CA2228966C - Detergent compositions containing amine and specially selected perfumes - Google Patents

Abstract

Laundry detergent compositions containing amine detersive surfactants and specially selected perfume components which reduce the malodor of the amine are provided. More specifically, the specially selected perfume components a re selected from the group consisting of dodecahydro-3a,6,6,9A-tetramethylnapht ho (2,1-B) furan,3,3-dimethyl-5-(2,2,3 trimethyl-3 cyclopenten-1-yl)-4 pentenol , methyl lonone, cis 3 hexenyl iso butyrate, undecalactone, phenyl ethyl pheny l acetate, hexyl-ortho-hydroxybenzoate, and mixtures thereof.

Description

I
DETERGENT COMPOSITIONS CONTAINING AMINE
AND SPECIALLY SELECTED PERFUMES
TECHNICAL FIELD
This invention relates to laundry detergent compositions containing amine detersive surfactants and specially selected perfume components which reduce the malodor of the amine.
BACKGROUND OF THE INVENTION
It has long been known that certain amines are effective detergent surfactants. However, a problem associated with many amines is an unattractive odor resembling fish which remains present in detergent compositions containing the amine and even in fabrics which have been washed with the amine-containing detergent.
It has now been found that including a certain amount of specially selected perfume components in the laundry detergent can markedly reduce or eliminate this malodor.
SUMMARY OF THE INVENTION
In one embodiment there is provided a laundry detergent composition in liquid form comprising: (a) from about 0.05% to about 10%, by weight of detergent composition of an amine detersive surfactant of the formula:
Rl-X-(CHZ)"N(R3)(R4) wherein RI is a C6-C1z alkyl group; n is from about 2 to about 4, X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R-0 are individually selected from H, C~-C4 alkyl, or (CHZ-CHZ-O(RS)) wherein RS is H or methyl; (b) FROM ABOUT 0.00001% to about 5%, by weight of the composition, of a perfume component selected from the group consisting of dodecahydro-3a,6,6,9A-tetramethylnaphtho (2,1-B) furan, 3,3-dimethyl-5-(2,2,3 trimethyl-3 cyclopenten-1-yl)-4 pentenol, methyl lonone, cis hexenyl iso butyrate, undecalactone, phenyl ethyl phenyl acetate, hexyl-ortho-hydroxybenzoate, and mixtures thereof; and (c) from about 1 to about 95%, by la weight of the composition, of other non-amine detersive surfactants selected from anionic, nonionic, ampholytic, cationic, zwitterionic, and mixtures thereof.
These perfume components act to reduce the malodor associated with amine surfactants. Preferably the perfume components is selected from the group consisting of dodecahydro-3a,6,6,9A-tetramethylnaphtho (2,1-B) furan, 3,3-dimethyl-5-(2,2,3 trimethyl-3 cyclopenten-1-yl)-4 pentenol, methyl lonone, cis hexenyl iso butyrate, undecalactone, phenyl ethyl phenyl acetate, hexyl-ortho-hydroxybenzoate, and mixtures thereof; and The compositions of this invention preferably further comprise a performance enhancing amount of a detergent-compatible enzyme selected 6rom the group consisting of proteax, lipase, amylase, ceUulase, peroxidase, and mixtures thereof.
All parts, percentages and ratios used herein are expressed as percent ,weight unless otherwix specified.
DESCRIPTION OF THE INVEN~~
The laundry detergent compositions herein comprix an effective amount of a perfume component which acts to reduce the malodor associtated with the amine surfactant. By "effective amount" means an amount sufficient to reduce the amino-type odor of the detergent compositions. Preferably, the detergent compositions herein will comprise from about 0.00001 % to about 5, more preferably about 0.00001% to about 2%, most preferably about 0.0001% to about 0.5%, by weight, of speasUy selected perfume components. The perfume components which have been found to reduce the amine malodor are thox with a low solubility in water, i.e., they have a partition coeffcient value, (clogP), egos! to or higher than 2.0, at standard conditions of 25oC and 760 mm Hg in a water/octanol system.
Additionally the perfume components of this invention should have a boiling point greater than 200oF. The perfume components also have a unique properly of having a low odor detection threshold (ODT) lower than about 300 PPB, preferably equal to or Iowa than shout 0.1 PP8. Than parameters ue fully explained in 'Compilation of Odor and Taste T'tueshold Value Dsts. (ASTM DS 48 A)'. Edited by F. A Fauatari, Inta~nationa! Businaa Machines, HopweU Juntion , NY.
Examples of preferred perfume components are thox selected from the group coos;sting of dodxahydro-3a,6,6,9A-tetmrnr<hytnaphtho (2,1-g) furan, 3,3-dimahyl-5-(Z,2,3 tlimathyt-3 cyclopenten-1-yl)-4 p~u~o~ lono ne, cis 3 hexaryi iso butyrate, undecalactone, Phenyl ethyl Phenyl acetate, hexyl-ortho-hydruxybenzoate, and mixtures thereof.
It is preferred that the speaally selected perfume components herein be mixed together prior to addition to the laundry detergent composition. Those perfume components may be combined with other perfume ingredients before addition to the composition.
The perfume containing these specially selected perfume components is preferably sprayed onto the final granular detergent composition or mixed into the final liquid laundry detergent in a manner which does not adversely affect the perfume.
The amine - Although certain amines are effective surfactants, when present in sufficient amounts, many posses an unattractive amine-type malodor which makes them undesirable for laundry applications. Amines suitable for use in the detergent compositions herein include those according to the formula:
Rl-X-(CH2)n-N~3)~4) wherein Rl is a C6-C12 alkyl group; n is from about 2 to about 4, X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are individually selected from H, C 1-C4 alkyl, or (CH2-CH2-O(RS)) wherein RS is H or methyl.
Preferred amines include the following:
Rl-(CH2)2-NH2 Rl-O-(CHa)3-NH2 Rl-C(O)-NH-(CH2)3 N(CFi3)2 Rl-N(CHZ-CH(OITj-RS)2 wherein Rl is a C6-C 12 alkyl group and RS is H or CH3.
In a highly preferred embodiment, the amine is described by the formula:
Ri-C(O)-NH-(CH2)3-N(CH3)2 wherein Rl is Cg-C12 alkyl.
Particularly preferred amines include those selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C 12 bis(hydroxyethyl~mine, Cg-C12 bis(hydroxyisopropyl)amine, and Cg-C12 amido-propyl dimethyl amine, and mixtures.
The laundry detergent compositions of the present invention typically comprise from about 0.5% to about 10%, preferably from about 1% to about 5%, by weight of amine surfactants.
Non-Amine n~P~Pnt Surfactants - A wide range of non-amine, secondary surfactants can be used in the detergent composition of the present invention.
By "non-amine" is meant herein any detersive surfactant which does not have the unattractive "amine" malodor associated with its use in a detergent composition.
Included in this definition of non-amine, therefor, is amine oxides.which do not have an amine-type odor.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these w~ is given in US Patent 3,664,961 issued to Norris on May 23, 1972. The laundry detergent compositions of the present invention typically comprise from about 1°/. to about 95%, preferably from about 3% to about 40%, more preferably from about 5% to about 25%, by weight of such secondary, non-amine surfactants.
One class of preferred anionic surfactants to be used in this invention are the alkyl alkoxylated sulfate surfactants which are water soluble salts or acids of the formula RO(A)mSO,M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C 10-C24 ~ ~omPonent, prefasbly a C 12-C 18 ~Y1 or hydroxyalkyl, more preferably C 12-C 15 ~ or hydroxyalkyi, A is an ethoxy or propoxy unit, m is ,greater than zero, typically betyv~ 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a canon which can be, for example, a metal canon (e.g., sodium, potassium, lithium, calaum, ntagnaium, ecc ) ammonium or sub~nium canon. Alkyl ethoxylued sulfates as well as ~ ProPoxY~~d are contemplated herein. Specific examples of substituted atnrnonium canons ittchrde ethanol-, triahanol-, rr~yl_ ~~yl, yl-ammomium rations and quaternary ammonium rations such as tetrameth yl-ammonium ~ PiP~~m rations and those derived from alkylarnines such as ~~ ~~Y~~ylamine. mixtures thereof and the like. Exemplary surfactants aro a 12-C 1 s ~ Poke ( 1.o) sulfate (e I2-c 1 sE( 1.oj~, c 12-C 15 alkyl poiyethoxylate (2.25) sulfate (C 12-C 1 SE(2.25~, C 12-C 15 FYI
poiyethoxylste (3.0) sulfate (C 12'C 1 SF(3.0~, and C 12-C 15 ~ poiyethoxytate (4.0) site (C 12~ 1 SE(4.0~, wherein M is conveniently selected from sodium and potassium.
Another useful and preferred class of anionic s<ufiaants are the alkyl sulfate p~ ~ a!~ sulfates which era wale soluble salts or acids of the formula ROS03M wherein R preferably is a C8-C 18 hydrocubyl, preferably an alkyl or hydroxyalkyl having a C 10-C 18 FYI component, more preferably a C 12-C 15 a~ or hydroxyalkyl, and M is H or a ration, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Other suitable anionic surfactants that can be used are alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous S03 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.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula R3-CH(S03 M)-C(O)-OR4 wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof; R4 is a C 1-C6 hydrocacbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R3 is C 10-C 16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is 016 ~Yl.
Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-022 primary of secondary alkanesulfonates, Cg-024 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, Cg-024 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide);
alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl ~ phenol ethylene oxide ether sulfates, parai~n sulfonates, alkyl phosphates, isethionates such as the aryl isethionates, N-aryl taurates, alkyl succinamates and ' sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12-C 1 g monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C 12 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2p)k_ CH2C00-M+ ~,,~h~ R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwarez, Perry and Berth). A
variety of such ~t$ ~e d~ g~erally disclosed in U.S. Patent 3,929,678, iced December 30, 1975 to Laughlin, tt al. at Column 23, line 58 through Column 29, line 23 .
One class of nonionic s~rrfactants useful in the present invention are condensates of ethylene oxide with s hydrophobic moiety to provide a surfactant having an average hydrophilic-Gpophilic balance (HI.8) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group wtuch rs condensed with any particular hydrophobic group can be readily adjusted to yidd a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic dements.
Espaialty preferred nonionic surfactants of this type are the C9-C I 5 PAY
doo~l ~Oxylatas containing 3-12 moles of ethylene oxide per mole of alcohol, p~~ C12'C15 P~nnu'Y alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
Another dasa of nonionic s<rrfactants comprises alkyl polyglucoside compounds of general fonau4 R~CnH2n0)t~c whadn Z is a moiety derived from glucox; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, thn compounds including less than I0~/. unrfatty d~hol and less than 50'/~ short chain alkyl polyglucosides. Compounds of this type and their use in d~aBeM are disclosed in F.P-8 0 070 077, 0 075 996 and 0 094 118.
Very suitable as nonionic surfactants are poly hydroxy fatty acid amide sirr&aaras of the formula R2_C(O)-N(R 1 )-Z.
wherein R 1 is H, or R 1 is C 1 ~ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is CS_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a Linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or as alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight alkyl or alkenyl chain such as coconut alkyl or mixtures thereo>~ and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
krghly preferted nonionics are amine oxide surfactants. The compositions of the present invention may comprise amine oxide in acxordance with the general formula I:
RI~O~c(PO~O)zN(OXCH2R'~.qH20 (n In general, it can be seen that the structure (I) provides one long-chain moiety R1(EO~(POh,(BO~ and two short chain moieties, CH2R'. R' is preferably selected from hydrogen, methyl and -CH20H. In general R1 is a primary or branched hydroca:byl moiety which can be saturated or unsat<usted, preferably, R 1 is a Primacy alkyl moiety. When x+y+z = 0, Rl is a hydrocarbyl moiety having chainlength of from about 8 to about 18. When x+y+z is different from 0, R1 may be somewhat longer, having a chainlength in the range C 12-C24. The general formula also encompasxs amine oxides wherein x+y+z = 0, R 1 = Cg-C l g, R' = H and q =

2, Pr~IY 2. These amine oxides are illustrated by C 12.14 ~~~Yi amine oxide,hexsdecyl dimahylamine oxide, octadecylamine oxide and their hydrates, ~peaally the dihydrsta as dixlosed in U.S. Patents 5,075,501 and 5,071,594.
The invardon also encompasses amine oxides wherein x+y+z is dif~'erent from zero, speeiseally x+y+z is from about 1 to about 10, Rl is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in thex embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy;
PO
repraa~ts propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 9Q°C, pm;ne oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
Preferred commercially available amine oxides are the solid, dehydrate ADMOXM 16 and ADMOX 18, ADMOX 12 and especially A,DMOX 14 from Ethyl Corp.
Preferred embodiments include hexadecyldimethylamine oxide dehydrate, octadecyldimethylamine oxide dehydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, and tetradecytdimethylamine oxide dehydrate.
Whueas in certain of the preferred embodiments R' = H, there is some latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments wherein R' = CH20H, such as hexadecylbis(2-hY~xY~thYl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hY~xYethyl~ne oxide and oleylbis(2- hydroxyethyl~n~ine oxide.
Cationic detaaive ~rr~ccan~ ~i~le for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl B~P~ ~ples of such cationic surfactants include tha ammonium surfactants such as aUcyldimethylammonium halogenides, and those surfactants having the formula [R2(OR3h,J(R4(OR3 )y12R5~-wherein R2 is as alkyl or alkyl benryl group having from about 8 to about 18 carbon atoms in the alkyl chtin, each R3 is selected from the group consisting of -CH2CH2-, -~2~~3~'. -CH2CH(CHZOH)-, -CH2CH2CH2-, and mixtures thereof each R4 is sdaxed from the group consisting of CI-C4 alkyl, C -C h ring struc~ura formed by joining the ~ R41 4 Y~oxY~cyt, benzyl gr~Ps. -CH2CHOH
CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose polymer having a molecular wdght less than about 1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon stoma of R2 plus RS is not moro than about 18; each y is from 0 to about 10 and the sun, of the y values is from 0 to about 15; and X is any compatible anion.
Frefa~red cuionic surfactants are the water-soluble quaternary ammonium compounds useful in tix present composition having the formula R1R2R3R4N+X- (i) wherein R 1 is Cg-C l 6 alkyl, each of R2, R3 and R4 is independently C 1-C4 alkyl, CI-C4 hydroxy alkyl, benzyl, and -(C2H40}xH where x has a value from 1 to 5, and X is an anion. Not more than one of R2, R3 or R,4 should be benryl.
The preferred alkyl chain length for R 1 is C 12-C 15 P~~1~'lY 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. Preferred groups for R2Rg and Rd are methyl and hydroxyethy) groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
>:xamples'of 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 methyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12-15 Yl l~Ydroxyethyi ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl ttirntthyl ammonium methyl sulphate;
lauryl dimethyl benryl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein Rl is -CH2-O.C(p).C12-14 ~Yl and R2R3R4 are methyl).
Other cationic surfactants useful herein are also described in U. S. Patent 4,228,044, Carrrbre , issued October 14, 1980.
$y~,g - T to compositions according to tha pr~aar< invention ~ may further comprise a builds systan. Any conventional builder system is suitable for use herein indudmg auurrinosiliate nutaials, silicsta, Polycarboxylates and fatty acids, mstaials such as ethylenediamine tetraacetate, metal ion sequestrants such as amnopotyphosphonstes, particulatfy ethylenediamine trtramrthylene phosphoric acid sad diethylene triamine pentamethylenephosphonic sad. Though less preferred for obvious environmental reasons, phosphate builders can also be used herein.
Suitable polycarboxylata builders for use herein include atric acid, preferably in the foam of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH~,~COOH) wherein R is C 10.20 alkyl or alkenyl, preferably C 12-16~

or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
Specific examples include lauryl succinate , myristyl succinate, palmityl succinate 2-dodecenylsuccinate, Z-tetradecenyl succinate. Succinate builders are preferably used .
in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated C 10.18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
Detergency builder salts are normally included in amounts of from 3% to 50%
by weight of the composition preferably from 5% to 30% and most usually from 5%
to 25% by weight.
Optional Deter~rrent Ingredients: - Preferred detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits. Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, . 13-glucanases, arabinosidases or mixtures thereof.
A preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with the lipolytic enzyme variant D96L at a level of from 50 LU to 8500 LU per liter wash solution.
The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM
1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about SOKDa, an isoelectric point of 5.5 and containing 415 amino acids. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in United States Patent No. 5,520,838 issued May 28,1996 (Novo).
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
Peroxidssc-containing detergent compositions are disclosed, for example, in PCT
International Application WO 89/099813 and in Canadian Patent application EP
No. 2,122,987 filed October 28, 1992.
Said cellulases andlor ptroxidases.are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
Preferred commercially available protease enzymes include those sold under the trademarks Alcalase, Savinase, Primase, Durazym,, and Esperase by Novo Nordisk A/S (Denmark), those sold under the trademarks Maxatase, Maxacal and Maxapem by Grist-Brocades,- those sold by Gmencor International, and those sold undo the trademarks Opticlean and Optima~e by Solvay Fnzymea. Also professes described in our co-pending appUcation CA 2173105 can be included in the detergent composition of the imrention. Protease enzyme may be incorporated into the compositions in u;cordance with the invention at a lend of from 0.0001'/.
to 2°/.
active a~zyme by weight of the composition.
A prefaced protease herein referred to as "Proteax D' is a carbonyl hydrolsse variant having an amirro acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino aad for the amino acid residue at a position in said carbonyl hydrolase equivalent to position +76, preferably also in comb'u~ation 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, +I28, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the rurrnbering of Bacillus ~nyloliquefaciercs subtilisin, as described in the concurrently filed patent application of A. Baeck et al. entitled "Protease-Containing Cleaning Compositions" having U.S. Patent No. 5679630 issued October 21, 1997.
F~ghly preferred enzymes that can be included in the detergent compositions of the present invention include Gpases. It has been found that the cleaning performance on greasy soils is synergistically improved by using Gpases.
Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological aoss-reaction with the antibody of the lipase, produced by the microorganism Pseudonrwas Jluorescens 1AM 1057. This lipase is available from Amano Pharmacartical Co. Ltd., Nagoya, Japan, under the trade mark Lipase P
»Arnano,"
hereinafter referred to as "A~rnano.P». Further suitable lipases are fipases such as M1 LipsseR and LipomaxR (Gist-Brocades). I~ghlY preferred .Lipase are the D96L
4Po~o variant of the native lipase derived from Humicola lanuginosa as described in US Patent No. 5837010. Preferably the Humicola lanuginosa strain DSM 4106 is used. This enzyme is incorporated into the composition in accordance with the invention at a levd of from 50 LU to 8500 LU per liter wash solution.
DIY ~ v~ant D96L is present at s levd of from 100 LU to 7500 LU pa liter of wash solution. More preferably at a level of from 150 LU to 5000 LU per liter of wash solution.
By D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 viz. wherein the naive lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L).
According to this noma~clature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
Also ~ritable are autinases [EC 3.1.1.50] which can be considered as a specdal kind of lipase, sandy lipases which do not require interfaaal uxivation.
Addition of cutinsaes to detergent compositions have been described in e.g. WO-A 88/09367 (Gara~cor).
The lipases and/or cutinaxs are norntally incorporated in the detergent composition st levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.

Amylases (& and/or Q) can be included for removal of carbohydrate-based stains. Suitable amylases are Termamyl~ (Novo Nordisk), FungamylR and BANK
(Novo Nordisk).
The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
Said enzymes are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in European Patent Publication 553607 published August 4, 1993. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
Other components used in detergent compositions may be employed, such as soil-suspending agents, soil-release polymers, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and other perfumer.
Soil Release Anent - Arry soil release agents known to thox skilled in the art can be employed in the practice of this invention. Prefaced polymeric soil releaser agents are characterized by having both hydrophilic xgments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic xgments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, save as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil releax agent to be more easily cleaned in later washing procedures.
Useful soil rdease polymers are described in U.S. Pata~t 4,000,093, issued Decanter 28, 1976 to Ncol et al., European Patent Application 0 219 048, published April 22, 1987 by Kud et al. U.S. Patent 3,959,230 to Flays, issued May 25; 1976, U.S. Patent 3,893,929 to Basadur issued July 8, 1975, U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al., U.S. Patent 4,721,580, issued January 26, 1988 to Cossdidc, U.S. Patent 4,702,857, issuod October 27, 1987 to Gosse4nk, U.S. Patent 4,877,896, issued October 31, 1989 to Maldonsdo et al.
If utilized, soil rdease agents will generally comprise from about 0.01 % to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
~~- The detergent compositions herein may also optionally contain one or more iron and manganese chelating agents as a builder adjunct material. Such chelating agents can be selected from the group consisting of am;no carboxylates, amino phosphonates, polyfunctionally -substituted aromatic chelating agents and mixtures thereo>; all as hereinafter defined. Without intending to be bound by theory, it is believed that the b~~t of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
If utilized, these chelating agents will generally comprise from about 0.1 %
to about 10% by weight of the detergent compositions herein. More preferably chelating agents will comprise from about 0.1% to about 3.0~/° by weight of such compositions.
Cl_av .~ ~I -1'he compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposidon properties. Liquid detergent compositions which contain these compou~s typically contain from about 0.01 % to 5%.
The most preferred soil rdease and anti-redeposit;on agent is ethoxylated tYl~apentamine. Exemplary ethoxylated amines are firrtha descr,'b~ in U. S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removaUanti-redeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
Other clay soil removaUanti-redeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions hereof. Another type of preferred anti-redeposition agent includes the carboxymethylcellulose (CMC) materials.
~~.~~.AQI~ - Polymeric dispersing agents can advantageously be utilized in the compositions hereof. These materials can aid in calcium and magnesium hardness control. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. The compositions hereof will generally comprise from 0% to about 5%
of polymeric dispersing agent.
Suitable polymeric dispersing agents for ux herein are described in U.S.
Patent 3,308,067, Diehl, issued March 7, 1967, and European Patent App4eation No.
66915, published December 15, 1982, Brig - Any suitable optical brightenen or other brightening or whitening agents known in the art can be incorporated into the detergent compositions hereof.
The compositions hereof will generally comprise atom 0% to about 5% of brightener Commercial optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, mtthinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5~ and 6-membered-ring heterocycles, and other misceUacteous agents. Examples of such brighteners are discloxd in "The Production and Application of Fluarescertt Brightening Agents", M. Zahradnik, Published by John Whey & Sons, New York (1982 Suds Supi~messur. -Compounds known, or which become known, for reducing or suppressing the formation of suds can be incorporated into the compositions of the prexnt imemion. Suitable suds supprcssors are described in. ICirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Whey 8t Sons, Inc., 1979), U.S. Patent 2,954,347, issued September 27, to St. John, U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo a at., U.S.
Patent 4,265,779, issued Msy 5, 1981 to Gandolfo et al. and European Patent Publication 354016, published February 7, 1990, U.S. Pstent 3,455,839, German Patent Application DOS 2,124,526, U.S. Pata~t 3,933,672, Bartolotta et al., and U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987.
The vompositions hareof will generally comprix from 0°/. to about 5%
of suds suppressor.
Other ~ ~ The compositions herein may also contain other perfume ingredients such as aldehydes, ketones, alcohols and esters. They have been described by Parry in Parry's Cycloyedia of Perfumarv (1925) Vol. I and II
published by P. Blakiston's Son & Co.; and also by Bedoukian in Perfumarv and Flavoring Synthet~ (1967), published by Elsevier Publishing Company.
A wide variety of other ingredients useful in detergent compositions can be included in the compositions hereof, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, bleaches, bleach activators, enzyme stabilizing systems, etc.
Lei uid Comnositions - The laundry detergent compositions herein preferably have a pH in a 10% solution in water at 20oC of between about 5 and about 12, more preferably between about 8 and about 12 for granular compositions.
Liquid detergent compositions can contain water and other solvents as carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
Preferred liquid laundry detergent compositions hereof will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and 11.0, preferably between about 7.0 and 8.5, The liquid detergent compositions herein preferably have a pH in a 10% solution in water at 20oC of between about 6.5 and 11.0, preferably 7.0 to 8.5. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
Preferably, the liquid compositions according to the present invention are in "concentrated 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. The level of water is less than 50%, preferably less than 30% by weight of the detergent compositons.
Said concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs.
The liquid compositions are especially effective when applied directly to soils and stains in a pretreatment step.
The detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
The detergent compositions according to the present invention include compositions which are to be used for cleaning of substrates, such as fabrics, fibers, hard surfaces, skin etc., for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automaticand non-automatic dishwashing compositions.

The following examples illustrate the compositions of the present invention.

All parts, percentages and ratios used herein are by weightotherwise specified.
unless EXAIyIPLE I

A "fresh~citrus" perfume is prepared using the following components:

PERFUM1E A % BY

WEIGFIZ' Alpha terpineol 1.80 Citronellol 1.50 Citronellyl acetate 1.08 Geraniot 1.26 Isobornyl acetate 1.08 Linaloot 1.44 Linalyl acetate 2.10 , Campl~ne 0.78 Fenchyl acetate 0.12 Alpha pinene 1.50 Beta pinene 1.08 Citral 2.40 Citrathal 0.74 Citronella) nitrite 0.84 Dihydromyrcenol 0.60 Dipenteae 3.00 Geranyl nitrite 0.60 Lemon oil 0.30 Orange oil 2x rectified 2.40 p~y 1.26 Pseudo linalyl acetate 1.20 dodecahydro-3a,6,6,9Axerramethylnaphtho (2,1-B) furan 5.00 Other perfume components 72.74 100.00 This perfume is then useful in detergent compositions, particularly when amine surfactants are present. The perfume can be used at a level of from about 0.01% to about 1%, by weight of the detergent composition.

The dodecahydro-3a,6,6,9A-tetramethylnaphtho (2,1-B) furan is substituted with an equal amount of one or more of the following perfume components: 3,3-dimethyl-5-(2,2,3 trimethyl-3 cyclopenten-1-yl)-4 pentenol, methyl lonone, cis hexenyl iso butyrate, undecalactone, phenyl ethyl phenyl acetate, hexyl-ortho-hydroxybenzoate, and mixtures thereof. , EXAMPLE II
A "fresh" perfume is prepared using the following components:
~E1~FLJME B % BY
~V_EIGHT' IFF-917* 92.00 Dodecahydro-3a,6,6,9A-tetramethylnaphtho (2,1-B) furan 0.30 3,3-dimethyl-5-X2,2,3 trimethyl-3 cyclopenten-1-yl)-4 pentenol 0.15 Methyl lonone 1.55 Cis 3 hexenyl iso butyrate 0.25 IJndecalactone 0.30 Phenyl ethyl phenyl acetate 1.15 Hexyl-ortho-hydroxybenzoate 4.30 100.00 *Supptied by International Flavor and Fragrance Company of New Jersey This perfume is then useful in detergent compositions, particularly when amine surfactants are present. The perfume can be used at a level of from about 0.01% to about 1%, by weight ofthe detergent composition.
E~~AMPLE III-VIII
The following liquid detergent compositions are made In edient Exam le III Exam le IV

Wt % Wt Sodium C12-l5alkyl polyethoxylate13.50 13.70 (2.5) sulfate Sodium 12-15 1 sulfate 4.50 4.00 Ethanol 3.50 2.64 Monoethanolamine 1.00 0.75 C 10 amido ro ldameth i amine 1.75 1.3 Pro andiol 7.50 7.50 C12-13A1 1 0l etho late 9 2.00 0.63 C12-14 1 ucose amide 4.50 3.35 C12-14 fa acid 2.00 3.50 Sodium toluene sulfonate 2.50 2.25 Citric acid 3.00 2.65 PERFRJMfC A 0.01 1.00 , Enzymes ~ 0.05 0.05 Borax _ 3.50 3.50 Sodium h droxide to H 8.0 2.95 to H =8.02.10 to H =
7.6 Tetraeth lene entamine etho fated1.18 1.18 Water to 100% to 100%

Perfume A may be substituted with an equal amount of Perfume B.
The Clp amidopropyldimethyl amine is substituted with an equal amount of the following amines: octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C

bis(hydroxyethyl)amine, Cg-C 12 bis(hydroxyisopropyl)amine, and Cg, C~, C 11 or C 12 amido-propyl dimethyl amine, and mixtures.
The follovtring enzymes are used: protease, lipase, amylase, cellulase, peroxidase, and mixtures thereof.
In edient Exam le V

Wt%

Sodium C12-15 1 0l etho late 2.5 sulfate 9.40 Sodium 12-15 1 sulfate 3.10 Ethanol 2.18 Monoethanolamine 1.00 C10 amido ro Idimeth 1 amine surfactant 4.30 Pro andiol 3.20 C12-13A1 1 0l etho late 9 1.00 C12-14 1 ucose amide 2.00 C 12-14 fa acid 1.00 Sodium toluene sulfonate 2.25 Citric acid 1.80 P~ A 0.5 E es 0.05 Borax -Sodium h droxide to H 8.0 2.07 to H
= 8.0 Tetraeth lene entamine etho fated 15-18 1.00 Water to 100%

The C 1 p amidopropyldimethyl amine is substituted with an equal amount of the following amines: octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C12 bis(hydroxyethyl)amine, Cg-C 12 bis(hydroxyisopropyl)amine, and Cg, Cg, C 11 or C 12 amido-propyl dimethyl amine, and mixtures.
' The following enzymes are used: protease, lipase, amylase, cellulase, peroxidase, and mixtures thereof.
Perfume A may be substituted with an equal amount of Perfume B.

ZO
In edient Exam le VI Exam le VII

Wt% Wt%

Sodium C12-15 1 0l etho late 3 13.70 13.70 sulfate Sodium 12-15 1 sulfate 4.00 4.00 Ethanol 2.64 2.64 Monoethanolamine 0.75 0.75 O 1 amine 3,0 C 12 amido ro Idimeth 1 amine -- 0.5 Pro andiol 7.50 7.50 C12-13AI I of etho late 9 0.63 0.63 C12-14 I ucose amide 3.35 3.35 C 12-16 fa acid 3.50 3.50 Sodium toluene sulfonate 2.25 2.25 Citric acid 2.65 2.65 PERFUME A 0.25 0.05 E a 0.1 0.075 Borax 3.50 3.50 Sodium h droxide 2.1 to H 2.1 to H
= 7.6 = 7.6 Tetraeth lene entamine etho fated 1.18 1.18 Water, & other o tional in edientsto 100% to 100%

Perfume A may be substituted with an equal amount of Perfume B.
The amines are substituted with an equal amount of the following amines:
hexyl amine, decyl amine, dodecyl amine, Cg-C 12 bis(hydroxyethyl)amine, Cg-C

bis(hydroxyisopropyl)amine, and Cg_11 amido-propyl dimethyl amine, and mixtures.
The following enzymes are used: protease, lipase, amylase, cellulase, peroxidase, and mixtures thereof.
In edient Exam le VIII

Wt%

Sodium C12-15 I of etho late 3 sulfate 13.70 Sodium 12-15 1 sulfate 4,00 Ethanol 2.64 Monoethanolamine 0.75 O I amine C12 bis h dro eth 1 amine 2.0 Pro andiol 7.50 C12-13AI 1 0l etho late 9 0.63 ' C12-14 1 ucose amide 3.35 C12-16 fa acid 3.50 Sodium toluene sulfonate 2.25 Citric acid 2.65 PERFLTME B 0.75 E a 0.25 Borax 3.50 Sodium h droxide 2.1 to H =
7.6 Tetraeth lene entamine etho fated 15-18 1.18 Water, & other o tional in edients to 100%

Perfume B may be substituted with an equal amount of Perfume A.
The C 12 bis (hydroxyethyl) amine is substituted with an equal amount of the following amines: octyl amine, hexyl amine, decyl amine, dodecyl amine, Cg-C

bis(hydroxyethyl)amine, Cg-C12 bis(hydroxyisopropyl)amine, and Cg-12 amido-propyl dimethyl amine, and mixtures.
The following enzymes are used: protease, lipase, amylase, cellulase, peroxidase, and mixtures thereof.
All detergent compositions in the above examples have a significantly reduced amine malodor as compared to equal formulations which do not contain the perfume components included above.
A

Claims (7)

CLAIMS:

1. A laundry detergent composition in liquid form comprising:
(a) from about 0.05% to about 10%, by weight of detergent composition of an amine detersive surfactant of the formula:
R1-X-(CH2)n-N(R3)(R4) wherein R1 is a C6-C12 alkyl group; n is from about 2 to about 4, X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH2-O(R5)) wherein R5 is H or methyl;
(b) FROM ABOUT 0.00001% to about 5%, by weight of the composition, of a perfume component selected from the group consisting of dodecahydro-3a,6,6,9A-tetramethylnaphtho (2,1-B) furan, 3,3-dimethyl-5-(2,2,3 trimethyl-3 cyclopenten-1-yl)-4 pentenol, methyl lonone, cis 3 hexenyl iso butyrate, undecalactone, phenyl ethyl phenyl acetate, hexyl-ortho-hydroxybenzoate, and mixtures thereof; and (c) from about 1 to about 95%, by weight of the composition, of other non-amine detersive surfactants selected from anionic, nonionic, ampholytic, cationic, zwitterionic, and mixtures thereof.

2. A laundry detergent composition according to Claim 1 further comprising a performance enhancing amount of a detergent-compatible enzyme selected from the group consisting of protease, lipase, amylase, cellulase, peroxidase, and mixtures thereof.

3. A laundry detergent composition according to Claim 1 wherein said amine is selected from the following:
R1-(CH2)2-NH2 R1-O-(CH2)3-NH2 R1-C(O)-NH-(CH2)3-N(CH3)2 R1-N(CH2-CH(OH)-R5)2 wherein R1 is a C6-C12 alkyl group and R5 is H or CH3.

4. A laundry detergent composition according to Claim 3 wherein said amine is the following:
R1-C(O)-NH-(CH2)3-N(CH3)2 wherein R1 is C8-C12 alkyl.

5. A laundry detergent composition according to Claim 3 wherein said amine is selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, C8-C12 bis(hydroxyethyl)amine, C8-C12 bis(hydroxyisopropyl)amine, and C8-C12 amido-propyl dimethyl amine, and mixtures.

6. A laundry detergent composition according to Claim 5 further comprising builders and other detergent ingredients.

7. A laundry detergent composition according to Claim 1 wherein said perfume component reduces the malodor of said amine surfactant.