together the polyalkyleneimine backbone has a molecular weight prior to ethoxylation of about 600 daltons; and d) the balance carriers and adjunct ingredients.
3. A composition according to Claim 2 wherein said adjunct ingredients are selected from the group consisting of builders, optical brighteners, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti- shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti corrosion agents, and mixtures thereof.
4. A composition according to Claim 2 wherein R* has the formula:
Figure imgf000043_0001
R2 and R3 are each hydrogen, R4, R^ and R^ are taken together to form C6-C30 substituted or unsubstituted phenyl, naphthyl, and mixtures thereof.
5. A composition according to Claim 2 wherein said β-ketoester is selected from the group consisting of 3,7-dimethyl-l,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate, 2,6-dimethyl-7- octen-2-yl 3-(4-nitrophenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(β- naphthyl)-3 -oxo-propionate, 3,7-dimethyI-l,6-octadien-3-yl 3-(4-methoxyphenyl)-3- oxo-propionate, (a,a-4-trimethyl-3 -cyclohexenyl)methyl 3 -(β-naphthyl)-3 -oxo- propionate, 3,7-dimethyl-l,6-octadien-3-yl 3-(a-naphthyl)-3-oxo-propionate, cis 3- hexen-1-yl 3-(β-naphthyl)-3-oxo-propionate, 9-decen-l-yl 3-(β-naphthyl)-3-oxo- propionate, 3,7-dimethyl-l,6-octadien-3-yl 3 -(nonanyl)-3 -oxo-propionate, 2,6- dimethyl-7-octen-2-yl 3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3- oxo-butyrate, 3,7-dimethyl-l,6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2- yl 3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-l,6-octadien-3-yl 3-(β- naphthyl)-3-oxo-2,2-dimethylpropionate, 3,7-dimethyl-l,6-octadien-3-yl 3-(β- naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3-(β-naphthyl)-3- oxo-propionate, 3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-propionate, and mixtures thereof.
6. A composition according to Claim 2 wherein R is linalool, dihydromyrcenol, and mixtures thereof; R1 has the formula:
Figure imgf000044_0001
wherein R4, R^, and R^ are taken together to form a β-naphthyl unit; R2 and R3 are each hydrogen.
7. A composition according to Claim 2 further comprising at least about 0.001% of a protease enzyme wherein said protease enzyme is a Protease B variant of BPN' wherein Tyr 17 is replaced with Leu.
8. A composition according to Claim 2 further comprising at least about 0.001 % of a lipolase enzyme derived from Humicola lanugmosa.
9. A composition according to Claim 2 further comprising a hydrophilic dispersant having the formula:
E R'
I I
[E2N-R] [N-R]x[N-R]yNE2 wherein R is ethylene; R' is -RNE2; E is an ethyleneoxy unit having the formula:
-(CH2CH20)mH wherein m has an average value of from about 15 to about 18; x is 2 or 3; y is 0 or 1; and x + y = 3.
0. A laundry detergent composition comprising: a) from about 0.01 % by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01% by weight, of a β-ketoester having the formula:
Figure imgf000045_0001
wherein R is linalool, dihydromyrcenol, and mixtures thereof; R1 has the formula:
Figure imgf000045_0002
wherein R , R^5 and R" are taken together to form a β-naphthyl unit; R^ and R3 are each hydrogen; c) from about 0.01 % by weight, of an ethoxylated polyalkyleneimine having the formula:
E B
I I
[E2NCH2CH2]w[NCH2CH2]x[NCH2CH2]yNE2 wherein B is a continuation by branching; E is an ethyleneoxy unit having the formula:
-(CH2CH20)mH wherein m has an average value of about 20; the values of w, x, and y are such that when taken together the polyalkyleneimine backbone has a molecular weight prior to ethoxylation of about 600 daltons; and d) the balance carriers and adjunct ingredients.
11. A laundry detergent composition comprising: a) from about 0.01 % by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01% by weight, of 3,7-dimethyl-l,6-octadien-3-yl 3-(β- naphthyl)-3-oxo-propionate; c) from about 0.01% by weight, of an ethoxylated polyalkyleneimine having a backbone molecular weight prior to ethoxylation of about 600 daltons and an average degree of ethoxylation per N-H unit of about 20; d) from about 0.001% by weight, of an enzyme, said enzyme selected from the group consisting of protease, lipolase, cellulase, amylase, peroxidases, and mixtures thereof; e) from about 0.1 % of an ethoxylated polyamine dispersant wherein said dispersant has a backbone molecular weight prior to ethoxylation of about 189 daltons and an average degree of ethoxylation per N-H unit of from about 15 to about 18; and f) the balance carriers and adjunct ingredients.
12. A method for providing an enduring fragrance to fabric comprising the step of contacting fabric in need of cleaning with an aqueous solution containing a least 50 ppm of a laundry detergent composition which comprises: a) from about 0.01 % by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof; b) from about 0.01% by weight, of a β-ketoester having the formula:
Figure imgf000046_0001
wherein R is alkoxy derived from a fragrance raw material alcohol; R*, R and R3 are each independently hydrogen, C1-C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C30 substituted or unsubstituted cyclic alkenyl, C2- C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl, C6-C30 substituted or unsubstituted aryl, C2-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or unsubstituted alkyleneoxyalkyl, C7-C20 substituted or unsubstituted alkylenearyl, Cg-C20 substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof; provided at least one R^, R^, or R3 is a unit having the formula:
Figure imgf000047_0001
wherein R4, Jt?, and R° are each independently hydrogen, C \ -C30 substituted or unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched alkyl, C3-C30 substituted or unsubstituted cyclic alkyl, C1-C30 substituted or unsubstituted linear alkoxy, C3-C30 substituted or unsubstituted branched alkoxy, C3-C30 substituted or unsubstituted cyclic alkoxy, C2-C30 substituted or unsubstituted linear alkenyl, C3-C30 substituted or unsubstituted branched alkenyl, C3-C3Q substituted or unsubstituted cyclic alkenyl, C2-C30 substituted or unsubstituted linear alkynyl, C3-C30 substituted or unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted alkylenearyl; or R4, R , and R" can be taken together to form C6-C30 substituted or unsubstituted aryl; and mixtures thereof; c) from about 0.01 % by weight, of an ethoxylated polyalkyleneimine having the formula:
E B
I I
[E2NCH2CH2] w [NCH2CH2]x[NCH2CH2]y NE2 wherein B is a continuation by branching; E is an ethyleneoxy unit having the formula: -(CH2CH20)mH wherein m has an average value of about 20; the values of w, x, and y are such that when taken together the polyalkyleneimine backbone has a molecular weight prior to ethoxylation of about 600 daltons; and d) the balance carriers and adjunct ingredients.
PCT/US1999/014831 1998-06-30 1999-06-30 Laundry compositions comprising ethoxylated polyalkyleneimines which enhance the beta-keto ester fragrance delivery system WO2000000580A1 (en)

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US6699823B2 (en) 1998-07-10 2004-03-02 Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
US6790815B1 (en) 1998-07-10 2004-09-14 Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
US7012047B2 (en) 1998-07-10 2006-03-14 Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
US6906012B1 (en) 1999-11-09 2005-06-14 Procter & Gamble Company Detergent compositions comprising a fragrant reaction product
WO2002055648A1 (en) * 2001-01-13 2002-07-18 Henkel Kommanditgesellschaft Auf Aktien Gels for the targeted release of odoriferous substances
US8895496B2 (en) 2002-11-25 2014-11-25 Colgate-Palmolive Company Functional fragrance precursor
US8592361B2 (en) 2002-11-25 2013-11-26 Colgate-Palmolive Company Functional fragrance precursor
US8895495B2 (en) 2002-11-25 2014-11-25 Colgate-Palmolive Company Functional fragrance precursor
US8901068B2 (en) 2002-11-25 2014-12-02 Colgate-Palmolive Company Functional fragrance precursor
US8906843B2 (en) 2002-11-25 2014-12-09 Colgate-Palmolive Company Functional fragrance precursor
US8278230B2 (en) 2007-06-05 2012-10-02 The Procter & Gamble Company Perfume systems
WO2016090623A1 (en) * 2014-12-12 2016-06-16 The Procter & Gamble Company Liquid cleaning composition
WO2020030469A1 (en) * 2018-08-10 2020-02-13 Basf Se Process for manufacturing alkoxylated polyethyleneimines
WO2020030760A1 (en) * 2018-08-10 2020-02-13 Unilever Plc Detergent
CN112513237A (en) * 2018-08-10 2021-03-16 巴斯夫欧洲公司 Process for preparing alkoxylated polyethyleneimines
CN112567011A (en) * 2018-08-10 2021-03-26 联合利华知识产权控股有限公司 Detergent composition
CN112567011B (en) * 2018-08-10 2022-04-15 联合利华知识产权控股有限公司 Detergent composition
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