WO2001023274A1 - Detergent package with means to mask amine malodours - Google Patents

Abstract

A specially-suited package comprising: a container (20) having at least one compartment for storing a liquid (24); a dispensing opening (30) in liquid communication with said at least one compartment; a closure for sealing the opening; and a plastic member impregnated with a perfume composition wherein the plastic member (36) is in communication with said compartment so that upon being released from the plastic member the perfume composition effectively suppresses malodors, particularly those malodors emanating from nitrogenous compounds.

Description

DETERGENT PACKAGE WITH MEANS TO MASK AMINE MALODOURS

TECHNICAL FIELD

The present invention relates to packages to contain and store liquid or gel compositions such as detergent, cleaning, fabric care, and personal care compositions, particularly liquid detergent compositions suitable for use in manual dishwashing operations The packages are particularly suited for stoπng detergent compositions containing malodor-generating compounds and suppressing the malodors emanating from such detergent compositions

BACKGROUND OF THE INVENTION

Liquid or gel detergent products are widely-used by consumers for a variety of cleaning tasks mclude the cleaning of hard surfaces (floors, ovens and ranges, countertops). clothing and textile articles, and dishes, cook ware and other kitchen articles One example of a liquid cleaning product is a light-duty liquid (LDL) detergent composition which is useful for manual dishwashing Such products are generally formulated to provide a number of widely diverse performance and aesthetics properties and characteristics First and foremost, liquid and gel dishwashing products must be formulated with types and amounts of surfactants and other cleamng adjuvants that will provide acceptable solubihzation and removal of food soils, especially greasy soils, from dishware bemg cleaned with, or m aqueous solutions formed from, such products Thus, there is a continuing effort by formulators of liquid dishwashing compositions to incorporate additional components into LDL detergents to provide consumers with improved cleaning benefits

One example of a component which can improve the cleamng performance of liquid dishwashing detergent compositions is a nitrogenous compound such as a diamme which aids in particular m the cleaning of greasy, hydrophobic soils on dishware or other kitchen articles However, diamines can also cause extremely potent malodors, for example the unpleasant fragrance associated with permanent kits commonly used to curl hair are generated by diamines Other nitrogen-containing surfactants and polymers can provide both cleaning and sudsmg advantages, but frequently contam amine impurities as by-products in commercial materials When the composition pH approaches or exceeds the pKa of these amine impurities, the resultant free amine can be malodorous Consequently . it has been particularly difficult to formulate a malodor- free light duty liquid at pH higher than 8 5

Amines are just one example of detergent components which provide functional benefits to a liquid detergent composition but are frequently not used because of the undesirable odor associated with them Typically malodors associated with detergent products are "masked" (covered up) by placing a perfume composition in the liquid dishwashing detergent, which masks the malodors emanating from the liquid detergent when used m sufficient quantities These perfumes also provide the added benefit that a desirable fragrance, such as a lemon scent, can be imparted to the liquid detergent product

However, some malodors cannot be masked simply by adding perfumes to the detergent For example, when a particular malodor is highly volatile (and therefore diffuses quickly into the air) and/or when a particular malodor is extremely potent, it may be difficult to add a sufficient amount of perfume without givmg the liquid dishwashing detergent a strong, perfumed odor Given the foregoing there is a continumg need to find ways to control the malodors emanating from such cleaning-enhancing components

Accordingly, a benefit of the present invention is that a package is provided for holding a liquid detergent composition comprising certain nitrogen-contaimng components which is effective at suppressing the malodors associated with such components Preferably these malodors are suppressed and neutralized while they are still within the confines of the package, thus preventing the malodors from ever being detected by the consumer

An additional benefit of the present mvention is that it offers a way of imparting two distinct and different fragrant scents to a consumer product This could be a useful way to convey to a consumer, via an olfactory signal, that a detergent product has two distinct benefits, for example that its detergent composition is both tough on grease, while at the same time is gentle and mild to the skm

The benefits of this invention can be included in containers for a broad variety of liquid and gel detergent, cleamng. fabric care, and personal care products Such products may include LDLs. detergents for use in automatic dishwashing machines, laundry detergents, fabric softeners, deodorizers and refreshers, liquid hand soap, shampoo, after shave, cologne and personal deodorants, other personal care compositions, hard surface cleaners, and a vaπety of other home and personal care products in which odor-emanatmg compounds like amines may be present and it is desirable to mask or suppress any malodors that they may generate

SUMMARY OF THE INVENTION

It has now been determined that when a liquid or gel (hereinafter referred to as liquid) composition such as a liquid dishwashing detergent which contains malodor-generating compounds like ammes is stored in a package constructed according to the present invention, then the odors typically associated with the malodor-generating compounds are effectively suppressed by neutralization, modification, or masking and thus not physically sensed by the consumer This specially-suited package comprises a container having at least one compartment for storing a liquid, a dispensing opening m liquid communication with said at least one compartment, a closure for sealing the opening, and a plastic member impregnated with a perfume composition, wherein the plastic member is in communication with said compartment so that upon being released from the plastic member, the perfume composition effectively suppresses malodors

A second embodiment of the invention consists of the combination of the above specially- suited package and a liquid such as a detergent composition placed inside the package In this second embodiment, the combmation compπses a contamer having at least one compartment for storing a liquid, a liquid composition such as a detergent, cleaning product, or a fabric care or personal care product disposed within this compartment comprismg a first perfume composition, a dispensing opening in liquid communication with said at least one compartment, a closure for sealing the opening, and a plastic member which comprising a second perfume composition, wherein the plastic member is m communication with said compartment so that the second perfume composition effectively suppresses malodors by neutralization, modification, or masking In fact, both perfume compositions may contπbute to odor-suppression and. preferably, neither perfume composition has the same formulation of the other

The present invention also separately relates to a perfume-impregnated material which releases fragrance materials or odor neutrahzers in a gaseous phase whereby the fragrance materials or odor neutrahzers mask malodors or neutralize or modify malodor-generating compounds and thus effectively suppress malodors

All parts, percentages and ratios used herein are expressed as percent by weight unless otherwise specified All documents cited are. in relevant part, incorporated herein by reference

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description taken in conjunction with the accompanying drawings in which

Fig 1 is a cross-sectional side view of an exemplary bottle made in accordance with the present invention.

Fig 2 is an enlarged partial cross-sectional side view of the upper portion of the bottle of Fig 3 is a perspective view of a perfume-impregnated plastic member m the form of an annular disk suitable for use with the bottle of Fig 1 ,

Fig 4 is an enlarged partial cross-sectional side view of the upper portion of another preferred bottle made m accordance with the present invention, wherein the perfume-impregnated plastic member is provided as a cylindrical sleeve, and

Fig 5 is an enlarged partial cross-sectional side view of the upper portion of yet another preferred bottle made in accordance with the present mvention, wherein a perfume-impregnated plastic member m the form of a rod is provided

DETAILED DESCRIPTION OF THE INVENTION

Definitions - The present detergent compositions comprise an "effective amount" or a "'grease removal-improving amount^" of individual components defined herein By an "effective amount" of the diamines herein and adjunct ingredients herein is meant an amount which is sufficient to improve, either directionally or significantly at the 90% confidence level, the performance of the manual dishwashing composition against at least some of the target soils and stams Thus, in a composition whose targets include certain grease stams. the formulator will use sufficient diamine to at least directionally improve cleamng performance against such stams

By "light-duty liquid (LDL) detergent composition" it is meant a detergent composition which is employed in manual (I e hand) dishwashing

By "kitchen articles" it is meant cookware, flatware, dishes and dishware. silverware and other articles commonly found m the kitchen and used for the preparation, consumption and serving of food as well as those articles used for cleaning up at the conclusion of a meal or other food preparation

By "nitrogenous compounds" it is meant those compounds containing nitrogen and related to ammonia or ammomum Such compounds include amines, polyammes. amme oxide surfactants, amides, surfactants in which the hydrophilic. polar groups are neutralized by an ammounium cation, alkanolamme solvents (e g monoethanolamme. diethanolamine, and tπethanolamine) and other similar compounds which are typically used in detergent or cleaning compositions

By "malodor" it is meant any detectable odor associated with and originating m any component of a detergent composition, particularly short-chain fatty acids or an amine or other nitrogenous compound related to ammonia or ammonium By "amine" it is meant any deπvative of ammonia or ammomum in which one or more of the hydrogen atoms is replaced by an alkyl group, a cyclic hydrocarbon group, a fatty alkyl group or an aromatic group

By "scent" it is meant any detectable odor associated with and originating in a fragrance material or an odor neutrahzer

By "volatility" it is meant the tendency of a liquid material to pass into the vapor state at a given temperature

The present invention is directed to a package suitable for containing a liquid detergent, cleamng. fabric care, or personal care composition and a combination of such a package and the composition, particularly a liquid dishwashing detergent composition, having particular attributes A package designed accordmg to the present mvention is particularly suited to suppress or mask the malodors generated by nitrogenous compounds found in such a composition contained inside the package These nitrogenous compounds may be added to the liquid composition either intentionally to provide some performance benefit for the detergent, cleaning, fabric care or personal care composition, or they may be introduced inadvertently as impurities in the surfactant additives (particularly in amme oxide, betaine and polyhydroxy fatty acid amide surfactants) and in amine- containing polymers

Referring to Fig 1. an exemplary bottle 20 made in accordance with the present invention is illustrated While the present mvention will be described herein with respect to the exemplary bottle 20 for simplicity and clarity, the present mvention can also be adapted for use with other types of hollow containers storing a material other than a liquid, such as granular or powdered mateπals The bottle 20 comprises a hollow bod) 22 for storing a liquid 24 and has a closed bottom 26. at least one side wall 28, and a dispensing opening 30 disposed opposite the closed bottom 26 A male threaded finish 32 is disposed adjacent the opemng 30 for removeablly receivmg a female threaded closure 34 which prevents inadvertent spillage of the liquid 24 from the bottle 20 The threaded fimsh 32 can be integrally formed with the hollow body 22. or it can be provided as a separate structure which is attached to the hollow body 22 by an adhesive, friction welding, or any other method which provides a liquid tight seal between the fimsh 32 and the hollow body 22 The closure 34 preferably has an open position for dispensing the liquid 24 from the bottle 20 and a closed position for sealing the opening 30 The closure can be provided as is known in the art and may be of the flip top, turret cap, or push pull type, the latter being illustrated in Figs 1 and 2 The cap can be formed from such materials as a copolymer of high density polyethylene and polypropylene by injection molding Alternatively, a simple threaded cap, such as that illustrated in U S Patent No 4,981,239 to Cappel et al , can be provided or a snap-fitted closure, such as that described m U S Patent No 5,865,331 to Jacobs, both patents being incorporated herein by reference, can be used As will be appreciated, other closure and fimsh configurations can also be used which provide manual dispensmg of the bottle^'s contents and provide a closed-end compartment for retaining the contents until dispensation is desired

While the present invention is described herein with respect to a bottle havmg a single compartment, it will be appreciated that the present invention can be adapted for use with a multi- compartmented bottle, such as that described in U S Patent No 4,678,103 to Dirksmg which is fully incorporated herein by reference Further, the present mvention can be adapted for use with other types of hollow containers for storing liquids such as. LDLs. detergents for use m automatic dishwashing machines, laundπ detergents, fabric softeners, deodoπzers and refreshers, liquid hand soap, shampoo, after shave, cologne and personal deodorants, other personal care compositions, hard surface cleaners, and a variety of other home and personal care products Further, the hollow container 22 can be provided ith multiple finishes, closures, and side walls as desired The hollow container 22 is preferably formed by blow molding from a thermoplastic, such as high density polyethylene, although other materials and manufacturing processes can be employed For example, the bottle 20 can be formed by injection molding, rotational molding, thermoform molding, and the like using suitable mateπals known m the art

In accordance with one aspect of the present invention, a perfume-impregnated plastic member in the form of a substantially round annular disk 36 is preferably disposed adjacent to the dispensing opening 30, between the closure 34 and the finish 32 of the bottle 20, wherein the annular disk 36 includes a perfume composition which effectively suppresses malodors by neutralization, modification, or masking A significant amount of this suppression will preferably take place in the hollow container 22 as odor neutrahzers and fragrance materials diffuse out and are released from the annular disk 36 and mask or neutralize the malodors that have diffused out of the liquid detergent composition and accumulated in the hollow container 22. particularly in the headspace 46 or on the interior of the side walls 28 More preferably, the annular disk 36 is disposed between the inner surface 38 of the closure 34 and the top surface 40 of the fimsh 32 such that the closure 34, when threaded onto the finish 32, secures the annular disk 36 in place The annular disk 36 mcludes a hole 42 through which the liquid 24 can pass so that the liquid 24 can be dispensed from the hollow bod\ 22 through the closure 34 The annular disk 36 is preferably sized such that a sufficient portion of its surface area is exposed to the head space 46 (hereinafter referred to as the "active surface area") of the bottle 20 to effectively suppresses malodors generated by the liquid 24 As used herein, the phrase "head space" is intended to refer to the portion of the internal volume of the bottle 20 which is not occupied by the liquid 24 As will be appreciated, the volume of the head space 46 can vary from about 0 cm³ for a bottle which is fully filled to a maximum based upon the total internal volume of the bottle 20 as a function of the internal height 47 and other dimensions of the bottle 20 For a bottle 20 having a total internal volume of between about 25 ml and about 2000 ml, the active surface area of the annular disk 36 is preferably between about 1 cm' and about 1000 cm², and more preferably between about 1 cm² and about 10 cm² The annular disk 36 generally has an average thickness of between about 2 mm and about 20 mm, depending on the size of the bottle 20. the finish 32 and the closure 34 The ratio of the surface area of the perfume-impregnated plastic member which is exposed to the compartment for storing the liquid to the volume of the compartment is preferably between about 0 0005 1 cm²/ml and about 10 1 cm²/ml. more preferably between about 0 001 1 cm²/ml and about 0 01 1 cm²/ml

The annular disk 36 is formed from a perfume-impregnated material 44 and may be formed mto the disk-like shape by stamping The perfume-impregnated mateπal 44 contains an impregnating perfume composition which in turn compπses odor-neutrahzers and optionally fragrance materials as set forth m more detail below The perfume-impregnated material 44 can be formed from polymeπc and composite materials and an impregnating perfume composition Suitable materials include the fiber-reinforced composite materials and resms (particularly noted for their ability to contam an antimicrobial additne) disclosed in U S Pat No 5,919,554, to Watterson III et al , issued July 6, 1999, which is hereby incorporated by reference Further suitable polymer materials include low density polyethylene, expandable polystyrene compositions, high density polyethylene, blended polyethylene and carbon black, polyene/alpha-olefin copolymers, poly-alpha- olefins, polyolefins, polyethylene oxides, olefin polymers and co-polymers, chlorinated PVC, polyepsilon caprolactone co-polymers, styrene acrylonitπle co-polymers, co-polymers of epsilon caprolactone with 1.4-butane diol , polyesters, chlormated polyethylene, plasticized polyepsilon caprolactone co-polymers containing dimethyl phthalate plasticizers, maleic anhydride modified adducts of polyepsilon caprolactone pohols and ethylenically unsaturated monomer, polyurethane polymers having lactone backbones, polyurethane polyether resms wherein the resm is obtained by reactmg a polyfunctional lactone with a long chain polyalkylene diol and a urethane precursor and resms havmg polyurethane backbones, and mixtures thereof All of these mateπals are discussed in greater detail m U S Pat No 4,521,541, to Rutherford et al , issued June 4, 1985, which is hereby incorporated by reference Other perfume-impregnated materials suitable for use with the present invention can mclude foams, polymeric laminate structures compπsmg cardboard, celluosic. or other material layers, and the like

The perfume-impregnated material 44 will comprise from about 1% to about 30%, preferably from about 2 % to about 25 %, more preferably from about 5 % to about 20%, most preferably from about 8% to about 15%, by weight of impregnating perfume composition The components of this impregnating perfume composition will now be discussed m detail a) Odor Neutrahzers

Odor neutrahzers work differently than the fragrance mateπals which are discussed at greater length below They mask malodors by reducing the amount of the malodor-generating component which is responsible for the malodor A suitable odor neutralizer is any chemical species that upon reacting with a malodor-generating compound (such as amines and other nitrogeneous compounds) yields products which generate little or significantly less malodor than the malodor-generating compound itself Thus when the perfume-impregnated plastic member herein releases the odor neutralizer m a gaseous phase, the odor neutralizer reacts with one or more malodor-generatmg compounds to effectively suppress malodors

A preferred species of odor neutrahzers are aldehydes It is well known that aldehydes react with amines m a Schiff reaction to produce a Schiff base and water H R^b— C=O + R^a— NH₂ » R^a— N = CH- R^b + H₂O

(aldehyde) (amme) (Schiff base)

In the above reaction. R^a and R^b are both aliphatic substituents In the present invention the amme may be a diamine mcluded for the benefits it provides on tenacious, hydrophobic and greasy soils See the discussion of diamines below

Schiff bases generate little or no malodor and thus by reactmg an aldehyde with a amine they reduce the amount of the amme which is present to generate malodors In the present invention, malodors emitted by amines in the liquid detergent composition and aldehydes released from the perfume-impregnated material 44 react in the gas phase or on the inner surfaces of the bottle 20 To prevent the amme from forming m excess m the headspace and to thus obtain the best possible malodor-suppression benefits, it is important that the rate of diffusion/release of the aldehydes from the perfume-impregnated material 44 mto the headspace 46 must exceed both the steady-state rate of migration of amme malodors from the liquid to gas phase and the rate of consumption of the aldehydes m the Schiff base reaction between amme and aldehyde

Specific aldehydes suitable for use m the present mvention include para-tertiary-Butyl- alpha-methly hydrocinnamic aldehyde, 4-(4-Methyl-4-hydroxyamyl)-3-cyclohexane-l- Carboxaldehyde, hydroxycitronellal, and a_pha-methyl-beta-3,4-methylenedιoxy- phenylpropionaldehyde, as well as most other aldehydes For example, C_D-C_2. aldehydes, methyl nonyl acetaldehyde, citronellal. iso butyl citral, iso cyclo citral, mandarin aldehyde, methyl octyl acetaldehyde, oncidal, pre cyclemone B. iso dihydro lavendulyl aldehyde, oxy aldehyde, cyclac C, homo cuminic aldehyde 50%. hydrotropic aldehyde, 2, 6. nonadienal, tπplal. vandor B. adoxal, anisic aldehyde, butyl cinnamic aldehyde, citronellyl oxy acetaldehyde, floralozone. florhydral, hehotropm, myrac aldehyde, lyral, cymal, amyl cinnamic aldehyde, hexyl cinnamic aldehyde, ethyl vanillin, hehonal. ins aldehyde, vanillin, cinnamic aldehyde, cuminic aldehyde, undecalactone, allyl caprylate. benzaldehyde, nonalactone, precyclemone B, prunohde, koavone. okoumal, phenyl acetaldehyde. and phenyl acetaldehyde dimethyl acetal are also useful herein Many odor neutrahzers, e g several different species of aldehydes, emit a characteristic scent and can also serve in the present mvention as a fragrance material From about 10% to about 100%, preferably from about 20% to about 75%. most preferably from about 30% to about 65%, by weight of the impregnating perfume compositions of the present invention will consist of an odor neutralizer b) Fragrance Mateπals

The impregnating perfume compositions in the perfume-impregnated material 44 contain fragrance materials which mask the presence of malodors emanating from malodor-generating compounds like ammes These fragrance materials mask the malodors by providing scents which compete with the malodors for access to the nasal receptor sites

Under typical usage conditions, malodors associated with malodor-generating compounds such as ammes and other nitrogenous components of a dish detergent product are liberated from the dish detergent product as soon as the detergent is exposed to air (e g the bottle is opened and the product is then applied to a dish surface or diluted further with water) Generally such malodors will have accumulated in the headspace 46 m the container between uses by the consumer Once the malodors are free of the detergent container, they diffuse into the surrounding air, move to the nasal receptor sites and provide an adverse olfactory signal which consumers instantly associate with the product While not intending to be limited by theory, it is believed that the ability of fragrance materials contamed m the present impregnatmg perfume compositions to mask malodors is related to the amount of tune that the scents emanating from the fragrances require to diffuse mto the air and hence move from the detergent packages to the nasal receptor sites Thus the fragrance mateπals present in the impregnating perfume compositions are selected primarily on the basis of their volatility

Highly volatile fragrance mateπal are prefeπed fragrance materials for inclusion in the impregnating perfume compositions of the present invention Highly volatile fragrance mateπals have lower boiling points than other substances and so the scents from these mateπals quickly diffuse mto the air, and compete with the malodors to bmd to the nasal receptor sites, becoming the first odors recognized and identified by the brain Because the scents form the highly volatile fragrance materials are more volatile and arrive before the amine malodors at the nasal receptor sites, when the amme malodors do finally amve the nasal receptor sites have already been occupied thus effectively masking the recognition of the amine malodors

The present impregnating perfume compositions may comprise from about 0 5% to about 4%, preferably from about 1% to about 3%. by weight, of the highly volatile fragrance mateπals Highly volatile fragrance mateπal have a boiling point of below about 180°C, preferably below about 160°C . most preferably below about 140°C, under 1 atmosphere of pressure

Most low molecular weight aldehydes (as discussed above), ketones. and esters have relatively low boiling points and are thus prefeπed examples of highly volatile fragrance mateπals suitable for use in the present invention Examples of suitable ketones and esters can be found in U S Pat No 5,874,073 to Kaiser et al. issued February 23. 1999, which is hereby incorporated by reference Further nonhmiting examples of suitable highly volatile fragrance materials and their respective boiling point values under 1 atmosphere of pressure include the following

Fragrance Material Boiling Point (°C)

Methyl acetoacetate 172

Cyclohexyl alcohol 161

3-Methyl-l-pentanol 151

1,3-Dιmethylbutyal acetate 148

Isopropyl 2 -methylbutyrate 138 ethyl-2-methylbutyrate 131 It is preferable that the present impregnating perfume compositions also constitute volatile fragrance materials As used m this present mvention, volatile fragrance mateπals are less volatile than the highly volatile fragrance matenals and have a boiling pomt of between about 180°C and about 260°C. more preferably between about 185°C and about 240°C, most preferably between about 190°C and about 220°C, under 1 atmosphere of pressure

The impregnating perfume compositions of the present invention are more effective at masking malodors originating in nitrogenous compounds and other compounds when both highly volatile and volatile perfume compositions are present The combmation of such perfume compositions effectively mask these malodors because they mclude highly -volatile fragrance mateπals. which aπive at the nasal receptor sites before the malodors. therefore effectively masking the malodors However, it is possible that after sufficient time has passed and the malodors have arπved in the physical proximity of the nasal receptors sites, scents already resident in the sites may degrade or migrate out of them, thus giving the malodors an opportunity to bind with the sites and thereby making the odors perceptible to consumers This is especially the case if there is a higher concentration of malodors or the malodors are more potent than the scents from highly volatile fragrance materials

To prevent this, it is preferable to mclude volatile fragrance materials in the perfume composition which are not as volatile as the highly volatile fragrance materials The scents from these fragrance mateπals should aπive either simultaneously or soon after the malodors and compete with the malodors for the sites vacated as scents emitted by the highly volatile fragrance materials degrade or migrate out of the nasal receptor sites

The impregnating perfume compositions of the present mvention may comprise from about 15% to about 40%. preferably from about 20% to about 35%, most preferably from about 20% to about 30%, by weight of volatile fragrance materials

Nonhmiting examples of suitable volatile fragrance materials and their respective boiling point values under 1 atmosphere of pressure mclude the following

Fragrance Material Boiling Point (°C)

3.7-dιmethyl-l,6-octadιen-3-ol 198

3,7-dιmethyl-7-hydroxy octan-1-al 241 n-decyl aldehyde 215 benzaldehyde 179 anisic aldehyde 248 benzyl acetate 215 allyl hexanoate 185 methyl-2-ammobenzoate 237

2-cιs-3,7-dιmethyl-2,6-octadιen-l-ol 227

3.7-dιmethyl-trans-2.6-octadιen- 1 -ol 230

3,7-dιmethyl-6-octen-l-ol 225

2,6-dιmethyl-7-octen-2-ol 208

2-phenylethyl alcohol 220

1 -methyl-4-ιso-propyl- 1 -cyclohexen-8-ol 219

1-1 -methyl-4-ιso-propenyl-6-cyclohexen-2-one 231 para-tertiary-amyl cy^rclohexanone 211 cyclohexanyl 2-tertιary butyl acetate 241 benzyl acetate 211

The boilmg point of many perfume materials are disclosed m, e g . "Perfume and Flavor Chemicals (Aroma Chemicals)." S Arctander, published by the author, 1969, incorporated herein by reference Other boilmg point values can be obtained from different chemistry handbooks and databases, such as the Beilstein Handbook. Lange's Handbook of Chemistry, and the CRC Handbook of Chemistry and Physics When a boiling pomt is given only at a different pressure, usually lower pressure than the normal pressure of one atmosphere, the boilmg pomt at normal or ambient pressure can be approximately estimated by using boilmg point-pressure nomographs, such as those given m "The Chemist's Companion." A J Gordon and R A Ford. John Wiley & Sons Publishers, 1972, pp 30-36 When applicable, the boiling point values can also be calculated by computer programs, based on molecular structural data, such as those described in "Computer- Assisted Prediction of Normal Boilmg Points of Pyrans and Pyrroles." D T Stanton et al, J Chem Inf Comput Sci , 32 (1992). pp 306-316, "Computer-Assisted Prediction of Normal Boilmg Points of Furans, Tetrahydrofurans. and Thiophenes." D T Stanton et al, J Chem Inf Comput Sci , 31 (1992), pp 301-310, and references cited therein, and "Predicting Physical Properties from Molecular Structure." R Murugan et al, Chemtech. June 1994, pp 17-23 All the above publications are incorporated herein by reference

While the shape of the annular disk 36 is preferred for the present invention, it will be appreciated that other shapes and configurations can be substituted for the annular disk 36 For example, a perfume-impregnated member in the shape of a polyhedral can be used Further, the perfume-impregnated member can be disposed at other locations of the bottle For instance, as shown in Fig 4, a cylmder or sleeve 48 can be disposed within the finish 32 such that the inner surface 50 of the sleeve 48 is exposed to the head space 46 of the bottle 120 The sleeve 48 can be secured in place using an adhesive or interference fit Alternatively, the perfumed-impregnated member can be integrally formed with a portion of the closure 34 and/or the bottle 120 such the perfiime-impregnated member is exposed to the head space 46 of the bottle 120 Processes which might be used to integrally form these closures and bottles include bi-mjection molding and the like

Referring to Fig 5. yet another prefeπed bottle made in accordance with the present invention is illustrated The bottle 220 mcludes a perfume-impregnated member in the form of a rod 52 which is attached to and extends from the closure 34 mto the head space 46 of the bottle 220 The rod 52 can extend the entire internal height of the bottle 220, or less if desired, so that more of the rod 52 is exposed to the head space 46 as the liquid is dispensed from the bottle 220 and the volume of the head space 46 increases The rod 52 can be formed integrally with the closure 34 or can be separately attached to the closure 34 by any suitable mechanical (e g , interference fit) or chemical (e g . adhesive) means as is known in the art

The perfume-impregnated member may also take the form of the dipstick of a pump for dispensing the liquid disposed within a compartment of the package herein In such a package, the perfume-impregnated member may be affixed to, or integrally formed with, a portion of the closure of the package, and would ordmaπly extend the entire internal height, or most of the height, of the package to facilitate dispensing of the liquid

In another embodiment, the perfume-impregnated member may be m the form of a flexible sheet, strip or bag that coats all or part of the internal surface of the compartment for storing the liquid in the package of the present invention This could provide a perfume-impregnated member having much larger "active surface area" to effectively suppress malodors generated by the liquid disposed withm the package

Liquid Compositions

The package discussed above may be used to contam several different types of liquid compositions which will typically contain malodor-generating compounds which may be added either mtentionally to provide some performance benefit for the detergent, cleaning, fabric care, or personal care composition or may be introduced inadvertently as impurities in one of the additives of the composition These liquid compositions include LDLs. detergents for use in automatic dishwashing machines, laundry detergents, fabric softeners, deodorizers and refreshers, liquid hand soap, shampoo, after shave, cologne and personal deodorants, other personal care compositions, hard surface cleaners, and a vaπety of other home and personal care products in which odor-emanatmg compounds like ammes may be present and it is desirable to mask or suppress any malodors that they may generate Thus many different types of liquid detergent compositions contain active ingredients which are also malodor-generating compounds For example, a malodor-generating compound which is used in shampoos is a cationic polymer compπsing nitrogenous monomeric units such as dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate etc See e g , U S Pat No 5.624,666, to Coffindaffer et al . issued April 29, 1997. which is hereby incorporated by reference

Other malodor-generating compounds which can be useful in hair and skm-care products as well as other liquid detergents include polymers such as gums and resms which are pπmaπly derived from natural sources, crosshnked nomonic polyacrylate polymers and crosslinked cationic polyacrylate polymers such as homopolymers, copolymers. and terpolymers of quaternary ammonium or cationic amine-substituted monomer units, polysacchaπde polymers such as those derived from cellulose and starch, protein polymers, carboxyhc acid polymers such as crosshnked acrylic acid homopolymers or copolymers, substituted or unsubstituted. linear or branched polyacrylamide polymers, copolymers of alkyl vmyl ethers and maleic anhydπde, polyvinyl (N- pyrro dones), silicone polymer materials (excluding the volatile silicone deπvatives useful as a malodor-producing liquid earner descπbed herembelow) such as polydimethylsiloxane gums, silicone elastomers, siloxane gums, resin reinforced siloxanes. and crosshnked siloxane polymers, as well as silicone copolymers useful as hair styling polymers, and mixtures thereof, as disclosed in U S Pat No 5,919,400, to Kaiser et al . issued July 6, 1999. which is hereby incorporated by reference

The malodor-generating amine-substituted groups mentioned above, e g =N — C(=0) — monomer groups which provide dye-transfer inhibition benefits, can also be used in liquid fabric softener products See e g . U S Pat No 5.804,219, to Tπnh et al , issued September 8, 1998, which is hereby incorporated by reference

Amide-based nonionic surfactants such as hydrocarbylamidoalkylenesulfobetaine. which are often used in liquid detergents such as countertop, glass and surface cleaners, can also be a potent-source of malodors See e g , U S Pat No 5.108,660. to Michael, issued April 28, 1992 which is hereby incorporated by reference The liquid detergent products herem may themselves contam additional fragrance mateπals which not only provide additional malodor-suppression effects but also offer a way of incorporating mto a consumer product two distinct and different "fragrances" — with one fragrance bemg found in the liquid detergent composition while the other is m the perfume-impregnated mateπal 44 This could be a useful way to convey to a consumer via an olfactory signal, that a detergent product has two distinct benefits, for example that its detergent composition is both tough on grease, while at the same time is gentle and mild to the skin

These liquid detergent products and the malodor-generating compounds they contain which have been previously mentioned, are discussed only as examples to be illustrative of the breadth and benefits of the present mvention. but are not meant to limit the scope of the malodor-suppression technology to the malodor-generating compounds or the liquid detergent products which have been specifically mentioned

Such liquid detergents generally comprise an anionic surfactant, a solvent, an amine having a pKa with greater than about 8 0. and wherein the composition has a pH of from about 8 5 to about 12 The liquid detergent also preferably comprises a perfume composition comprising from about 30% to about 100% of an odor neutralizer capable of forming a Schiff base when reacted with the amme Other liquid detergents herem compπse a nitrogen-containing polymer or a nitrogen- containing surfactant, wherem the mtrogen-contaimng surfactant is selected from the group consisting of amme oxides, amphoteπc surfactants, glucose amides, and mixtures thereof and the amme is present as an impurity at a level of at least 1 ppm of the mtrogen-contaimng surfactants and the mtrogen-contaimng polymers

The perfume compositions designed to suppress malodors such as nitrogenous malodors comprise fragrance materials which will now be set forth in more detail below If desired, the present liquid compositions will compπse from about 0 01% to about 3%. preferably from about 0 01% to about 0 5%, more preferably from about 0 02% to about 0 2%. and most preferably from about 0 03% to about 0 08%. by weight of perfume composition

The relation between the volatility of a fragrance material and its performance as well as the benefits and operative mechanisms of odor neutralizing aldehydes have been previously discussed above Another important parameter of a fragrance material is the degree of hydrophobicity Liquid detergent compositions of the present invention may be heavily diluted, having formulas containing as much as 80 % of water Thus while the product is being stored, hydrophobic fragrance materials are more likely to concentrate themselves at the interface between the liquid detergent composition and the headspace m the detergent container (e g squeeze bottle) in which the liquid dishwashing detergent is contamed When the product is used by a consumer, those fragrance mateπals which are more hydrophobic will be positioned on the liquid detergent-air interface and thus more readily evaporate mto the air to provide pleasant fragrant signaling

The degree of hydrophobicity of a fragrance material can be coπelated with its octanol/water partitionmg coefficient ("P") The octanol/water partitioning coefficient of a fragrance material is the ratio between its equihbπum concentration in octanol and in water A fragrance material with a greater partitionmg coefficient P is more hydrophobic Conversely, a fragrance material with a smaller partitionmg coefficient P is more hydrophilic The prefeπed fragrance matenals of the present mvention have an octanol/water partitionmg coefficient P of 1000 or greater Since the partitionmg coefficients of the fragrance mateπals normally have high value, they are more conveniently given in the form of their logaπthm to the base 10, log P

The perfume compositions of the present invention may comprise from about 20 % to about 70 % , preferably from about 30 % to about 60 %. most preferably from about 40 % to about 55 % of fragrance materials which have ClogP values, as described hereinafter, of greater than about 2 5 The logP values of many perfume mgredients have been reported, for example, the Pomona92 database, available from Daylight Chemical Information Systems. Inc (Daylog CIS). Irvme. Calif , contams many values, along with citations to the original literature However, the logP values are most conveniently calculated by the "CLOGP" program, also available from Daylight CIS This program also lists experimental logP values when they are available in the Pomona92 database The "calculated logP" (ClogP) is determined by the fragment approach of Hansch and Leo (cf , A Leo, in Comprehensive Medicmal Chemistry, Vol 4. C Hansch, P G Sammens, J B Taylor and C A Ramsden, Eds , p 295, Pergamon Press. 1990, incorporated herem by reference) The fragment approach is based on the chemical structure of each perfume ingredient, and takes mto account the numbers and types of atoms, the atom connectivity, and chemical bonding The ClogP values, which are the most reliable and widely used estimates for this physicochemical property, are used instead of the experimental logP values in the selection of perfume ingredients which are useful m the present invention

Nonhmiting examples of suitable fragrance materials and their respective ClogP values include the following

Perfume Matenal ClogP Benzyl acetate 2 0

Ethyl-2-methylbutyrate 2 2

Furfuryl valerate 2 7

Isobutyl benzyl carbmol 2 9 para-Ethyl-alpha, alpha-dimethylHydro- 3 4 cmnamaldehyde

Isobutyl caproate 3 8

4-tert -butylcyclohexyl acetate 4 1

Perfume compositions which may be added to detergent compositions of the present invention may also mclude from about about 0 10 % to about 4 %, preferably from about 0 15 % to about 2 5 %, most preferably from about 0 20 % to about 2 0 %, of the highly volatile fragrance materials descπbed above They may also comprise from about 30% to about 80%, preferably from about 30% to about 50%, more preferably from about 35% to about 50%, and most preferably from about 40% to about 45%, of volatile fragrance mateπals as described above

Perfume compositions suitable for incorporation into the liquid detergents of the present mvention are discussed at greater length m the PCT application of Kaiser et al entitled "Perfume Compositions and Methods to Mask Amme Malodors," application number US 00/06606, havmg been filed on March 14, 2000. which is hereby incorporated by reference

In addition, it may be desirable to incorporate mto the present liquid detergent compositions complexing agents which have an internal cavity and are capable of forming complexes with the fragrance material mgredients of the perfume compositions Prefeπed complexing agents are cyclodextrin molecules that are known for their ability to form complexes with perfume ingredients and have typically been taught as a perfume caπier In addition, cyclodextrin molecules also appear to be surprisingly effective at reducing malodors generated by nitrogenous compounds, such as ammes

Thus in one embodiment of the present invention, the liquid detergent compositions comprise an anionic surfactant, a solvent and fragrance materials, wherein a portion of the fragrance materials are complexed with water-soluble cyclodextrin molecules while another portion are uncomplexed Thus the present detergent compositions may contain fragrance materials which are complexed with cyclodextrin as well as free fragrance materials which when brought into the presence of cyclodextrin molecules are not incorporated into the molecule's cavity and remain as free molecules Further discussion of the use of cyclodextrin and fragrance materials m a liquid detergent composition may be found m the pending provisional application of Foley et al , entitled "Detergent Compositions with Perfume Complexes to Mask Malodors," having P&G Case No 7806P2, Seπal No 60/204287, filed on May 15. 2000, incorporated herein by reference

Components which perform useful functional, detersive or aesthetic benefits m a liquid detergent composition prepared according to the present mvention will now be described in sentam These components described below are particularly suitable for formulating a LDL composition Other components as well as their ensemble combination in vaπous kinds of liquid detergent formulations are discussed m the numerous references which have been incorporated herem

Diammes - As noted above, diamines may be used herein in detergent compositions in combination with detersive surfactants at levels which are effective for achieving at least a directional improvement in cleamng performance In the context of a hand dishwashing composition, such "usage levels" can vary dependmg not only on the type and severity of the soils and stams. but also on the wash water temperature, the volume of wash water and the length of time the dishware is contacted with the wash water

Since the habits and practices of the users of detergent compositions show considerable vaπation, the composition will preferably contam at least about 0 1 %, more preferably at least about 0 2%, even more preferably at least about 0 25%, even more preferably still at least about 0 5%, by weight of said composition of diamine The composition will also preferably contain no more than about 15%, more preferably no more than about 10%, even more preferably no more than about 6%, even more preferably no more than about 5%, even more preferably still no more than about 1 5%, by weight of said composition of diamine

In one of its several aspects, this mvention provides a means for enhancing the removal of greasy/oily soils by combimng the specific diamines of this invention with surfactants Greasy/oily "everyday" soils are a mixture of triglycerides, hpids, complex polysacchaπdes. fatty acids, inorganic salts and protemaceous matter

Thus diammes, in combination with amphoteπc and anionic surfactants in the specific ratios discussed below, offer the benefit of improved grease and tough food cleaning which allows the elimination or reduction m the amount of divalent ions in the preferred embodiments of the present formula This improved cleanmg is a result of diammes' proclivity as a buffering agent to increase the alkalinity of the dishwashing composition The superior rate of dissolution achieved by divalent ion elimination even allows the formulator to make hand dishwashmg detergents, especially compact formulations, at even significantly higher viscosities (e g , 1,000 centipoise or higher) than conventional formulations while maintaining excellent dissolution and cleamng performance This has significant potential advantages for making compact products with a higher viscosity while mamtammg acceptable dissolution By "compact" or "Ultra" is meant detergent formulations with reduced levels of water compared to conventional liquid detergents For "compact" or "Ultra" formulations, the level of water is less than 50%, preferably less than 30% by weight of the liquid dishwashing detergent compositions Said concentrated products provide advantages to the consumer, who has a product which can be used m lower amounts and to the producer, who has lower shipping costs For compositions which are not meant to be concentrated, a suitable water level is less than about 85 %, more preferably less than about 70 % by weight of the liquid dishwashing detergent compositions

Preferred organic diammes are those m which pKl and pK2 are m the range of about 8 0 to about 11 5, preferably m the range of about 8 4 to about 11, even more preferably from about 8 6 to about 10 75 Prefeπed materials for performance and supply considerations are 1,3- bιs(methylamιne)-cyclohexane Ka=10 to 10 5), 1,3 propane diamine (pKl=10 5. pK2=8 8), 1,6 hexane diamine (pKl=l 1. pK2=10). 1.3 pentane diamme (Dytek EP) (pKl=10 5. pK2=8 9), and 2-methyl 1,5 pentane diamine (Dytek A) (pKl=l 1 2, pK2=10 0) Other preferred mateπals are the pπmary/pπmary diammes with alkylene spacers ranging from C4 to C8 In general, it is believed that primary diammes are prefeπed over secondary and tertiary diamines

Definition of pKl and pK2 - As used herein, "pKal" and "pKa2" are quantities of a type collectively known to those skilled in the art as "pKa " pKa is used herein in the same manner as is commonly known to people skilled in the art of chemistry Values referenced herein can be obtained from literature, such as from "Critical Stability Constants Volume 2. Amines^' by Smith and Martel, Plenum Press, NY and London, 1975 Additional information on pKa's can be obtained from relevant company literature, such as information supplied by Dupont. a supplier of diammes

As a working definition herein, the pKa of the diammes is specified in an all-aqueous solution at 25°C and for an ionic strength between 0 1 to 0 5 M The pKa is an equihbπum constant which can change with temperature and ionic strength, thus, values reported in the literature are sometimes not in agreement depending on the measurement method and conditions

Further discussion of the pKl and pK2 values and diammes as well as examples of preferred diamines can be found in the PCT application of Joanna M Clarke entitled "Diols and Polymeric Glycols for Improved Dishwashing Detergent Compositions", having publication number PCT WO 00/46331, published August 10, 2000, incorporated herein by reference

Anionic Surfactants - The anionic surfactants useful in the present mvention are preferably selected from the group consisting of linear alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosmates, taurinates. and mixtures thereof An effective amount, typically from about 0 5% to about 90%, preferably about 5% to about 50%, more preferably from about 10 to about 30%, by weight of anionic detersive surfactant can be used in the present invention

Suitable examples of anionic surfactants may be found m the PCT application of Chandπka Kastuπ et al . entitled "Liquid Detergent Compositions Compπsmg Polymeric Suds Enhancers", having publication number PCT WO9927058A1, published June 3, 1999. which is incorporated above Further examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Vol I and II by Schwartz, Perry and Berch) A variety of such surfactants are also generally disclosed m U S Patent 3,929,678, issued December 30, 1975 to Laughhn, et al at Column 23, line 58 through Column 29. lme 23 Suitable anionic surfactants may further be found m U S Pat No 5,415.814 issued 16 May 1995, to Ofosu-Asante et al . all of which are hereby incorporated by reference

Amphotenc surfactants - The amphoteπc surfactants useful in the present invention are preferably selected from amme oxide surfactants Amine oxides are semi-polar surfactants and include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms, water-soluble phosphme oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consistmg of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms, and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms

Further amphotenc surfactants, and amine oxides in particular, are disclosed m the PCT application of Joanna M Clarke entitled "Diols and Polymeric Glycols for Improved Dishwashing Detergent Compositions", havmg publication number PCT WO 00/46331. published August 10, 2000, which is hereby incorporated in its entirety, by reference Particular suitable for use herein. because they are low-foaming, it may be desirable to use long chain amme oxide surfactants which are more fully described m U S Pat Nos 4,316.824 (Pancheπ), 5,075,501 and 5,071,594, incorporated herein by reference

Preferably the amphotenc surfactant is present m the composition m an effective amount, more preferably from about 0 1% to about 20%, even more preferably about 0 1% to about 15%, even more preferably still from about 0 5% to about 10%.by weight

Secondary Surfactants - Secondary detersive surfactant can be selected from the group consisting of nomomcs, catiomcs, ampholytics. zwitteπomcs, and mixtures thereof By selecting the type and amount of detersive surfactant, along with other adjunct ingredients disclosed herem, the present detergent compositions can be formulated to be used m the context of laundry cleamng or in other different cleamng applications, particularly including dishwashing The particular surfactants used can therefore vary widely depending upon the particular end-use envisioned Suitable secondary surfactants are described in detail m the copendmg provisional patent application of Chandπka Kastuπ et al , entitled "Liquid Detergent Compositions Comprising Polymeric Suds Enhancers", having publication number PCT WO9927058A1, published June 3, 1999, which is incorporated above

Ratio of anionic to amphotenc to diamme

In the compositions of the present invention the ratio of the anionic surfactant amphoteπc diamine is from about 100 40 1 to about 9 0 5 1. by mole, preferably the ratio of the anionic surfactant amphotenc diamme is from about 27 8 1 to about 11 3 1, by mole It has been found that detergent compositions containing anionic surfactant, amphotenc surfactant and diamme in this specific ratio range provide improved low temperature stability, deliver better grease removal and tough food cleamng benefits at pH less than 12 5, and improved hard water cleaning

In another aspect of the present mvention the mole ratio of anionic surfactant to diamme of greater than 9 1, preferably greater than 20 1, has been found to give improved low temperature stability, deliver better grease removal and tough food cleaning benefits and improved hard water cleamng

Solvents - A vanety of water-miscible liquids such as lower alkanols diols. polyols, ethers, ammes and polymeric glycols which comprise ethylene oxide (EO) and propylene oxide (PO) groups and the like may be used in the present invention Particularly prefeπed are the C 1 - C4 alkanols, diols and the above mentioned polymeric glycols When present the composition will preferably contam at least about 0 01%, more preferably at least about 0 5%. even more preferably still, at least about 1% by weight of the composition of solvent The composition will also preferably contam no more than about 20%, more preferably no more than about 10%, even more preferably, no more than about 8% by weight of the composition of solvent

Further examples of suitable solvents as well as their concentrations for use in a LDL compositions are disclosed in the PCT application of Joanna M Clarke entitled "Diols and Polymeric Glycols for Improved Dishwashing Detergent Compositions", having publication number PCT WO 00/46331, published August 10, 2000. incorporated above and m the copendmg provisional patent application of Chandπka Kasturi et al . entitled "Liquid Detergent Compositions Compπsing Polymenc Suds Enhancers", havmg publication number PCT WO9927058A1, published June 3. 1999. which is incorporated above

Buffenng Agents — Dishwashing compositions of the invention will be subjected to acidic stresses created by food soils when put to use, I e , diluted and applied to soiled dishes The compositions of the present invention will preferably

a pH of at least about 8 5, preferably at least about 10, more preferably, at least about 10 5, the compositions of the present invention will also have a pH of no more than about 12, preferably no more than about 11 5. more preferably no more than about 10 9 Because the detergent compositions of the present mvention are largely alkaline, the detergent compositions will contain a buffenng agent capable of providmg a generally more alkaline pH in the composition and in dilute solutions Dishwashing compositions of the present invention will thus contain from about 0 5% to 15%, preferably from about l% to 12% most preferably from about 2% to 10%, by weight, of a buffering agent The pKa value of this buffering agent should be about 0 5 to 1 0 pH units below the desired pH value of the composition (determmed as descπbed above) Preferably, the pKa of the buffering agent should be from about 7 to about 12 Under these conditions the buffering agent most effectively controls the pH while usmg the least amount thereof

Prefeπed inorganic buffers/alkalmity sources include the alkali metal carbonates, alkali metal hydroxides and alkali metal phosphates, e g , sodium carbonate, sodium hydroxide, sodium polyphosphate

The buffering agent may be an active detergent in its own right, or it may be a low molecular weight, organic or inorganic material that is used in this composition solely for maintaining an alkaline pH Preferred buffering agents for compositions of this invention are mtrogen-contammg matenals Further examples of suitable buffenng agents may be found m the PCT application of Joanna M Clarke entitled "Diols and Polymenc Glycols for Improved Dishwashmg Detergent Compositions", havmg publication number PCT WO 00/46331, published August 10, 2000. incorporated above

OPTIONAL DETERGENT INGREDIENTS

Polymeric Suds Stabilizer - The compositions of the present invention may optionally contain a polymeric suds stabilizer These polymeric suds stabilizers provide extended suds volume and suds duration without sacnficing the grease cutting ability of the liquid detergent compositions

One prefeπed polymeπc suds stabilizer is (N.N-dιmethylammo)alkyl acrylate esters, namely

When present m the compositions, the polymeπc suds booster may be present in the composition from about 0 01% to about 15%. preferably from about 0 05% to about 10%. more preferably from about 0 1% to about 5%. by weight See PCT application of Chandnka Kasturi et al , entitled "Liquid Detergent Compositions Compπsmg Polymeπc Suds Enhancers", havmg publication number PCT WO9927058A1, published June 3. 1999. which is incorporated above

Builder - The compositions according to the present invention may further compnse a builder system Because builders such as citric acid and citrates impair the stability of enzymes in LDL compositions, it is desirable to reduce the amounts of or completely remove the builder salts normally utilized in LDL compositions incorporating enzymes When a detergent composition mcludes propylene glycol solvent as a part or a whole of the detergent's earner, enzymes are more stable and higher amounts of builder salts may be added

If it is desirable to use a builder, then any conventional builder system is suitable for use herein including aluminosihcate materials, silicates, polycarboxylates and fatty acids, materials such as ethylene-diamme tetraacetate, metal ion sequestrants such as aminopolyphosphonates. particularly ethylenediamine tetramethylene phosphomc acid and diethylene tπamine pentamethylene-phosphonic acid Though less prefeπed for obvious environmental reasons, phosphate builders can also be used herem

Further discussion of suitable builders can be found m the PCT patent application of Joanna M Clarke entitled "Diols and Polymeric Glycols for Improved Dishwashmg Detergent Compositions", havmg publication number PCT WO 00/46331, published August 10, 2000, incorporated above

If detergency builder salts are included, they will be mcluded in amounts of from 0 5 % to 50 % by weight of the composition, preferably from 5% to 30%, and most usually from 5% to 25% by weight

Enzymes - Detergent compositions of the present mvention may further comprise one or more enzymes which provide cleaning performance benefits Said enzymes include enzymes selected from cellulases, hemicellulases. peroxidases, proteases, gluco-amylases. amylases, hpases. cutmases, pectinases, xylanases, reductases. oxidases, phenoloxidases, hpoxygenases, hgnmases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases or mixtures thereof A prefeπed combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, hpase, cutinase and/or cellulase Enzymes when present in the compositions, at from about 0 0001% to about 5% of active enzyme by weight of the detergent composition Prefeπed proteolytic enzymes, then, are selected from the group consisting of Alcalase ® (Novo Industπ A/S), BPN'. Protease A and Protease B (Genencor), and mixtures thereof Protease B is most prefeπed Prefeπed amylase enzymes include TERMAMYL®, DURAMYL® and the amylase enzymes those described in WO 9418314 to Genencor International and WO 9402597 to Novo Further non-limiting examples of suitable and preferred enzymes are disclosed m the PCT application of Joanna M Clarke entitled "Diols and Polymeric Glycols for Improved Dishwashmg Detergent Compositions", having publication number PCT WO 00/46331. published August 10, 2000. incorporated above

Because hydrogen peroxide and builders such as citric acid and citrates impair the stability of enzymes m LDL compositions, it is desirable to reduce or eliminate the levels of these compounds in compositions which contam enzymes Hydrogen peroxide is often found as an impunty in surfactants and surfactant pastes As such, the preferred level of hydrogen peroxide in the amme oxide or surfactant paste of amine oxide is 0-40 ppm, more preferably 0-15 ppm Amme impurities in amine oxide and betaines. if present, should be minimized to the levels refeπed above for hydrogen peroxide and preferably should be less than 1 ppm Magnesium ions

While it is prefeπed that divalent ions be omitted from LDL compositions prepared accordmg to the present mvention. alternate embodiments of the present mvention may mclude magnesium ions

It is desirable to exclude all divalent ions from the present LDL compositions, because such ions may lead to slower dissolution as well as poor rmsmg, and poor low temperature stability properties Moreover, formulating such divalent ion-containing compositions in alkaline pH matrices may be difficult due to the incompatibility of the divalent ions, particularly magnesium, with hydroxide ions

Nonetheless, the presence of magnesium ions offers several benefits Notably, the inclusion of such divalent ions improves the cleaning of greasy soils for various LDL compositions, in particular compositions containing alkyl ethoxy carboxylates and/or polyhydroxy fatty acid amide This is especially true when the compositions are used m softened water that contains few divalent ions

But in the present invention, these benefits can be obtained without the inclusion of divalent ions In particular, improved grease cleaning can be achieved without divalent ions by the inclusion of organic diamines in combmation with amphotenc and aniomc surfactants m the specific ratios discussed above while enzymes have been shown to improve the skin mildness performance of the present LDL compositions

If they are to be mcluded m an alternate embodiment of the present LDL compositions, then the magnesium ions are present at an active level of from about 0 01 % to 1 %, preferably from about 0 015 % to 0 5 %. more preferably from about 0 025 % to 0 1 %, by weight The amount of magnesium ions present in compositions of the invention will be also dependent upon the amount of total surfactant present therein, mcludmg the amount of alkyl ethoxy carboxylates and polyhydroxy fatty acid amide

Preferably, the magnesium ions are added as a hydroxide, chloπde. acetate, sulfate, formate, oxide or mtrate salt to the compositions of the present invention Because during storage, the stability of these compositions becomes poor due to the formation of hydroxide precipitates m the presence of compositions containing moderate concentrations of hydroxide ions, it may be necessary to add certain chelating agents Suitable chelating agents are discussed further below and m U S Pat No 5,739,092. issued April 14. 1998, to Ofosu-asante. incorporated herein by reference Chelating Agents - The detergent compositions herein may also optionally contam one or more iron and/or manganese chelating agents Such chelating agents can be selected from the group consisting of ammo carboxylates, ammo phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therem, all as heremafter defined Without mtendmg 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

Ammo carboxylates useful as optional chelating agents mclude ethylenediammetetrace- tates, N-hydroxyethylethylenediaminetπacetates, nitnlo-tπ-acetates, ethylenediamine tetrapro- pnonates, tπethylenetetraam ehexacetates, diethylenetπaminepentaacetates, and ethanoldi- glycines, alkah metal, ammomum, and substituted ammonium salts therein and mixtures therein

Ammo phosphonates are also suitable for use as chelating agents in the compositions of the mvention 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 m the compositions herein See U S Patent 3,812,044, issued May 21, 1974. to Connor et al Prefeπed compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dιhydroxy-3.5-dιsulfobenzene

A prefeπed biodegradable chelator for use herem is ethylenediamine disuccmate ("EDDS"), especially the [S.S] isomer as descπbed in U S Patent 4.704.233. November 3, 1987, to Hartman and Perkins

The compositions herem may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder Similarly, the so called "weak" builders such as citrate can also be used as chelating agents

If utilized, these chelating agents will generally compπse from about 0 1% to about 15% 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

Other Perfumes

In addition to the perfume and fragrance matenals mentioned above, the present detergent compositions may also include various other natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil. cedar, and the like Finished perfumes can compπse extremely complex mixtures of such ingredients Further examples of perfume mgredients useful herein can be found in the PCT application "Dishwashmg Detergent Compositions Containing Organic Diammes for Improved Grease Cleaning, Sudsmg, Low Temperature Stability and Dissolution", havmg publication number PCT WO 99/63034, published December 9, 1999, incorporated herem by reference It should be noted that these additional mgredients which come under the headmg "Other Perfumes" are included in addition to the perfume composition formulations discussed above

Other Ingredients - The detergent compositions will further preferably comprise one or more detersive adjuncts selected from the following soil release polymers, polymenc dispersants, polysacchaπdes, abrasives, bacteπcides and other antimicrobials, tarnish inhibitors, builders, enzymes, dyes, buffers, antifungal or mildew control agents, insect repellents, perfumes, hydrotropes, thickeners, processing aids, suds boosters, bπghteners. anti-coπosive aids, stabilizers antioxidants and chelants A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, antioxidants, processing aids, and dyes or pigments If high sudsmg is desired, suds boosters such as the Ci Q-Ci alkanolamides can be incorporated into the compositions, typically at 1%-10% levels The Ci 0-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 amme oxides, betaines and sultames noted above is also advantageous

An antioxidant can be optionally added to the detergent compositions of the present invention They can be any conventional antioxidant used in detergent compositions, such as 2.6- dι-tert-butyl-4-methylphenol (BHT). carbamate. ascorbate. thiosulfate, monoethanolamme(MEA). diethanolamine, tπethanolamme. etc It is preferred that the antioxidant. when present, be present m the composition from about 0 001% to about 5% by weight

Various detersive mgredients employed in the present compositions optionally can be further stabilized by absorbmg 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 bemg absorbed mto the porous substrate In use. the detersive ingredient is released from the substrate into the aqueous w ashing liquor, where it performs its mtended detersive function

To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C 13.15 ethoxylated alcohol (EO 7) nomomc surfactant Typically, the enzyme/surfactant solution is 2 5 X the weight of silica The resulting powder is dispersed with stirring in silicone oil (vanous silicone oil viscosities in the range of 500-12,500 can be used) The resultmg 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, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions

Further, these hand dishwashmg detergent embodiments preferably further comprises a hydrotrope Suitable hydrotropes include sodium, potassium, ammomum or water-soluble substituted ammomum salts of toluene sulfomc acid, naphthalene sulfomc acid, cumene sulfonic acid, and xylene sulfomc acid Non-Aqueous Liquid Detergents

The manufacture of liquid detergent compositions which comprise a non-aqueous caπier medium can be prepared accordmg to the disclosures of U S Patents 4,753.570, 4,767,558, 4,772,413, 4,889,652, 4,892,673, GB-A-2,158,838, GB-A-2.195, 125, GB-A-2.195.649, U S 4,988,462, U S 5.266,233. EP-A-225,654 (6/16/87). EP-A-510.762 (10/28/92). EP-A-540.089 (5/5/93), EP-A-540,090 (5/5/93), U S 4,615,820, EP-A-565.017 (10/13/93). EP-A-030,096 (6/10/81), incorporated herem by reference Such compositions can contam vaπous particulate detersive ingredients stably suspended therem Such non-aqueous compositions thus compπse a liquid phase and. optionally but preferably, a solid phase, all as described m more detail heremafter and in the cited references

The compositions of this invention can be used to form aqueous ashmg solutions for hand dishwashing Generally, an effective amount of such compositions is added to water to form such aqueous cleaning or soaking solutions The aqueous solution so formed is then contacted with the dishware, tableware, and cooking utensils

An effective amount of the detergent compositions herein added to water to form aqueous cleamng solutions can comprise amounts sufficient to form from about 500 to 20.000 ppm of composition in aqueous solution More preferably, from about 800 to 5.000 ppm of the detergent compositions herem will be provided m aqueous cleaning liquor

The following examples are illustrative of the present invention, but are not meant to limit or otherwise define its scope All parts, percentages and ratios used herein are expressed as percent by weight unless otherwise specified EXAMPLES

Several annular disks are made from perfume-impregnated plastics of different compositions and then placed m the closure of a container, such as disclosed in Fig 1, suitable for holdmg the liquid detergent compositions disclosed below The plastics have the following compositions

50% low density polyethylene 50% low density polyethylene 30% ethylvinylacetate 30% ethylvinylacetate 20% hydroxycitronellal 10% alpha-methyl-beta-3,4- methylenedioxy-phenylpropionaldehyde

5% Cyclohexyl alcohol 5% benzyl acetate

50% low density polyethylene 30% ethylvinylacetate 15% lyral 5% Isopropyl 2-methylbutyrate

Light duty liquid dishwashmg detergent compositions prepared according to the present invention are then dispensed mto the container During storage, the perfume-impregnated plastic disks release the odor neutrahzers and fragrance materials in a gaseous phase so that they effectively suppress malodors generated by amines m the liquid detergent composition The compositions are as follows

Table I

Example 1 Example 2 Example 3 Example 4

AEO 6S¹ 26 1 26 1 26 1 26 0

Amme oxide² 6 5 6 5 6 5 6 5

Citπc acid 2 6 2 6 2 6 —

Potassium carbonate — — — 0 75

Sodium carbonate ~ — — 1 75

Suds boosting polymer³ 0 2 0 2 0 2 0 2

Sodium cumene sulfonate 3 50 3 50 3 50 4 0

Propylene glycol 9 8 9 8 9 8 4 0

Nomonic surfactant⁴ 3 0 3 0 3 0 2 9

Diamme 0 50 0 50 0 50 0 50

Perfume composition⁶ 0 05 0 05 — 0 15

Water-soluble cyclodextnn — — 0 5

& fragrances⁷

Water & mmors BAL BAL BAL BAL

Total surfactant active 36 % 36 % 36 % 35 4%

Viscosity (cps @ 20°C) 780 780 780 650 pH @ 10% 10 8 10 8 10 8 10 8

1 Sodium C 12-13 alkyl ethoxy sulfate containing an average of 0 6 ethoxy groups

2 C₁₂-C₁₄ alkyl dimethyl amine oxide

3 Polymer is (N,N-dιmethylamιno)ethyl methacrylate homopolymer

4 Nonionic may be either Cl 1 Alkyl ethoxylated surfactant containing 9 ethoxy groups or CIO Alkyl ethoxylated surfactant containing 8 ethoxy groups

5 1,3 bιs(methylaπ_ιne)-cyclohexane

6 The perfume composition is that described in table II

7 The cyclodextrm and fragrance materials are selected as directed by the disclosure of the pending provisional application of Foley et al . "Detergent Compositions with Perfume Complexes to Mask Malodors," havmg P&G Case No 7806P2. Serial No 60/204287, filed May 15, 2000, incorporated herein by reference Table II

A perfume composition of the present invention is as follows:

Fragrance Material Weight % benzyl acetate 28.09 ethyl-2 -methyl butyrate 0.70 ortho tertiary butyl cyclohexanyl 14.04 acetate para-Ethyl-alpha, alpha-Dimethyl 0.28

Hydrocinnamaldehyde

P. T. Bucinal 42.13

3 -Cyclohexane- 1 -Carboxaldehyde, 4- 14.04 (4-Hydroxy-4-Methyl Pentyl) Watermint 0.70

Claims

WHAT IS CLAIMED IS

1 A package for storing a liquid, compnsmg a contamer havmg at least one compartment for storing a liquid, a dispensing opening in liquid communication with said at least one compartment, a closure for sealing said opening, and a perfume-impregnated plastic member, wherein said perfume-impregnated plastic member is in communication with said compartment

2 A package for storing a liquid accordmg to claim 1 wherein the perfume-impregnated plastic member comprises a perfume composition comprismg from about 10%) to about 100% of an odor neutralizer, and said plastic member releases the odor neutralizer m a gaseous phase whereby the odor neutralizer is capable of reacting with one or more malodor-generating compounds to suppress malodors

3 A package for stormg a liquid accordmg to claim 2 wherein one of the malodor generatmg compounds is an amme and the nonodiferous reaction product is a Schiff base

4 A package for stormg a liquid according to claim 3 wherem the odor neutralizer is selected from the group consistmg of para-tertiaiy-Butyl-alpha-methly hydrocmnamic aldehyde, 4-(4- Methyl-4-hydroxyamyl)-3-cyclohexane-l-Carboxaldehyde. hydroxy citronellal. and alpha-methyl - beta-3.4-methylenedιoxy-phenylpropιonaldehyde, and mixtures thereof

5 A package for stormg a liquid accordmg to claim 1 wherein the perfume-impregnated platic member compπses a perfume composition comprising from about 0 5% to about 4% of fragrance mateπals havmg a boilmg pomt of less than about 180°C. and said plastic member releases fragrance materials in a gaseous phase so that upon being released the fragrance materials effectively suppress malodors

6 A package for storing a liquid accordmg to claim 1 wherein the perfume-impregnated plastic member comprises a perfume composition comprising from about 15% to about 40% of fragrance matenals havmg a boiling point of between about 180°C and about 260°C, and said plastic member releases fragrance mateπals m a gaseous phase so that upon bemg released the fragrance mateπals effectively suppress malodors

7 The package of claim 1 wherein said plastic member is disposed adjacent said dispensing opening

8 A perfume-impregnated mateπal compπsing a perfume composition, wherein the perfume composition compπses from about 10% to about 100% of an odor neutralizer and said perfume- impregnated matenal releases the odor neutralizer m a gaseous phase whereby the odor neutralizer is capable of reactmg with one or more malodor-generatmg compounds to suppress malodors

9 A perfume-impregnated member according to claim 8 wherein the odor neutralizer is selected from the group consisting of para-tertiary-Butyl-alpha-methly hydrocinnamic aldehyde, 4- (4-Methyl-4-hydroxyamyl)-3-cyclohexane-l-Carboxaldehyde, hydroxycitronellal, and alpha- methyl-beta-3,4-methylenedιoxy-phenylpropιonaldehyde. and mixtures thereof

10 A perfume-impregnated member according to claim 8 wherein the perfume composition comprises from about 15% to about 40% of fragrance materials havmg a boilmg point of between about 180°C and about 260°C

11 The package of claim 1. wherein the surface area of said plastic member which is exposed to said compartment is between about 1 cm² and about 10 cm²

12 The package of claim 1 , wherein the ratio of the surface area of said plastic member which is exposed to said compartment to the volume of said compartment is between about 0 0005 1 cm²/ml and about 10 1 cm²/ml

13 The package of claim 1, wherein the perfume-impregnated plastic member comprises a perfume composition compπsing a fragrance material selected from the group consistmg of methyl acetoacetate, cyclohexyl alcohol. 3 -methyl- 1-pentanol, 1.3-Dιmethylbutyal acetate, isopropyl 2- methylbutyrate, ethyl-2-methylbutyrate. and mixtures thereof

14 The package of claim 1, wherein said perfume-impregnated plastic member comprises a polymer matenal selected from the group consistmg of low density polyethylene, expandable polystyrene compositions, high density polyethylene, blended polyethylene and carbon black, polyene/alpha-olefin copolymers, poly-alpha-olefins, polyolefins, polyethylene oxides, olefin polymers and co-polymers, chlorinated PVC, polyepsilon caprolactone co-polymers, styrene acrylonitπle co-polymers, co-polymers of epsilon caprolactone with 1 ,4-butane diol, polyesters, chlormated polyethylene, plasticized polyepsilon caprolactone co-polymers contaimng dimethyl phthalate plasticizers, maleic anhydride modified adducts of polyepsilon caprolactone polyols and ethylemcally unsaturated monomer, polyurethane polymers having lactone backbones, polyurethane polyether resms wherem the resm is obtamed by reactmg a polyfunctional lactone with a long chain polyalkylene diol and a urethane precursor and resms havmg polyurethane backbones, and mixtures thereof

15 The package of claim 1, wherem said plastic member is an annular disk which is disposed adjacent to said dispensing opening

16 The package of claim 15, wherem the average thickness of said disk is between about 2 mm and about 20 mm

17 A package for storing a liquid, compnsmg a container having at least one compartment for storing a liquid, a liquid disposed within said compartment compnsmg a first perfume composition, a dispensmg opening in liquid communication with said at least one compartment, a closure for sealing said opening, and a plastic member comprising a second perfume composition, wherem said plastic member is in communication with said compartment and said second perfume composition comprises an odor neutralizer, and said plastic member releases the odor neutralizer m a gaseous phase whereby the odor neutralizer is capable of reactmg with one or more malodor-generating compounds to suppress malodors

18 A package for storing a liquid detergent according to claim 17. wherein the liquid detergent further compnses a) an amonic surfactant, b) a solvent, c) an amine having a pKa of greater than about 8 0, and wherem the first perfume composition compπses from about 30 % to about 100 % of an odor neutralizer which is capable of forming a Schiff base when reacted with an amme, and wherem the composition has a pH of from about 8 5 to about 12

19 A package for stoπng a liquid detergent according to claim 18, wherem the first perfume composition further comprises from about 0 10% to about 4% of fragrance mateπals havmg a boilmg pomt of less than about 180°C

20 A package for storing a liquid detergent accordmg to claim 19. wherem the first perfume composition further comprises from about 20%) to about 70% of fragrance materials having a ClogP value of greater than about 2 5

21 A package for stoπng a liquid detergent according to claim 18, wherein the liquid detergent further comprises an amphotenc surfactant, a low molecular weight, malodor-generating organic diamme havmg a pKl and a pK2, wherem the pKl and the pK2 of said diamine are both m the range of from about 8 0 to about 11 5. and wherem the mole ratio of said amonic surfactant to said amphotenc surfactant to said diamine is from about 100 40 1 to about 9 0 5 1

22 A package for stormg a liquid detergent accordmg to claim 17, wherem the liquid detergent further comprises nitrogenous compounds in which an amine is present as an impurity at a level of at least 1 ppm of the nitrogenous compounds

23 A package for stormg a liquid detergent according to claim 17. wherem the liquid detergent further comprises a mtrogen-contaimng polymer or a mtrogen-contaimng surfactant, wherem the nitrogen-containing surfactant is selected from the group consisting of amme oxides, amphotenc surfactants, glucose amides, and mixtures thereof and the amme is present as an impurity at a level of at least 1 ppm of the mtrogen-contaimng surfactants and the nitrogen-containing polymers

24. A package for storing a liquid detergent according to claim 17, wherein the liquid detergent further comprises water-soluble cyclodextrin molecules.