Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUSH1468 H
Publication typeGrant
Application numberUS 08/234,077
Publication dateAug 1, 1995
Filing dateApr 28, 1994
Priority dateApr 28, 1994
Also published asEP0679714A2, EP0679714A3
Publication number08234077, 234077, US H1468 H, US H1468H, US-H-H1468, USH1468 H, USH1468H
InventorsJill B. Costa, Michael S. Showell
Original AssigneeCosta Jill B, Showell Michael S
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergent compositions containing cellulase enzyme and selected perfumes for improved odor and stability
US H1468 H
Abstract
A detergent composition containing cellulase and perfume is provided. Specifically, the detergent composition comprises: (a) a cellulase enzyme; and (b) a perfume containing at least 25% by weight of at least one fragrance material selected from the group consisting of aliphatic ketones with a molecular weight of between 200 and 350 AMU, aromatic ketones with a molecular weight of between 150 and 350 AMU, aliphatic aldehydes with a molecular weight of between 160 and 350 AMU, aromatic aldehydes with a molecular weight of between 150 and 350 AMU, condensation products of aldehydes and amines with a molecular weight between 190 and 350 AMU, aromatic and aliphatic lactones with a molecular weight between 140 and 350 AMU, aromatic and aliphatic ethers with a molecular weight between 150 and 350 AMU, aliphatic alcohols with a molecular weight between 200 and 350 AMU, aromatic and aliphatic esters with a molecular weight between 190 and 350 AMU and mixtures thereof. The perfume is substantially free of halogenated fragrance materials and nitromusks.
Images(15)
Previous page
Next page
Claims(12)
What is claimed is:
1. A detergent composition comprising:
(a) a cellulase enzyme; and
(b) a perfume containing at least 25% by weight of at least one fragrance material selected from the group consisting of aliphatic ketones with a molecular weight of between 200 and 350 AMU, aromatic ketones with a molecular weight of between 150 and 350 AMU, aliphatic aldehydes with a molecular weight of between 160 and 350 AMU, aromatic aldehydes with a molecular weight of between 150 and 350 AMU, condensation products of aldehydes and amines with a molecular weight between 190 and 350 AMU, aromatic and aliphatic lactones with a molecular weight between 140 and 350 AMU, aromatic and aliphatic ethers with a molecular weight between 150 and 350 AMU, aliphatic alcohols with a molecular weight between 200 and 350 AMU, aromatic and aliphatic esters with a molecular weight between 190 and 350 AMU and mixtures thereof;
wherein said perfume is substantially free of halogenated fragrance materials and nitromusks.
2. The detergent composition of claim 1 wherein said enzyme is a fungal cellulase.
3. The detergent composition of claim 1 further comprising from about 1% to about 55% of a surfactant.
4. The detergent composition of claim 3 wherein said surfactant is selected from the group consisting of alkyl benzene sulfonates, alkyl ester sulfonates, alkyl ethoxylates, alkyl phenol alkoxylates, alkylpolyglucosides, alkyl sulfates, alkyl ethoxy sulfate, secondary alkyl sulfates and mixtures thereof.
5. The detergent composition of claim 1 further comprising at least about 1% by weight of a detergency builder.
6. The detergent composition of claim 1 wherein said perfume is present in an amount from about 0.001% to about 5% by weight of said composition.
7. The detergent composition of claim 1 further comprising adjunct ingredients selected from the group consisting of bleaches, bleach activators, suds suppressors, enzyme stabilizers, polymeric dispersing agents, dye transfer inhibitors, soil release agents and mixtures thereof.
8. The detergent composition of claim 1 wherein said composition is in the form of agglomerates and the density of said detergent composition is at least about 650 g/l.
9. The detergent composition of claim 1 further comprising a polyhydroxy fatty acid amide for use as a surfactant.
10. A detergent composition according to claim 1 wherein said composition is in the form of a laundry bar.
11. A detergent composition according to claim 1 wherein said composition is in the form of a liquid.
12. A method of laundering fabrics comprising the step of contacting said fabrics with an aqueous medium containing an effective amount of a detergent composition according to claim 1.
Description
FIELD OF THE INVENTION

The present invention generally relates to detergent compositions containing celluase enzyme and selected perfumes. More particularly, the invention relates to detergent compositions incorporating perfumes which counteract the residual malodors associated with cellulase enzyme, the feedstock in which cellulases are contained, and cellulase treated laundry. Also, the perfumes selected herein exhibit improved compatibility with the cellulase enzyme contained in the detergent composition. The detergent composition of the invention may be formulated as a liquid, granular, or laundry bar composition.

BACKGROUND OF THE INVENTION

In the art of detergency, formulators have used enzymes in detergent compositions for a variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, and for the prevention of refugee dye transfer, and for fabric restoration. Typically, enzymes such as protease, amylases, lipases, cellulases and peroxidases have been used for such purposes. One major drawback to the use of enzymes in detergents is the unpleasant odor contribution such enzymes and the feedstocks in which the enzymes are usually contained and delivered. These enzymes and their feedstocks are complex mixtures obtained from fermentation processes and they typically contain many offensive odor contaminants which ultimately find their way into the detergent products in which the enzymes are included. The resulting malodors in such detergent compositions does not appeal to consumers. Additionally, the detergency enzymes have a tendency to leave residual odors on the fabric itself which leads to consumer dissatisfaction, as well.

In the past, these drawbacks have often been countered by limiting the level of enzyme used in the composition. However, this approach restricts product efficacy and does not entirely eliminate the malodor problem. Another approach entails "purifying" the enzyme so as to reduce the amount of malodor constituents in the enzyme itself prior to incorporation into the detergent. More particularly, detergent compositions containing protease enzyme have been purified such that they do not have a detectable odor in distilled water at specified concentration levels. While this approach provides a viable option, it requires an additional step in the manufacture of the detergent (i.e. the purifying step), thereby resulting in a more expensive product.

Other attempts in the art have also only focused on especially problematic enzymes. By way of example, there have been attempts directed to counteracting malodors associated with fabrics laundered with detergent compositions containing lipases. Enzymes such as lipases and protease have been known to exhibit offensive odors as contained in the detergent as well as to cause residual malodors on fabrics laundered with such protease or lipase-containing detergents. In that regard, certain perfumes have been used to mask the residual odors on fabrics caused by the lipase-containing detergents.

As is known, cellulase enzymes have been used in the art of detergency for purposes of providing fabric care as well as cleaning performance. It has also been known that perfumes may be included in cellulase-containing detergents. However, there is still a need for a detergent composition containing specific perfumes especially suitable for counteracting malodors associated with cellulase enzyme and its feedstock as well as the residual malodors which may be found on fabrics laundered with such cellulase-containing detergents. Moreover, it would be desirable to have a means by which the compatibility of the cellulase enzyme and perfume can be improved so as to provide a more stable detergent.

Accordingly, there remains a need for a cellulase-containing detergent composition which does not itself exhibit malodors or cause fabrics laundered such a composition to have residual malodors. There is also a need in the art for such a cellulase-containing detergent composition which exhibits improved stability.

BACKGROUND ART

The following references disclose proteases and lipases in detergents: Moeddel, U.S. Pat. No. 4,515,705 (Procter & Gamble); Behan et al, EP 430, 315 (Unilever); and, Watanabe et al, JP-A-63-334931 (Lion Co.). The following references disclose cellulase enzymes and their use in detergent compositions: Barbesgaard et al, U.S. Pat. No. 4,435,307 (NOVO Industries A/S); GB-A-2,075,028; GB-A-2,095,275; and GB-A-1,368,599.

SUMMARY OF THE INVENTION

The present invention meets the needs identified above by providing a cellulase-containing detergent composition which does not emit malodors that are offensive to consumers and which exhibits improved product stability. The cellulase-containing detergent composition achieves this by incorporating selected perfume formulations into the detergent which surprisingly reduce the odor problem associated with cellulase enzymes and their feedstock. Further, the selected perfume formulations used in the instant detergent composition are less interactive with cellulase enzymes and thus cause the overall stability of the detergent composition to be surprisingly improved. The cellulase enzymes contained in the detergent composition of the invention can be both bacterial and fungal cellulase, although fungal cellulases are preferred. Numerous perfume formulations suitable for use in the detergent of the invention can be prepared from known perfume or fragrance ingredients.

As used herein, the designation "AMU" refers to atomic weight and may also be expressed as g/mole. All percentages, ratios and proportions used herein are by weight, unless otherwise specified. All documents including patents and publications cited herein are incorporated herein by reference.

In accordance with one aspect of the invention, a detergent composition containing cellulase and perfume is provided. Specifically, the detergent composition comprises: (a) a cellulase enzyme; and (b) a perfume containing at least 25% by weight of at least one fragrance material selected from the group consisting of aliphatic ketones with a molecular weight of between 200 and 350 AMU, aromatic ketones with a molecular weight of between 150 and 350 AMU, aliphatic aldehydes with a molecular weight of between 160 and 350 AMU, aromatic aldehydes with a molecular weight of between 150 and 350 AMU, condensation products of aldehydes and amines with a molecular weight between 190 and 350 AMU, aromatic and aliphatic lactones with a molecular weight between 140 and 350 AMU, aromatic and aliphatic ethers with a molecular weight between 150 and 350 AMU, aliphatic alcohols with a molecular weight between 200 and 350 AMU, aromatic and aliphatic esters with a molecular weight between 190 and 350 AMU and mixtures thereof. The perfume preferably is substantially free of halogenated fragrance materials and nitromusks. The detergent composition surprisingly exhibits decreased malodors as compared with other cellulase-containing detergents which do not include perfume formulations as defined herein.

In another embodiment of the invention, a method of laundering soiled fabrics is provided. The method comprises the step of contacting the soiled fabrics with an aqueous medium containing an effective amount of a detergent composition as described herein. Yet another embodiment of the invention is directed to a laundry bar composition suitable for handwashing soiled fabrics. Other aspects of the invention include granular as well as liquid forms of the detergent composition described herein.

Accordingly, it is an object of the invention to provide a detergent composition containing cellulase enzyme which does not have the malodor problem normally associated with cellulase-containing detergents. It is also an object of the invention to provide such a cellulase-containing detergent which has improved stability as a result of improved compatibility of celluase enzyme and the perfume in the detergent. These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In its broadest aspect, the present invention is directed to a detergent composition containing a cellulase enzyme and a perfume as defined herein, together which provide a detergent having improved odor and stability. The perfumes suitable for use in the detergent composition can be formulated from known fragrance ingredients and preferably contain at least 25%, preferably from about 25% to about 40%, and most preferably from about 40% to about 60%, by weight of at least one fragrance material selected from several categories of perfume ingredients. For purposes of enhancing environmental compatibility, the perfume is substantially free of halogenated fragrance materials and nitromusks.

Cellulase Enzyme

The cellulase enzymes used in the instant detergent composition are preferably incorporated at levels sufficient to provide up to about 5 mg by weight, more preferably about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein preferably comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.

The cellulase suitable for 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. Pat. No. 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and 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. In addition, cellulase especially suitable for use herein are disclosed in WO 92-13057 (Procter & Gamble). Most preferably, the cellulases used in the instant detergent compositions are purchased commercially from NOVO Industries A/S under the product names CAREZYME® and CELLUZYME®.

Perfume

The detergent composition preferably comprises from about 0.001% to about 5%, more preferably from about 0.01% to about 2%, and most preferably from about 0.2% to 0.7% by weight of a perfume as described herein. The formulator has the luxury of choosing from a wide variety of perfume ingredients in order to arrive at a perfume formulation within the definition stated previously. Several perfume formulations are set forth in Example I hereafter. The perfume formulations can be prepared from perfume ingredients including but not limited to: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6, 10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; 7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; isohexenyl cyclohexyl carboxaldehyde; formyl tricyclodecane; condensation products of hydroxycitronellal and methyl anthranilate, condensation products of hydroxycitronellal and indol, condensation products of phenyl acetaldehyde and indol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin; heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin; decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane; beta-naphthol methyl ether; ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.

Particularly preferred perfume materials are those that provide the largest odor improvements in finished product compositions containing cellulases. These perfumes include but are not limited to: hexyl cinnamic aidehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7tetramethyl naphthalene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta-naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane; dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]blfuran; anisaldehyde; coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenyl acetate; and tricyclodecenyl propionate.

Other perfume materials include essential oils, resinoids, and resins from a variety of sources including but not limited to orange oil, lemon oil, patchouli, Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander, lavandin and lavender. Still other perfume chemicals include phenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2-(1,1-dimethylethyl)cyclohexanol acetate, benzyl acetate, orange terpenes, eugenol, diethylphthalate.

Detersive Surfactants

Preferably, the detergent composition comprises from about 1% to about 55%, more preferably from about 15 to 40%, by weight, of a detersive surfactant. Nonlimiting examples of surfactants useful herein include the conventional C11 -C18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10 -C20 alkyl sulfates ("AS"), the C10 -C18 secondary (2,3) alkyl sulfates of the formula CH3 (CH2)x (CHOSO3 - M+)CH3 and CH3 (CH2)y (CHOSO3 -M +) CH2 CH3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10 -C18 alkyl alkoxy sulfates ("AEx S"; especially EO 1-7 ethoxy sulfates), C10 -C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10 -C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C12 -C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12 -C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6 -C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12 -C18 betaines and sulfobetaines ("sultaines"), C10 -C18 amine oxides, and the like, can also be included in the overall compositions. The C10 -C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12 -C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10 -C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12 -C18 glucamides can be used for low sudsing. C10 -C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10 -C.sub. 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.

The C10 -C18 alkyl alkoxy sulfates ("AEx S"; especially EO 1-7 ethoxy sulfates) and C12 -C18 alkyl ethoxylates ("ALE") are the most preferred for the cellulase-containing detergents described herein.

Detergency Builders

Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.

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. Liquid 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 SiO2 :Na2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS6 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-Na2 SiO5 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 NaMSix O2x+1.yH2 O 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-Na2 SiO5 (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 Nov. 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 [(zAlO2)y ].xH2 O

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. Pat. No. 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 [(AlO2)12 (SiO2)12 ].xH2 O

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 Berg, U.S. Pat. No. 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also "TMS/TDS" builders of U.S. Pat. No. 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Pat. No. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers 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, oxydisuccinic 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 aeolite 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-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 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 dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published Nov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No. 3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No. 3,723,322.

Fatty acids, e.g., C12 -C18 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 orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

Adjunct Ingredients

The compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., colorants, dyes, etc.). The following are illustrative examples of such adjunct materials.

Other Enzymes--Additional enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration. The additional enzymes to be incorporated include proteases, amylases, lipases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders as well as their potential to cause malodors during use. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases.

Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 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.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the trade names ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application 130,756, published Jan. 9, 1985); Protease B (see European Patent Application Serial No. 87303761.8, filed Apr. 28, 1987, and European Patent Application 130,756, Bott et al, published Jan. 9, 1985); and proteases made by Genencor International, Inc., according to one or more of the following patents: Caldwell et al, U.S. Pat. Nos. 5,185,258, 5,204,015 and 5,244,791.

Amylases include, for example, α-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.

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. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticurn NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladloll. The LIPOLASE enzyme derived from Hutnicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein.

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. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published Oct. 19, 1989, by O. Kirk, assigned to Novo Industries A/S.

A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Pat. No. 3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Pat. No. 4,101,457, Place et al, issued July 18, 1978, and in U.S. Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al, issued Apr. 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Typical granular or powdered detergents can be stabilized effectively by using enzyme granuletes. Enzyme stabilization techniques are disclosed and exemplified in U.S. Pat. No. 3,600,319, issued Aug. 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published Oct. 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Pat. No. 3,519,570.

Enzyme Stabilizers - The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used.) Additional stability can be provided by the presence of various other art-disclosed stabilizers, especially borate species: see Severson, U.S. Pat. No. 4,537,706. Typical detergents, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12, millimoles of calcium ion per liter of finished composition. This can vary somewhat, depending on the amount of enzyme present and its response to the calcium or magnesium ions. The level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition. Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts. A small amount of calcium ion, generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water. In solid detergent compositions the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.

It is to be understood that the foregoing levels of calcium and/or magnesium ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions can be added to the compositions to provide an additional measure of grease removal performance. Accordingly, as a general proposition the compositions herein will typically comprise from about 0.05% to about 2% by weight of a water-soluble source of calcium or magnesium ions, or both. The amount can vary, of course, with the amount and type of enzyme employed in the composition.

The compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid). Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid) can also be used in place of boric acid.

Bleaching Compounds--Bleaching Agents and Bleach Activators--The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.

Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, U.S. patent application No. 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published Feb. 20, 1985, and U.S. Pat. No. 4,412,934, Chung et al, issued Nov. 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 to Burns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Pat. No. 4,915,854, issued Apr. 10, 1990 to Mao et al, and U.S. Pat. No. 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. Pat. No. 4,634,551 for other typical bleaches and activators useful herein.

Highly preferred amido-derived bleach activators are those of the formulae:

R1 N(R5)C(O)R2 C(O)L or R1 C(O)N(R5)R2 C(O)L

wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Pat. No. 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Pat. No. 4,966,723, issued Oct. 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazin-type is: ##STR1##

Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae: ##STR2## wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 ;l to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Pat. No. 4,545,784, issued to Sanderson, Oct. 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.

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. See U.S. Pat. No. 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. Nos. 5,246,621, 5,244,594; 5,194,416; 5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include MnIV 2 (u-O)3 (1,4,7-trimethyl-1,4,7-triazacyclononane)2 (PF6)2, MnIII 2 (u-O)1 (u-OAc)2 (1,4,7-trimethyl-1,4,7-triazacyclononane)2- (ClO4)2, MnIV 4 (u-O)6 (1,4,7-triazacyclononane)4 (ClO4)4, MnIII MnIV 4 (u-O)1 (u-OAc)2- (1,4,7-trimethyl-1,4,7-triazacyclononane)2 (ClO4)3, MnIV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH3)3 (PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. Nos. 4,430,243 and 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following U.S. Pat. Nos. 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084.

As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.

Polymeric Soil Release Agent--Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. 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 washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

The polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4 -C6 alkylene or oxy C4 -C6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C1 -C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C1 -C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C1 -C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4 -C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3 S(CH2)n OCH2 CH2 O--, where M is sodium and n is an integer from 4-6 as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink.

Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1 -C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093, issued Dec. 28, 1976 to Nicol, et al.

Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C1 -C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published Apr. 22, 1987 by Kud, et al. Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975.

Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters. Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.

If utilized, soil release 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%.

Chelating Agents - The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S]isomer as described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.

Clay Soil Removal/Anti-redeposition Agents - The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1, 1986. Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published Jun. 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published Jul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744, Connor, issued Oct. 22, 1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehi, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published Dec. 15, 1982, as well as in EP 193,360, published Sept. 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.

Brightener - Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein. 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, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Pat. No. 4,790,856, issued to Wixon on Dec. 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene; 1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole. See also U.S. Pat. No. 3,646,015, issued Feb. 29, 1972 to Hamilton. Anionic brighteners are preferred herein.

Dye Transfer Inhibiting Agents - The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.

More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-Ax -P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: --NC(O)--, --C(O)O--, --S--, --O--, --N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The N-O group can be represented by the following general structures: ##STR3## wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the disclosures of which are incorporated herein by reference.) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. Compositions containing PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.

The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention are those having the structural formula: ##STR4## wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the trade name Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.

Of course, it will be appreciated that other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.

Suds Suppressors--Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front-loading European-style washing machines.

A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Pat. No. 2,954,347, issued Sept. 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18 -C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexaalkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40° C. and about 50° C., and a minimum boiling point not less than about 110° C. (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100° C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.

Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Pat. No. 3,933,672, Bartolotta et al, and in U.S. Pat. No. 4,652,392, Baginski et al, issued Mar. 24, 1987.

An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:

(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25° C.;

(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3 SiO1/2 units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to SiO2 units of from about 0.6:1 to about 1.2:1; and

(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.

In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and preferably not linear.

To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Pat. No. 4,978,471, Starch, issued Dec. 18, 1990, and 4,983,316, Starch, issued Jan. 8, 1991, 5,288,431, Huber et al., issued Feb. 22, 1994, and U.S. Pat. No. 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.

The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.

The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L 101.

Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. Pat. Nos. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6 -C16 alkyl alcohols having a C1 -C16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol+silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.

The compositions herein will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.

Fabric Softeners--Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Pat. No. 4,062,647, Storm and Nirschl, issued Dec. 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Pat. No. 4,375,416, Crisp et al, March 1, 1983 and U.S. Pat. No. 4,291,071, Harris et al, issued Sept. 22, 1981.

Other Ingredients--A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C10 -C16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The C10 -C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium salts such as MgCl2, MgSO4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.

Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.

To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D 10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13-15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 × the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photo activators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent 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., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.

The detergent compositions herein 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 about 11, preferably between about 7.5 and 10.5. Liquid dishwashing product formulations preferably have a pH between about 6.8 and about 9.0. Laundry products are typically at pH 9-11. 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.

In order to make the present invention more readily understood, reference is made to the following examples, which are intended to be illustrative only and not intended to be limiting in scope.

EXAMPLE I

This Example illustrates several perfume formulations (A-C) made in accordance with the invention for incorporation into cellulase-containing detergent compositions. The various ingredients and levels are set forth in Table I below.

              TABLE I______________________________________              (% Weight)Perfume Ingredient   A       B       C______________________________________Hexyl cinnamic aldehyde                10.0    --      5.02-methyl-3-(para-tert-butylphenyl)-                5.0     5.0     --propionaldehyde7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-                5.0     10.0    10.0tetramethyl naphthaleneBenzyl salicylate    5.0     --      --7-acetyl-1,1,3,4,4,6-hexamethyltetralin                10.0    5.0     10.0Para-(tert-butyl) cyclohexyl acetate                5.0     5.0     --Methyl dihydro jasmonate                --      5.0     --Beta-napthol methyl ether                --      0.5     --Methyl beta-naphthyl ketone                --      0.5     --2-methyl-2-(para-iso-propylphenyl)-                --      2.0     --propionaldehyde1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-                --      9.5     --hexamethyl-cyclopenta-gamma-2-benzopyraneDodecahydro-3a,6,6,9a-tetramethyl-                --      --      0.1naphtho[2,1b]furanAnisaldehyde         --      --      0.5Coumarin             --      --      5.0Cedrol               --      --      0.5Vanillin             --      --      5.0Cyclopentadecanolide 3.0     --      10.0Tricyclodecenyl acetate                --      --      2.0Labdanum resin       --      --      2.0Tricyclodecenyl propionate                --      --      2.0Phenyl ethyl alcohol 20.0    10.0    27.9Terpineol            10.0    5.0     --Linalool             10.0    10.0    5.0Linalyl acetate      5.0     --      5.0Geraniol             5.0     --      --Nerol                --      5.0     --2-(1,1-dimethylethyl)-cyclohexanol                5.0     --      --acetateOrange oil, cold pressed                --      5.0     --Benzyl acetate       2.0     2.0     --Orange terpenes      --      10.0    --Eugenol              --      1.0     --Diethylphthalate     --      9.5     --Lemon oil, cold pressed                --      --      10.0Total                100.0   100.0   100.0______________________________________
EXAMPLE II

This Example illustrates heavy duty granular detergents containing cellulase and the perfume formulations described in Example I. The ingredients in the typical granular detergents exemplified herein are set forth in Table II below.

              TABLE II______________________________________              (% weight)Base Formula         1       2       3______________________________________C12-13 linear alkylbenzene sulfonate                9.0     9.0     9.0(Na)C14-15 alkyl ethoxy (EO = 0.6) sulfate                1.6     1.6     1.6(Na)C12-18 alkyl sulfate                5.7     5.7     5.7Polyacrylate (MW = 4500)                3.2     3.2     3.2Aluminosilicate      26.3    26.3    26.3Sodium silicate      0.6     0.6     0.6Sodium carbonate     27.9    27.9    27.9Sodium sulfate       8.9     8.9     8.9Optical Brightener   0.2     0.2     0.2Polyethylene glycol (MW = 4000)                1.7     1.7     1.7AdmixPerborate            1.0     1.0     1.0Cellulase1 (5 CEVU/g)                0.6     0.6     0.6Protease2 (.0062 AU/g)                0.3     0.3     0.3Lipase3 (206 LU/l)                0.2     0.2     0.2Nonionic             3.0     3.0     3.0Spray-onPerfume A            0.4     --      --Perfume B            --      0.4     --Perfume C            --      --      0.4Misc. (water and other minors)                9.4     9.4     9.4                100.0   100.0   100.0______________________________________ 1 CAREZYME ® commercially sold by NOVO Industries A/S. 2 Protease enzyme made by Genenecor International Inc. according to Caldwell et al, U.S. Pat. No. 5,185,258. 3 LIPOLASE ® commercially sold by NOVO Industries A/S.

The base formula illustrated herein can be made via a variety of known processes including conventional spray drying techniques or agglomeration in apparatus such as powder mixers and fluid beds commercially available from Lldige and Aeromatic, respectively. Agglomeration is especially suitable for preparing modern compact granular detergents and entails initially forming a surfactant paste using standard mixers, after which the paste is agglomerated into agglomerates and dried. Such processing techniques are well known in the art. The enzymes such as cellulase are dry mixed into the base formula and the perfumes used herein are subsequently sprayed onto the base formula so as to form the final granular detergent compositions exemplified herein.

EXAMPLE III

This Example illustrates liquid laundry detergent compositions containing cellulase and the perfumes described in Example I. Table III illustrates the various ingredients of the liquid laundry detergent.

              TABLE III______________________________________              (% weight)Component            4       5       6______________________________________C14-15 alkyl ethoxy (EO = 2.25) sulfate                18.0    18.0    18.0N--Methyl N-1-Deoxyglucityl                5.0     5.0     5.0cocoamideNonionic1       2.0     2.0     2.0Citric Acid          3.0     3.0     3.0Oleic acid           2.0     2.0     2.0Ethanol              3.2     3.2     3.2Boric acid           3.5     3.5     3.5Monoethanolamine     1.1     1.1     1.11,2 Propanediol      8.0     8.0     8.0Sodium cumene sulfate                3.0     3.0     3.0Sodium hydroxide     3.8     3.8     3.8Polyacrylate         1.2     1.2     1.2Protease2 (.0145 AU/g)                0.3     0.3     0.3Lipase3 (200 LU/l)                0.3     0.3     0.3Cellulase4 (7.5 CEVU)                0.3     0.3     0.3Perfume A            0.3     --      --Perfume B            --      0.3     --Perfume C            --      --      0.3Misc. (water, brighteners, etc.)                45.0    45.0    45.0                100.0   100.0   100.0______________________________________ 1 Neodol 239 commercially available from Shell Oil Company 2 Protease enzyme made by Genencor International, Inc. according to Caldwell et al, U.S. Pat. No. 5,185,258. 3 LIPOLASE ® commercially available from NOVO Industries A/S 4 CAREZYME ® commercially available from NOVO Industries A/S
EXAMPLE IV

This Example illustrates laundry bars containing cellulase and a perfume in accordance with the invention. The laundry bars exemplified herein are prepared by standard extrusion processes so as to be suitable for handwashing soiled fabrics. Table IV sets forth the various ingredients in the laundry bars.

              TABLE IV______________________________________              (% weight)Component            7       8       9______________________________________C12-13 linear alkylbenzene sulfonate                10.0    10.0    10.0(Na)C14-15 alkyl sulfate (Na)                6.0     6.0     6.0C14-15 alkyl ethoxy (EO = 0.6) sulfate                3.0     3.0     3.0(Na)Sodium tripolyphosphate                7.0     7.0     7.0Sodium pyrophosphate 7.0     7.0     7.0Sodium carbonate     25.0    25.0    25.0Aluminosilicate      5.0     5.0     5.0Carboxymethyl cellulose                0.2     0.2     0.2Polyacrylate (MW = 1400)                0.2     0.2     0.2Brightener           0.2     0.2     0.2Protease1       0.3     0.3     0.3Cellulase2      0.3     0.3     0.3Lipase3         0.3     0.3     0.3Perfume A            0.4     --      --Perfume B            --      0.4     --Perfume C            --      --      0.4Misc. (water, fillers and other minors)                35.1    35.1    35.1                100.0   100.0   100.0______________________________________ 1 Protease enzyme made by Genencor International, Inc. according to Caldwell et al, U.S. Pat. No. 5,105,258. 2 CAREZYME ®  commercially sold by NOVO Industries A/S 3 LIPOLASE ® commercially sold by NOVO Industries A/S

Having thus described the invention in detail, it will be clear to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US4435307 *Apr 23, 1981Mar 6, 1984Novo Industri A/SDetergent cellulase
US4515705 *Mar 20, 1984May 7, 1985The Procter & Gamble CompanyCompositions containing odor purified proteolytic enzymes and perfumes
US4661289 *Aug 27, 1985Apr 28, 1987Lever Brothers CompanyDetergent compositions
US4973422 *Dec 15, 1989Nov 27, 1990The Procter & Gamble CompanyPerfume particles for use in cleaning and conditioning compositions
US5120463 *Apr 15, 1991Jun 9, 1992Genencor International, Inc.Degradation resistant detergent compositions based on cellulase enzymes
US5156761 *Mar 7, 1991Oct 20, 1992Dorrit AaslyngMethod of stabilizing an enzymatic liquid detergent composition
US5232851 *Oct 16, 1990Aug 3, 1993Springs Industries, Inc.Methods for treating non-dyed and non-finished cotton woven fabric with cellulase to improve appearance and feel characteristics
US5248434 *Apr 20, 1992Sep 28, 1993The Proctor & Gamble CompanyLiquid or gel bleaching composition containing amidoperoxyacid bleach and perfume
US5290474 *May 30, 1991Mar 1, 1994Genencor International, Inc.Detergent composition for treating cotton-containing fabrics containing a surfactant and a cellulase composition containing endolucanase III from trichoderma ssp
US5314637 *Mar 11, 1993May 24, 1994Showa Denko K.K.Detergent comprising isolated cellulase from bacillus ferm bp-3431 or a mutant strain thereof, surfactant and builder
EP0430315A2 *Sep 20, 1990Jun 5, 1991Unilever N.V.Perfumed laundry detergents
GB1368599A * Title not available
GB2075028A * Title not available
GB2095275A * Title not available
JPH02178397A * Title not available
WO1993004158A1 *Aug 17, 1992Mar 4, 1993Procter & GambleDetergent compositions containing lipase and terpene
WO1993011215A1 *Dec 1, 1992Jun 10, 1993Procter & GambleLiquid laundry detergents with citric acid, cellulase, and boric-diol complex to inhibit proteolytic enzyme
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5536438 *Nov 19, 1993Jul 16, 1996The Procter & Gamble CompanyMulti-purpose liquid cleaning composition comprising nonionic surfactants of different HLB values
US5565420 *Jun 6, 1995Oct 15, 1996The Procter & Gamble CompanyGranular detergent composition containing admixed fatty alcohols for improved cold water solubility
US5686376 *Nov 21, 1996Nov 11, 1997The Procter & Gamble CompanyChelating agents for improved color fidelity
US5759981 *Jun 12, 1995Jun 2, 1998The Procter & Gamble CompanyProcess for treating textiles and compositions therefor
US5762647 *Sep 16, 1996Jun 9, 1998The Procter & Gamble CompanyMethod of laundering with a low sudsing granular detergent composition containing optimally selected levels of a foam control agent bleach activator/peroxygen bleaching agent system and enzyme
US5776878 *Jan 11, 1995Jul 7, 1998The Procter & Gamble CompanyLiquid detergent compositions containing brighteners and polymers for preventing fabric spotting
US6017865 *Nov 22, 1996Jan 25, 2000The Procter & Gamble CompanyPerfume laundry detergent compositions which comprise a hydrophobic bleaching system
US6060441 *Apr 10, 1997May 9, 2000Henkel CorporationCleaning compositions having enhanced enzyme activity
US6228821Oct 25, 1999May 8, 2001Amway CorporationCleaning composition having enhanced fragrance and method of enhancing fragrance
US6296670 *Jun 26, 1997Oct 2, 2001The Procter & Gamble CompanyChelating agents for improved color fidelity
US6413920Jul 12, 1999Jul 2, 2002Procter & Gamble CompanyAmine reaction compounds comprising one or more active ingredient
US6451751Jul 12, 1999Sep 17, 2002The Procter & Gamble CompanyProcess for producing particles of amine reaction product
US6511948Jul 12, 1999Jan 28, 2003The Procter & Gamble CompanyAmine reaction compounds comprising one or more active ingredient
US6566312May 29, 2002May 20, 2003Procter & Gamble CompanyAmine reaction compounds comprising one or more active ingredient
US6699823Dec 5, 2002Mar 2, 2004Procter & Gamble CompanyAmine reaction compounds comprising one or more active ingredient
US6790815Mar 31, 2003Sep 14, 2004Procter & Gamble CompanyAmine reaction compounds comprising one or more active ingredient
US7012047Nov 18, 2003Mar 14, 2006Procter & Gamble CompanyAmine reaction compounds comprising one or more active ingredient
US7261742Jul 24, 2006Aug 28, 2007S.C. Johnson & Son, Inc.Method of deodorizing a textile
US7407515Apr 2, 2007Aug 5, 2008S.C. Johnson & Son, Inc.Method of deodorizing a textile
US7407922Oct 13, 2005Aug 5, 2008S.C. Johnson & Son, Inc.Deodorizing compositions
EP0971021A1 *Feb 15, 1999Jan 12, 2000THE PROCTER &amp; GAMBLE COMPANYProcess for producing particles of amine reaction product
EP0971024A1 *Oct 28, 1998Jan 12, 2000THE PROCTER &amp; GAMBLE COMPANYLaundry and cleaning compositions
EP0971025A1 *Oct 28, 1998Jan 12, 2000THE PROCTER &amp; GAMBLE COMPANYAmine reaction compounds comprising one or more active ingredient
EP0971026A1 *Feb 11, 1999Jan 12, 2000THE PROCTER &amp; GAMBLE COMPANYLaundry and cleaning compositions
EP1067116A1 *Apr 12, 2000Jan 10, 2001The Procter &amp; Gamble CompanyProcess for the production of imines
EP1067117A1 *Jul 9, 1999Jan 10, 2001THE PROCTER &amp; GAMBLE COMPANYProcess for making imine compounds
WO1996012781A1 *Oct 13, 1995May 2, 1996Jonathan Richard ClareDetergent composition
WO1996021718A1 *Jan 5, 1996Jul 18, 1996Carolyn Jayne BrownDetergent composition comprising zeolite map and amylase enzymes
WO1997007193A1 *Aug 9, 1996Feb 27, 1997Mcritchie Allan CampbellPerfumed bleaching detergent compositions
WO1997008283A1 *Aug 22, 1996Mar 6, 1997Procter & GambleDetergent composition with bleach system stabilized by enzymes
WO1997012953A1 *Sep 13, 1996Apr 10, 1997Jonathan Richard ClareDetergent composition containing particulate zeolite builder and lubricant therefor
WO1998008926A1 *Aug 26, 1996Mar 5, 1998Baeck Andre CesarCellulase activity control by a terminator
WO1998045396A1 *Apr 9, 1998Oct 15, 1998Henkel CorpCleaning compositions having enhanced enzyme activity
WO2000002981A2 *Jul 12, 1999Jan 20, 2000Procter & GambleLaundry and cleaning compositions
WO2000002982A2 *Jul 12, 1999Jan 20, 2000Procter & GambleLaundry and cleaning compositions
WO2000002986A2 *Jul 12, 1999Jan 20, 2000Procter & GambleProcess for producing particles of amine reaction product
WO2000002991A1 *Jul 12, 1999Jan 20, 2000Bettiol Jean Luc PhilippeAmine reaction compounds comprising one or more active ingredient
WO2001004084A1 *Jun 23, 2000Jan 18, 2001Besselievre RichardProcess for making amine compounds
Classifications
U.S. Classification510/101, 510/105, 510/320, 510/106, 510/444, 510/298, 510/102, 510/392, 510/103, 510/393
International ClassificationC11D3/50, C11D3/386, C11D3/60
Cooperative ClassificationC11D3/50, C11D3/38645
European ClassificationC11D3/386F, C11D3/50
Legal Events
DateCodeEventDescription
Feb 3, 1995ASAssignment
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:COSTA, JILL B.;SHOWELL, MICHAEL S.;REEL/FRAME:007323/0984
Owner name: PROCTER & GAMBLE COMPANY, THE, OHIO
Effective date: 19940427