GB2296261A - Odor control fabric treatment compositions - Google Patents

Abstract

Fabric treatment compositions comprise mesoporous molecular sieves for odor control. Preferred are mesoporous molecular sieves prepared by processes which utilize liquid-crystal templating with surfactant materials.

Description

ODOR CONTROL MESOPOROUS MOLECULAR SIEVES IN LAUNDRY DETERGENT AND FABRIC TREATMENT COMPOSITIONS FIELD OF THE INVENTION The present invention relates to laundry detergent and fabric treatment compositions comprising mesoporous molecular sieves for odor control on fabrics.

BACKGROUND OF THE INVENTION The suppression or elimination of odors, particularly undesirable odors, has been the objective of countless investigations. Malodors have their genesis in many forms but those that are of most consequence to human beings are those involving occasional or repeated daily exposure. As a consequence of normal daily activity, people and their clothing are exposed to a variety of malodors, some of which are produced by the wearer, as in the case of perspiration, and some are environmental malodors (e.g. cigarette smoke).

Cultural and aesthetic standards have influenced the permissible level of human and environmental malodors and control of these odors has been the focus of investigation for many centuries. In general, these investigations have been focused on either of two approaches, namely (a) odor masking, in which a substance of strong yet relatively pleasant odor is introduced into the proximity of a less pleasant odor source with the intent of overburdening the olfactory receptors with the dominant pleasant odor, or (b) sequestering the undesired odorous substance in a non-volatile form either by chemical reaction, adsorption or absorption on a sorbent material exhibiting a sorptive preference for the odorous substance.

Odor masking, although effective in the short term, has certain limitations.

First, masking does not remove or eliminate the source of the malodor. Secondly, when scents and perfumes are used to overcome malodors, the user must make sure an effective and constant level of masking agent is present to avoid too low a level of masking agent that may not be sufficient to cover-up the malodor. In turn, too high a level of masking agent may itself produce an undesirable effect. The premature depletion of the masking agent can be an additional concern.

Sequestration has thus become the method of choice for elimination and control of both human and environmental malodors. The more effective approach has been to sequester the undesired malodor primarily by adsorption.

By far the most commonly employed of the solid adsorbents is activated charcoal or active carbon, although silica gel, activated alumina, kieselguhr, Fullers earth and other clay minerals and zeolites, alone or in combination, have also been proposed as odor "adsorbents". In US Pat. No. 4,437,429, the use of a hydrated zeolite in admixture with clay is proposed as being particularly usefUl for the control of odors from pet litter. Though it is observed that the use of zeolites by themselves as litter material has generally been unsuccessful due to their poor water adsorption properties as compared with clays.

The best remedy for fabric malodor is the effective sequestering of malodorous molecules as they are either formed or come into contact with clothing.

The delivery of an effective, widely applicable malodor control agent via the laundering process is one object of the present invention.

The desire to provide a laundry detergent that provides laundered fabrics with malodor control that does not involve masking the malodors with perfumes, led to the investigation of adsorbents, chelants and other odor control agents. Activated charcoal, one of the most efficient adsorptive materials, along with finely divided aluminosilicate adsorbents and clays, have been excluded from use because they are either not compatible with fabric color (i.e. black charcoal on white clothing) or they are not compatible with the aqueous delivery system normally associated with laundry detergents.

Aluminosilicates in the form of microporous zeolites have long been of value in laundry detergent compositions as builders. They serve in general as ion exchange agents whose primary function is to remove calcium and magnesium ions from the laundry wash liquor and replace them with sodium, potassium or other suitable cations that do not decrease the surface activity of laundry detergent surfactants.

Thus zeolite ion exchange capacity can be tailored by varying the composition of the aluminosilicate framework. By modifying the ratio of silicon to aluminum atoms in the tetrahedral lattice of the zeolite, the number of cations that can be carried into the wash liquor can be controlled. Increasing the ratio of aluminum atoms in the tetrahedral array has the effect of introducing more anionic sites into the zeolite structure which are then made electronically neutral by the desired counter ions such as sodium, potassium, ammonium, etc. The ability to manipulate and control this and other properties of aluminosilicate zeolites1 for example, frame work composition and crystal structure, is key to their wide flinctionality and their high utility in chemical processes.

Typically, builder zeolites have pore sizes on the order of 2-7 angstroms which readily accommodate the sodium, potassium, calcium and magnesium anions that are involved in the ion exchange process of the laundry liquor. This "builder" role of zeolites is fundamental to the functioning of some synthetic laundering compositions. Additionally, it has long been known that these zeolite builders are deposited onto fabric during the wash cycle, usually residing among the interstices of the fabric weave.

Adsorption, and hence the sequestering, of odors such as ammonia as described in US Pat. No. 5,013,335 are accomplished by zeolitic material where selected synthesis and calcination affords porous molecular sieves with a pore size large enough to accommodate ammonia molecules. However, when applied to adsorption of molecules typically responsible for malodor, these common microporous zeolites fail in several ways. The surface of high aluminum containing zeolites have an abundance of bound cations and together with the associated "water of hydration" produce a hydrophilic surface barrier not compatible with the adsorption mechanism associated with the diffusion of larger, non-polar, non-charged organic species at the solid/air interface.Additionally, the pore size of common microporous zeolites is too small to allow interstitial permeation and adsorption of molecules having the size range of from 8 to 12 carbon atoms.

It has now been suprisingly discovered that laundry detergent and fabric treatment compositions comprising mesoporous molecular sieves of the type designated as M41 S, more specifically those sieves of the subclass designated !tCM- 41, which are formed by liquid crystal templating, effectively control malodor on fabric. These mesoporous molecular sieves may be delivered by a detergent composition during a laundry wash process, or may be directly applied to fabncs (e.g., by spraying on or dusting the fabric in need of malodor control).

BACKGROUND ART Aluminosilicate zeolites have been described as malodor control agents such as those described in US 5,254,337; US 5,184,630; 5,120,693; US 5,084,427 LS 5,013,335; US 4,826,497; US 4,795,482; US 4,437,429; WO 93/17661 and ip 6397159.

SUMMARY OF THE INVENTION The present invention relates to laundry detergent compositions comprising mesoporous molecular sieves for control of malodorous compounds that come into contact with clothing and other fabric in the course of normal usage. The mesoporous molecular sieves useful in the present invention have pore sizes from about 15 to about 100 angstroms, including members of the family of mesoporous molecular sieves designated by the Mobil Oil Corporation as M4 15. Preferred are mesoporous molecular sieves of the type designated as MCM-4 1 developed by the Mobil Oil Company, which provide enhanced odor control and laundry liquor compatibility according to the present invention.

The compositions of the present invention when practiced in the area of laundry detergent compositions will optionally comprise, detersive surfactants, builders, buffers, bleaching compounds, bleach activators, chelating agents, antiredeposition agents, dispersents, brightners, suds suppressers, hydrotropes, soil release agents, fabric softeners, filler salts, and mixtures thereof although this list is not meant to be inclusive or exclusionary. The present invention compositions therefore preferably comprises from about 1% to about 99% of such adjunct ingredients.

The mesoporous molecular sieves of the present invention have a pore size of from about 15 angstroms to about 100 angstroms and have a silicon atom to aluminum atom ratio > 50: 1, preferably > 200: 1, more preferably > 300:1. The silicon atom to aluminum atom ratio is defined as the number of atoms themselves; thus, for example, the formulator would employ a ratio of 100 silicate moieties to 1 aluminate moiety to provide a silicon atom to aluminum atom ratio of 50:1 The laundry detergent and fabric treatment embodiments of the present invention can comprise mesoporous molecular sieves of more than one particle size, that is, the same composition can comprise a range of particle sizes from 15 to 100 angstroms in any percentage or ratio the formulator prefers.

The mesoporous molecular sieves of the present invention may be calcined or uncalcined. The particle size of the mesoporous molecular sieve can have a particle size from about 1 micron to about 150 micron, but the particle size can be adjusted to any size the formulator prefers.

The present invention also relates to a method of controlling fabric malodor by applying to said fabric a mesoporous molecular sieve. Subsequent exposure of said fabric to malodors, whether the malodors are created either by the user (i.e.

perspiration) or the malodors are environmental (i.e. cigarette smoke), results in a decreased level of malodor present on said fabric after the source of malodor has been removed. This method of the present invention to control malodor on fabric may involve either contacting said fabric with a laundry detergent or a fabric treatment composition comprising mesoporous molecular sieves described further herein.

All percentages, ratios and proportions are by weight, unless otherwise specified. All documents cited are incorporated herein by reference in their entirety.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compositions and methods for controlling malodor on fabric. The malodor control can be delivered either in detersive laundry compositions comprising mesoporous molecular sieves, detersive surfactants and adjunct ingredients or, alternatively, as a fabric treatment composition. The fabric treatment composition of the present invention comprises mesoporous molecular sieves, suitable carrier and, optionally, perfumes.

Mesoporous Molecular Sieves: Recently, mesoporous molecular sieves (designated as M41S) have been described by the Mobil Oil Company. These materials possess a regular array of uniform, unidimensional mesopores, which can be systematically varied in size from about 15 to about 100 angstroms. They are described as bridging the gap between microporous (zeolites) and macroporous materials (e.g., amorphous aluminosilicates). These characteristics together with their high surface areas (up to 1000 m2/g) and their distinct adsorption properties (pore condensation without hysteresis) open up new potential applications.

As used herein, the term "mesoporous molecular sieves" means sieve materials characterized by possessing regular arrays of uniform channels of dimensions within the range of from about 15 angstroms to about 100 angstroms.

The description and preparation of mesoporous molecular sieves are known, having been described, for example, in: Beck, J.S., et al., J. Am. Chem. Soc., 1992, 114, pg.

10834-10843; Kresge, C.T., et al., Nature, 359, pg. 710-12, (1992); Beck, J.S., et al., Chem. Mater., 6, (1994), pg. 1816-21; Schmidt, R., et al., J. Chem. Soc., Chem.

Commun., (1994), pg. 1493-94; and Chen, C.-Y., et al., MicroporousMater., 2(1), pg. 17-26 (1993); US Patent No. 5,264,203, Beck et al., issued November 23, 1993; US Patent No. 5,250,282, Kresge et al., issued October 5, 1993; US Patent 5,057,296, Beck et al.; all incorporated herein by reference in their entirety.

Preferred are mesoporous molecular sieves prepared by known processes which utilize liquid-crystal templating with surfactant materials, as described, for example, in US Patent No. 5,102,643, Kresge et al., issued April 7, 1992; US Patent No. 5,098,684, Kresge et al., issued March 24, 1992; and US Patent No. 5,108,725, Beck et al.; the disclosures of all these patents being incorporated herein by reference in their entirety, as well as in certain of the above-incorporated references.

Most preferred are mesoporous molecular sieves having regular hexegonal array of uniform channels, for example the MCM41 mesoporous molecular sieves developed by Mobil. Such materials are known and are described in further detail in the above-incorporated references.

Further preferred mesoporous molecular sieves useful herein have a pore size of from about 15 to about 60 angstroms, more preferably from about 25 to about 60 angstroms, and most preferably from about 30 to about 50 angstroms. The preferred mesoporous molecular sieves of the present invention fUrther have a particle size from about 1 micron to about 150 micron, more preferably from about 10 micron to about 150 micron, and most preferably from about 20 micron to about 120 micron.

However, the material may be reduced in size by grinding if necessary by techniques well known in the art.

The ratio of silicon to aluminum atoms can be varied, allowing the formulator to not only choose the pore size of the mesopourous molecular sieve, but also the inherent charge density, and hence the hydrophobicity of the mesoporous molecular sieves prepared. The ability to vary the pore size allows the formulator to produce mesoporous molecular sieves of a specific pore size ranging from 15 to 100 angstroms or to optionally formulate an admixture of varying pore sizes to target a specific malodor species or a range of malodorous molecules.

The preferred materials have a highly hydrophobic character and low charge density. For example, the preferred mesoporous molecular sieve of the present invention will have a sorptive capacity for water at 250 C and 4.6 torr of less than 10 per cent. In one embodiment, the ratio of silicon atoms to aluminum atoms in the final mesoporous molecular sieve after calcination is > 200:1. Other embodiments of the present invention vary the ratio of silicon atoms to aluminum atoms in the final mesoporous molecular sieve after calcination from ratios of about 50:1 to greater than about 300:1 depending on the desired degree of charge density or composition of the crystalline lattice framework desired by the formulator. However, uncalcined mesoporous molecular sieves may be used.

Additionally, these sieves are readily held on the surface of (and fit into the interstices of) or otherwise are suitably retained on synthetic, blended synthetic and natural fabrics. A preferred embodiment employs a liquid crystalline surfactant as the organic templating material that is structurally similar to or closely mimics the aqueous solution confirmation of detersive surfactants or other laundry detergent adjunct ingredients, thereby producing a mesoporous molecular sieve that provides for, after appropriate removal of the organic templating agent, the adsorption of malodorous compounds when the mesoporous molecular sieve is in contact with the fabric.

The mesoporous molecular sieves of the present invention, once placed in the presence of an aqueous detersive surfactant, for example, when a fabric containing the molecular sieves of the present invention is laundered, exchange of the adsorbed malodorous materials into the laundry wash liquor occurs and the sieves are thereby re-generated. The mesoporous molecular sieves of the present invention, when hydrated by water, such as occurs in the laundering process, may be removed from the fabric by the mechanical action of the washing process but a fraction will remain on the fabric.

Thus, the mesoporous molecular sieves may posess the ability to re-generate both while on the fabric or in the laundry liquor, resulting in part from their resistance to structural deformation during the changing pH conditions of the laundry wash liquor. For example, the molecular sieves of the present invention are as stable at pH 11, which may occur at the outset of the wash cycle, as they are stable at pH 7.3, which typically occurs at the final rinse.

The fabric treatment embodiment of the present invention comprise mesoporous molecular sieves, suitable carrier and optionally perfUmes. Examples of suitable carriers are liquids such as water, methanol, ethanol, n-propanol or isopropanol, or a solid such as talc, or other inert filler salts as described herein. The mesoporous molecular sieves may be delivered by gaseous propellant in the form of a mist or aerosol, whether as a liquid or dry. This allows for direct application to the fabric (e.g., clothing, furniture fabrics, rugs) independent of a laundering process.

When the dry carrier embodiment of the present invention is applied as a fabric treatment, the adjunct ingredients will normally be inert filler salts that will serve as a desiccant to aid in removing moisture from the surrounding fabric, thereby allowing the malodor to partition more freely between the solid phase present (i.e.

the fabric surface and the sieve surface) and the gas phase.

The mesoporous molecular sieves of the present invention can also be delivered to the fabric by liquid applicator. Liquid sprays and roll-on devices are especially useful for targeting certain areas of clothing such as the under-arm or back where a person normally accumulates, through perspiration, most self-generated malodor. The carrier for such applications are compatible with the fabric and the sieves, and allow for clean non-odorous delivery. The suitable carriers of the present invention are chosen so as not to fill or otherwise occlude the pore openings and are therefore are preferably volatile short chained (preferably less than three carbon atom) solvents or water. Water, isopropanol, methanol, as well as other short chained polar liquids are especially suitable.

Perfumes are a preferred adjunct material for the fabric treatment embodiment of the present invention. Suitable perfumes are especially those with a low octanoMwater partition co-efficienct, logP < 2.0, as defined in "Theory & Practice of Industrial Phannacy", Lachman, L., et al., pg. 188-189, Lea & Febiger Pub., 3rd ed., 1986.

For the successful elimination of odors it is essential to effectively isolate the source molecules to a level beneath their detection threshold, which in almost all instances is an extremely low concentration level. For example, many mercaptans can be detected by the human olfactory system at a concentration level of 4.0 x 10-8 mg/liter of air. Since an ordinary "sniff' involves a quantity of ambient atmosphere of about 50 cc., it becomes apparent that a total amount of such a mercaptan which can be detected by the human sense of smell is only about 2.0 x 10-9 mg. Quantities this small exceed the analytical capability of essentially all types of test apparatus including the gas chromatograph, therefore human sensory evaluation is the best tool for determination of the presence of malodor.

Adiunct Inaredients: In addition to the mesoporous molecular sieves, the compositions of the present invention may include detersive surfactants, a suitable carrier, and/or other adjunct ingredients. The preferred adjunct ingredients also optionally comprise builders, buffers, bleaching compounds, bleach activators, chelating agents, antiredeposition agents, dispersents, brightners, suds suppressers, hydrotropes, soil release agents, fabric softeners, enzymes, enzyme stabilizers, perfumes, pigments, dyes, dye transfer inhibitors, filler salts and mixtures thereof.

Detersive Surfactants - Nonlimiting examples of surfactants useful herein typically at levels from about 1% to about 55%, by weight, include the conventional C"-C,g alkyl benzene sulfonates ("LAS") and primary, branched-chain and random Cl0-C20 alkyl sulfates ("AS"), the Cl0-Clg secondary (2,3) alkyl sulfates of the formula CH3(CH2)X(CHOSO3 M ) CH3 and CH3 (CH2)y(CHOSO3 M ) CIt,('lt, where x and (y+ I ) 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 C1o-Clg alkyl alkoxy sulfates ("AEXS";; especially EO 1-7 ethoxy sulfates), C1o-Cls alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the Cl0-Clg alkyl polyglycosides and their corresponding sulfated polyglycosides, and C 12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the Cl2-Clg alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6 C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Cl2-Cl8 betaines and sulfobetaines ("sultaines"), Cl0-Cl8 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 Cl2-Cl8 Nmethylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cl0-Cl8 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl Cl2-Cl8 glucamides can be used for low sudsing. Cl0-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain CtO-C,6 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.

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 metaphosphates), 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:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2SiO5 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 NaMSixO2x+ yH2O 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-1 1, as the alpha, beta and gamma forms. As noted above, the delta-Na2SiOs (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: MZ(zAlo2)y] xH20 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available.

These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 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: Nal2[(AI02)l2(Sio2)l2] xH2o 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.

Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 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.

Patents 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, 5trihydroxy 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 thereo Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially usefUl in such compositions and combinations.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.

Patent 4,566,984, Bush, issued January 28, 1986. UsefUl succinic acid builders include the Cs-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, 2dodecenylsuccinate (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 November 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 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-l hydroxy-1, l-diphosphonate and other known phosphonates (see, for example, U.S.

Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

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-4oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.

Patent Application 740,446, Bums et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Bums 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. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 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. 4,634,551 for other typical bleaches and activators useful herein.

Highly preferred amido-derived bleach activators are those of the fonnulae: RIN(R5)C(O)R2C(O)L or RlC(O)N(R5)R2C(O)L wherein Rl 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 ofthe nucleophilic attack on the bleach activator bv the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators ofthe above formulae include (s octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul- fonate, (6.decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 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. Pateni 4,966,723; issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazin-type is:

Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:

wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 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. Patent 4,545,784, issued to Sanderson, October 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. Patent 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. 5,246,621, U.S. Pat.

5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub.

Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include Mn'V2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mn1112(u-O)1 (u-OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2(ClO4)2, MngV4(u- 0)6(1,4,7-triazacyclononane)4(CI04)4, MnlllMnlV4(u-O)l(u-OAc)2 (1,4,7-trimethyl- 1,4,7-triazacyclononane)2(CIO4)3, MnlV(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. 4,430,243 and U.S. Pat. 5,114,611.The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 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.

Cheating 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, polyiunctionally-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. Patent 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. Patent 4,704,233, November 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.

Clav 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.

Patent 4,597,898, VanderMeer, issued July 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 June 27, 1984.

Other clay soil removaüantiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polvmeric 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), fimaric 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 Diehl, U.S. Patent 3,308,067, issued march 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. Watersoluble 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 December 15, 1982, as well as in EP 193,360, published September 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 acrylicimaleic/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, S- 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. Patent 4,790,856, issued to Wixon on December 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 ofthese brighteners include 4-methyl-7-diethyl- amino coumarin; 1, 2-bis(-venzimidazol-2yl)ethylene; 1,3 -diphenyl-phrazolines; 2,S-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. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.

Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions ofthe present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-stvle 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, Klrk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7. pates 430447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of panicular interest encompasses monocarboxylic fatty acid and soluble salts therein. Sce U S.

Patent 2,954,347, issued September 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 ClS-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines 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 I 100C (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. Patent 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. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Patent 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. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 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)3SiOI,2 units of SiO2 units in a ratio of from (CH3)3 Six"2 units and to SiO2 units of from about 0.6:1 to about 1.2:1; and (iii) from about I 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 polyethylenepolypropylene 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. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents 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 glycoMpolypropylene 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 glycoUpolypropylene 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 L101.

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. 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 2butyl 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.

Polvmeric 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) Cl-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form ofC1-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 Ct-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 MO3S(CH2),,OCH2CH2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 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 Cl-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 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., Cl-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethslene oxide backbones. See European Patent Application 0 219 048, published Apnl 22, 1987 by Kud, et al. Commercially available soil release agents ofthis 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. Patent 3,959,230 to Hays, issued May 25, 1976 and U S Patent 3,893,929 to Basadur issued July 8, 1975.

Another preferred polymeric soil release agent is a polyester with repeal 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. Patent 4,702,857, issued October 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. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S.

Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic endcapped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 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-1,2propylene 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%.

Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 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. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S.

Patent 4,291,071, Harris et al, issued September 22, 1981.

Enzvmes - 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 enzymes to be incorporated include proteases, amylases, lipases, cellulases, 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 and so on.In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and final cellulases.

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 tradenames 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 January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).

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

and TERMAMYL, Novo Industries.

The cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses final cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungous 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. CAREZYIE (Novo) is especially useful.

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 S3,20487, laid open to public inspection on February 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. lipolyticum 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 gladioli. The LIPOLASE enzyme derived from Humicola 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 October 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. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S.

Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.

Enzvme 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.

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.

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 ofthe 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--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, pyrrolidlne, piperidine and derivatives thereof.

The N-O group can be represented by the following general structures

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 useflil in the present invention are those having the structural formula:

wherein R, 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, R, 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 tradename 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, R, is anilino, R2 is N-2-hydroxyethyl-N-2methylamino 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 tradename 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 tradename 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 ofthe 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.

Malodor Control Testing Malodor control effectiveness testing is conducted against three commonly encountered environmental malodors: cigarette smoke, fried cooking odor and mildew odor. Expert panelists evaluate the relative malodor control performance of various mesoporous molecular sieves against a control sample. Testing is conducted as follows.

Prior to testing a bundle of 100% cotton 2T4T shirts are stripped by washing them twice in 99 gms of a perfume free laundry detergent (e.g., Tide-FreeQ sold by the Procter & Gamble Co.) and then running them through four clear rinses, all in water that is about 950 F. The shirts are machine dried at the cotton setting for 40 min. with a ten minute cool-down. Once the shirts are determined to be odor free, they are ready for use in testing and some are retained for use as test controls.

Each sample T-shirt is dosed with 110 gm of an aqueous solution containing 1 % of the mesoporous molecular sieve (MMS) to be tested, resulting in approximately 20 mg of MMS per gm of fabric. All samples are prepared in triplicate. Once the MMS to be evaluated is applied, the shirts are hang-dried for 2 hrs. The treated T-shirts and controls are then exposed to the following malodor treatments then evaluated by expert panelist.

(a) Ciaarette Smoke Test.

A modified 55 gal. drum, with lines attached to the sides for the purpose of hanging the test T shirts, is used for as a smoke pot. A filtered cigarette is lit and placed into ajar that is placed at the bottom of the drum. The drum is subsequently covered. After two minutes remove the cigarette and hang the test shirts and the control shirts in the drum then re-cover to retain the smoke. After 20 min. remove the shirts and immediately evaluate for malodor control.

(b) Cooking Oil-Test: A 30 gal galvanized trash can is modified by drilling a hole into the side for the purpose of passing through the electrical power cord of a frying skillet. The can is further modified so that the test shirts can be safely suspended within the can while sealed. Approximately 200 gm of soybean oil (e.g., Frymaxt!9 sold by the Procter & BR< Gamble Co.) that has been used several day in an institutional deep fryer, is placed into the skillet and heated on the setting of 2500 F with the 30 gal trash can lid slightly cracked to allow the resulting steam to escape. Heat for 5 min. then unplug the skillet and cool until the sizzling and popping inherent when used oil is heated, subsides.

Immediately remove the skillet lid and suspend the test shirts and the controls in the 30 gal can and seal the lid of the 30 gal can in place. Equilibrate the shirts in the can with the hot oil vapors for 15 minutes then remove and immediately evaluate for malodor control.

(c) Mildew Test: A 55 gallon drum is modified by drilling a small hole in the side ofthe drum to allow insertion of a mechanism that will allow the suspended test shirts to be periodically turned once the drum lid is sealed. The mildew odor is produced by placing several large pieces of miscellaneous type of fabric into the bottom of the modified drum with moisture for several weeks. During this time authentic culture media is also added. Within 2-3 weeks, the expert panelist can judge whether the container to exhibits a sufficient "mildew" malodor. Once deemed to have sufficient mildew odor the can is then used for testing. Suspend the test shirts and the controls in the sealed 55 gallon drum for 24 hours. Remove and immediately evaluate for malodor control.

Expert panelists evaluating the malodor control efficacy assign the following grades based on the descriptive scale below: Grade Condition 0 Clean fabric, not detectable malodor 1 1 think there is some detectable odor 2 Slight but identifiable malodor present 3 Definite malodor present 4 Strong malodor present 5 Most serious malodor The following embodiments illustrate, but are not limiting of, the present invention.

Examples The following table lists several examples of detersive compositions for the control of malodor on fabric containing mesoporous molecular sieves.

TABLE I Percent Composition Ingredients 1 2 3 4 5 6 7 Total surfactantl: 22.5 19.4 20.3 18.2 20.4 19.1 22.3 sodium sulfate 14.4 8.9 - 10.2 8.0 8.9 8.9 sodium carbonate 26.2 16.0 30.4 14.3 15.2 15.0 16.0 citric acid - 3.5 - - 7.0 4.0 3.5 zeolite - 26.3 20.5 21.0 12.0 20.0 25.2 poly acrylate 4500 - 3.2 - - 4.7 3.2 3.2 sodium silicate 1.2 0.6 - - - 1.0 0.6 soil release agent 0.6 - - 1.1 3.0 - - Mesoporous Molecular Sieves2: - - - - - - pore size: 30 angstrom 3.0 - - 10.0 10.0 - 20.0 pore size: 32 angstrom 2.0 2.5 - - - - - pore size: 40 angstrom 6.0 - - 10.0 25.0 - pore size: 45 angstrom 1.0 2.5 - 10.0 - - pore size: < 100 angstrom - - 26.0 - 5.0 - Balance adjunct ingredients to 23.1 17.1 2.7 15.2 4.7 3 8 0.3 100% 1. The Total Surfactants may comprise alkyl benzene sulfonates, linear alkyl sulfonates, NEODOL45-7, alkyl ethoxylates, alcohol ethoxylates, branched chain alkyl sulfonates and alkyl ethoxy sulfonates.

2. MCM-41 mesoporous molecular sieves developed by Mobil Oil Company Use of these detergent compositions comprising mesoporous molecular sleeves to wash fabrics in need of malodor control substantially reduces the malodor associated with the fabric following exposure to various sources of malodor.

Claims (11)

Claims

1. A fabric treatment composition comprising a mesoporous molecular sieve in an amount effective to control fabric malodor.

2. A composition according to Claim 1, consisting of: (a) at least 0.05%, by weight of a malodor control mesoporous molecular sieve; (b) from 1% to 99%, by weight of detersive surfactants; and (c) the balance adjunct ingredients.

3. A composition according to either of Claims 1 or 2 comprising a carrier adjunct material selected from the group consisting of water, methanol, ethanol, npropanol, isopropanol, and mixtures thereof.

4. A composition according to any of Claims 1 - 3 wherein the mesoporous molecular sieve has a pore size of from 15 angstroms to 60 angstroms.

5. A composition according to any of Claims 1 - 4 wherein the mesoporous molecular sieve has a silicon atom to aluminum atom content of greater than 50: 1, preferably greater than 200:1.

6. A composition according to any of Claims 1 - 5, wherein the adjunct ingredient is a member selected from the group consisting of builders, buffers, bleaching compounds, bleach activators, chelating agents, anti-redeposition agents, dispersents, brightners, suds suppressers, hydrotropes, soil release agents. fabnc softeners, enzymes, enzyme stabilizers, perfumes, pigments, dyes, dye transfer inhibitors, filler salts, and mixtures thereof.

7. A composition according to any of Claims 1 - 6 wherein more than one pore size mesoporous molecular sieve is present.

8. A composition according to any of Claims 1 - 7 wherein the mesoporous molecular sieves are prepared by a process which utilizes liquid-crystal templating with surfactant materials.

9. A composition according to any of Claims 1 - 8 comprising from 10 % to 50% by weight of detersive surfactants.

10. A composition according to any of Claims 1 - 9 wherein the mesoporous molecular sieves have a regular hexagonal array of uniform channels.

11. A method for preventing or reducing malodor on fabrics, said method comprising contacting a fabric in need of such treatment with a fabric treatment composition according to any of Claims 1 - 10.