Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase

Definitions

• the present invention relates to cleaning compositions, including laundry, dishwashing, hard surface cleaner, oral/dental cleaning compositions, comprising a cytochrome enzyme.
• 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 British Patent 1 ,372,034.
• Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
• amylolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.
• acylated citrate esters such as disclosed in Copending European Patent Application No. 91870207.7 and unsymetrical acyclic imide bleach activator of the following formula as disclosed in the Procter & Gamble co-pending patent applications US serial No. 60/022,786 (filed July 30, 1996) and No. 60/028,122 (filed October 15, 1996):
• oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
• Such bleaching agents are disclosed in U.S. Patent 4,483,781 , U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934.
• Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551.
• Peroxidase-containing detergent compositions are disclosed, for example, in PCT Intemational Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.
• Said peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
• Suitable metals in the rigid ligand complexes include Mn(ll), Mn(lll), Mn(IV), Mn(V), Fe(ll), Fe(lll), Fe(IV), Co(l), Co(ll), Co(lll), Ni(l), Ni(ll), Ni(lll), Cu(l), Cu(ll), Cu(ll), Cr(ll), Cr(lll), Cr(IV), Cr(V), Cr(VI), V(lll), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(ll), Ru(ll), Ru(lll), and Ru(IV).
• Preferred transition-metals in the instant transition-metal bleach catalyst include manganese, iron and chromium.
• Preferred oxidation states include the (II) and (III) oxidation states.
• Manganese(ll) in both the low-spin configuration and high spin complexes are included. It is to be noted that complexes such as low-spin Mn(ll) complexes are rather rare in all of coordination chemistry.
• the designation (II) or (III) denotes a coordinated transition metal having the requisite oxidation state; the coordinated metal atom is not a free ion or one having only water as a ligand.
• Preferred superstructures herein not only enhance the rigidity of the parent macrocycle, but also favor folding of the macrocycle so that it co-ordinates to a metal in a cleft.
• Suitable superstructures can be remarkably simple, for example a linking moiety such as any of those illustrated in 1.9 and 1.10 below, can be used.
• m and n are integers from about 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkyl- ammonium, halogen, nitro, sulfonate, or the like.
• the aromatic ring in 1.10 can be replaced by a saturated ring, in which the atom in Z connecting into the ring can contain N, O, S or C.
• MRL's preorganization built into the MRL's herein that leads to extra kinetic and/or thermodynamic stability of their metal complexes arises from either or both of topological constraints and enhanced rigidity (loss of flexibility) compared to the free parent macrocycle which has no superstructure.
• the linking moieties and parent macrocycle rings are combined to form ligands which have a significant extent of "fold", typically greater than in many known superstructured ligands in which a superstructure is attached to a largely planar, often unsaturated macrocycle. See, for example: D.H. Busch, Chemical Reviews, (1993), 93, 847 - 880.
• the preferred MRL's herein have a number of particular properties, including (1) they are characterized by very high proton affinities, as in so-called “proton sponges"; (2) they tend to react slowly with multivalent transition metals, which when combined with (1) above, renders synthesis of their complexes with certain hydrolyzable metal ions difficult in hydroxylic solvents; (3) when they are coordinated to transition metal atoms as identified herein, the MRL's result in complexes that have exceptional kinetic stability such that the metal ions only dissociate extremely slowly under conditions that would destroy complexes with ordinary ligands; and (4) these complexes have exceptional thermodynamic stability; however, the unusual kinetics of MRL dissociation from the transition metal may defeat conventional equilibrium measurements that might quantitate this property.
• Suitable MRL's are further nonlimitingly illustrated by the following compound:
• the MRL's herein are of course not limited to being synthesized from any preformed macrocycle plus preformed "rigidizing” or “conformation-modifying” element: rather, a wide variety of synthetic means, such as template syntheses, are useful. See for example Busch et al., reviewed in "Heterocyclic compounds: Aza-crown macrocycles", J.S. Bradshaw et. al.
• macrocyclic rings are covalently connected rings formed from four or more donor atoms (i.e., heteroatoms such as nitrogen or oxygen) with carbon chains connecting them, and any macrocycle ring as defined herein must contain a total of at least ten, preferably at least twelve, atoms in the macrocycle ring.
• a MRL herein may contain more than one ring of any sort per ligand, but at least one macrocycle ring must be identifiable. Moreover, in the preferred embodiments, no two hetero-atoms are directly connected.
• Preferred transition-metal bleach catalysts are those wherein the MRL comprises an organic macrocycle ring (main ring) containing at least 10-20 atoms, preferably 12-18 atoms, more preferably from about 12 to about 20 atoms, most preferably 12 to 16 atoms.
• Donor atoms herein are heteroatoms such as nitrogen, oxygen, phosphorus or sulfur, which when incorporated into a ligand still have at least one lone pair of electrons available for forming a donor-acceptor bond with a metal.
• Preferred transition-metal bleach catalysts are those wherein the donor atoms in the organic macrocycle ring of the cross-bridged MRL are selected from the group consisting of N, O, S, and P, preferably N and O, and most preferably all N.
• cross-bridged MRL's comprising 4 or 5 donor atoms, all of which are coordinated to the same transition metal.
• Most preferred transition- metal bleach catalysts are those wherein the cross-bridged MRL comprises 4 nitrogen donor atoms all coordinated to the same transition metal, and those wherein the cross-bridged MRL comprises 5 nitrogen atoms all coordinated to the same transition metal.
• Non-donor atoms of the MRL herein are most commonly carbon, though a number of atom types can be included, especially in optional exocyclic substituents (such as “pendant” moieties, illustrated hereinafter) of the macrocycles, which are neither donor atoms for purposes essential to form the metal catalysts, nor are they carbon.
• non- donor atoms can refer to any atom not essential to forming donor bonds with the metal of the catalyst.
• atoms could include heteroatoms such as sulfur as incorporated in a non-coordinatable sulfonate group, phosphorus as incorporated into a phosphonium salt moiety, phosphorus as incorporated into a P(V) oxide, a non-transition metal, or the like.
• all non-donor atoms are carbon.
• Transition metal complexes of MRL's can be prepared in any convenient manner. Two such preparations are illustrated as follows:
• Bcyclam (5,12-dimethyl-1 ,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane) is prepared by a synthesis method described by G.R. Weisman, et al., J.Amer.Chem.So ⁇ . (1990), 112. 8604.
• Bcyclam (1.00 g., 3.93 mmol) is dissolved in dry CH3CN (35 mL, distilled from CaH2). The solution is then evacuated at 15 mm until the CH3CN begins to boil. The flask is then brought to atmospheric pressure with Ar. This degassing procedure is repeated 4 times.
• Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
• One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
• Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718.
• detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.
• the surfactant is typically present at a level of from 0.1% to 60% by weight. More preferred levels of incorporation are 1 % to 35% by weight, most preferably from 1 % to 30% by weight of cleaning compositions in accord with the invention.
• Preferred surfactant systems to be used according to the present invention comprise as a surfactant one or more of the nonionic and/or anionic surfactants described herein.
• Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
• These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
• the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
• nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X- 45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
• the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention.
• the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
• About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products.
• nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C-11-C-15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C-14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C-15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of C14-C-15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, KyroTM EOB (the condensation product of C-13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol
• HLB in these products is from 8-11 and most preferred from 8-10.
• the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
• Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
• the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
• the preferred alkylpolyglycosides have the formula
• R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
• the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position). The additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-position.
• the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention.
• the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
• the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
• Examples of compounds of this type include certain of the commercially-available PlurafacTM LF404 and PluronicTM surfactants, marketed by BASF.
• nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
• the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
• This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11 ,000.
• Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
• Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C8-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cs-C-i ⁇ alcohol ethoxylates (preferably C-J O avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
• Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
• Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
• alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:
• alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C- ⁇ o-C-24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
• alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ⁇ -C ⁇ diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulf
• the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 3% to about 20% by weight of such anionic surfactants.
• Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m S03M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C-
• Exemplary surfactants are C ⁇
• the cleaning compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as the nonionic and/or anionic surfactants other than those already described herein.
• Cationic detersive surfactants suitable for use in the cleaning compositions of the present invention are those having one long-chain hydrocarbyl group.
• cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula :
• R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
• each R3 is selected from the group consisting of -CH2CH2-, -CH 2 CH(CH 3 )-, -CH 2 CH(CH2 ⁇ H)-, -CH2CH2CH2-, and mixtures thereof
• each R 4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, - CH 2 CHOH-CHOHCOR6CHOHCH 2 OH wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0
• R5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R ⁇ is not more than about 18
• each y is from 0 to about 10 and the sum of
• R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (II) :
• R6 is C-
• Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
• Ri is C8-C16 alkyl
• each of R2, R3 and R4 is independently C1-C4 alkyl, C-1-C4 hydroxy alkyl, benzyl, and -(C2H4o) ⁇ H where x has a value from 2 to 5, and X is an anion.
• R2, R3 or R4 should be benzyl.
• is C-12-C15 particulariy where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
• R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
• suitable quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide;
• CH2-CH2-O-C-C-12-I4 alkyl and R2R3R4 are methyl).
• Typical cationic fabric softening components include the water-insoluble quaternary-ammonium fabric softening actives or thei corresponding amine precursor, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate.
• Preferred cationic softeners among these include the following:
• DSOEDMAC di(stearoyloxyethyl) dimethylammonium chloride
• Biodegradable quaternary ammonium compounds have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlorides and methyl sulfates. Such quaternary ammonium compounds contain long chain alk(en)yl groups interrupted by functional groups such as carboxy groups. Said materials and fabric softening compositions containing them are disclosed in numerous publications such as EP-A-0,040,562, and EP-A-0,239,910.
• Q is selected from -O-C(O)-, -C(0)-0-, -0-C(0)-0-, -NR 4 -C(0)-, -C(O)-
• R is (CH 2 ) n -Q-T 2 or T3;
• R 2 is (CH 2 )m-Q-T 4 or T5 or R 3 ;
• R 4 is H or C1-C4 alkyl or C1-C4 hydroxyalkyl
• T1 , T 2 , T 3 , T 4 , T ⁇ are independently C11-C22 alkyl or alkenyl; n and m are integers from 1 to 4; and
• X * is a softener-compatible anion.
• Non-limiting examples of softener-compatible anions include chloride or methyl sulfate.
• the alkyl, or alkenyl, chain T1 , T 2 , T 3 , T 4 , T ⁇ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.
• the chain may be straight or branched.
• quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include :
• the cleaning compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8% by weight of such cationic surfactants.
• Ampholytic surfactants are also suitable for use in the cleaning compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
• One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.
• the cleaning compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.
• Zwitterionic surfactants are also suitable for use in cleaning compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.
• the cleaning compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1 % to about 10% by weight of such zwitterionic surfactants.
• Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
• R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms
• R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof
• x is from 0 to about 3
• each R ⁇ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
• the R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
• These amine oxide surfactants in particular include C10-C18 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
• the cleaning compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1 % to about 10% by weight of such semi-polar nonionic surfactants.
• Preferred amines according to the formula herein above are n-alkyl amines.
• Suitable amines for use herein may be selected from 1-hexylamine, 1- octylamine, 1-decylamine and laurylamine.
• Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl- oxypropylamine, lauryl amido propylamine and amido propylamine.
• R3 is either a CQ-C ⁇ ⁇ 2, preferably CQ-C ⁇ Q alkyl chain, or R3 is R4X(CH2) n , whereby X is -0-, -C(0)NH- or -NH- R4 is a C4-C12, n is between 1 to 5, preferably 2-3.
• R5 is H or C1-C2 alkyl and x is between 1 to 6 .
• R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.
• Preferred tertiary amines are R1 R2R3N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or
• R-j is CQ-C ⁇ alkyl
• n is 2-4, preferably n is 3
• R2 and R3 is C1-C4
• Most preferred amines of the present invention include 1-octylamine, 1- hexylamine, 1-decylamine, 1-dodecylamine,C8-10oxypropylamine, N coco 1- 3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-10 amidopropyldimethylamine and C10 amidopropyldimethylamine.
• metallo catalysts for color maintenance are described in copending European Patent Application No. 92870181.2.
• Dye fixing agents, polyolefin dispersion for anti-wrinkles and improved water absorbancy, perfume and amino-functional polymer for color care treatment and perfume substantivity are further examples of color care / fabric care technologies and are described in the co-pending Patent Application No. 96870140.9, filed November 07, 1996.
• Fabric softening agents can also be incorporated into cleaning compositions in accordance with the present invention. These agents may be inorganic or organic in type.
• Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in USP 5,019,292.
• Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-BO 011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919.
• Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.
• Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15% by weight, with the material being added as a dry mixed component to the remainder of the formulation.
• Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
• These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other solid components of the composition.
• compositions according to the present invention may further comprise a builder system.
• a builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl- succinic acid and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
• Phosphate builders can also be used herein. Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
• the selected polyesters herein contain about 46% by weight of dimethyl terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and have a molecular weight of about 3.000.
• the polyesters and their method of preparation are described in detail in EPA 311 342.
• chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1% by weight of total composition, in the formulas will provide improved through the wash stability of the detergent enzymes.
• Compositions comprising chlorine scavenger are described in the European patent application 92870018.6 filed January 31 , 1992.
• Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units.
• the side-chains are of the formula -(CH2CH2 ⁇ ) m (CH2)nCH3 wherein m is 2-3 and n is 6-12.
• the side-chains are ester-linked to the polyacrylate "backbone” to provide a "comb" polymer type structure.
• the molecular weight can vary, but is typically in the range of about 2000 to about 50,000.
• Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.
• compositions of the invention may contain a lime soap peptiser compound, which has preferably a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6.
• LSDP lime soap dispersing power
• the lime soap peptiser compound is preferably present at a level from 0% to 20% by weight.
• the cleaning compositions of the present invention can also include compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
• polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Addition of such polymers also enhances the performance of the enzymes according the invention.
• R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.
• polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-0 group forms part of the R-group.
• Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
• Another class of said polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-0 group is attached to the R-group.
• polyamine oxides wherein R groups can be aromatic such as phenyl.
• Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibifing properties.
• suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
• the polyamine oxides can be obtained in almost any degree of polymerisation.
• the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
• the average molecular weight is within the range of 500 to 1000,000; preferably from 1 ,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
• N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1 ,000,000, preferably from 5,000-200,000.
• Highly preferred polymers for use in detergent compositions according to the present invenfion comprise a polymer selected from N-vinylimidazole N- vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.
• Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.
• the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure.
• the cross- linked polymers entrap the dyes by swelling.
• the composifions of the invention may be used in essentially any washing or cleaning methods, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate rinse aid composition may be added.
• the process described herein comprises contacting fabrics with a laundering solution in the usual manner and exemplified hereunder.
• the process of the invention is conveniently carried out in the course of the cleaning process.
• the method of cleaning is preferably carried out at 5°C to 95°C, especially between 10°C and 60°C.
• the pH of the treatment solution is preferably from 7 to 12.
• a preferred machine dishwashing method comprises treating soiled articles with an aqueous liquid having dissolved or dispensed therein an effective amount of the machine dishwashing or rinsing composifion.
• a conventional effective amount of the machine dishwashing composition means from 8-60 g of product dissolved or dispersed in a wash volume from 3-10 litres.
• soiled dishes are contacted with an effective amount of the dishwashing composition, typically from 0.5-20g (per 25 dishes being treated).
• Preferred manual dishwashing methods include the application of a concentrated solution to the surfaces of the dishes or the soaking in large volume of dilute solution of the detergent composition.
• the enzymes levels are expressed by pure enzyme by weight of the total composition and unless otherwise specified, the detergent ingredients are expressed by weight of the total compositions.
• the abbreviated component identifications therein have the following meanings:
• Neodol 45-13 C14-C15 linear primary alcohol ethoxylate sold by Shell
• DTDMAMS Ditalllow dimethyl ammonium methylsulfate. SDASA 1 :2 ratio of stearyldimethyl amine:triple-pressed stearic acid.
• Nai2(A1 ⁇ 2Si ⁇ 2)i2- ⁇ f ⁇ O having a primary particle size in the range from 0.1 to 10 micrometers (Weight expressed on an anhydrous basis).
• Citric Anhydrous citric acid Citric Anhydrous citric acid.
• Carbonate Anhydrous sodium carbonate with a particle size between 200 and 900 micrometres.
• MA/AA 1 Random copolymer of 6:4 acrylate/maleate, average molecular weight about 10,000.
• PA30 Polyacrylic acid of average molecular weight of between about 4,500 - 8,000.
• PB1 Anhydrous sodium perborate monohydrate of nominal formula NaB ⁇ 2-H2 ⁇ 2.
• NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
• NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate.
• DTPA Diethylene triamine pentaacetic acid.
• MnTACN Manganese 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane.
• PAAC Pentaamine acetate cobalt(lll) salt PAAC Pentaamine acetate cobalt(lll) salt.
• Electron donor II Sodium sulfite Na2S03 photographic grade (pfs) 97 %. Sigma product S 6778.
• Cytochrome 1 0 0..0077 0 0..11 0 0..22 0 0..0077 0 0..11 0 0..22
• Brightener 1 0.2 0.2 0.2 0.2 0.2
• Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0
• Brightener 2 0.3 0.2 0.3 - 0.1 0.3
• Electron donor I 0.05 0.1 2.0 0.05 0.1 2.0
• Brightener 1 0.2 0.2 0.2 0.2 0.2
• Electron donor 1 0.01 0.05 0.09 0.9
• Electron donor 1 0.09 0.2 0.1
• Photoactivated bleach 30 ppm 20 ppm - 10 ppm
• liquid detergent formulations were prepared according to the present invention (Levels are given in parts per weight, enzymes are expressed in pure enzyme) :
• Electron donor I 0.07 0.15 0.1 0.2 0.8
• Brightener 1 0.2 0.07 0.1 - -
• liquid detergent formulations were prepared according to the present invention (Levels are given in parts per weight, enzymes are expressed in pure enzyme) :

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Citations (3)

• 1997
  • 1997-07-09 WO PCT/US1997/012446 patent/WO1999002641A1/en active IP Right Grant
  • 1997-07-09 EP EP97933516A patent/EP1002042B1/de not_active Expired - Lifetime
  • 1997-07-09 AT AT97933516T patent/ATE230012T1/de not_active IP Right Cessation
  • 1997-07-09 DE DE69718064T patent/DE69718064T2/de not_active Expired - Fee Related
  • 1997-07-09 ES ES97933516T patent/ES2185031T3/es not_active Expired - Lifetime
  • 1997-07-09 JP JP2000502143A patent/JP2001509540A/ja not_active Withdrawn
  • 1997-07-09 AU AU36683/97A patent/AU3668397A/en not_active Abandoned
• 1998
  • 1998-07-08 ZA ZA986052A patent/ZA986052B/xx unknown

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