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EP1161515B1 - Compositions de parfums masquant les mauvaises odeurs d'amines et procedes correspondants - Google Patents

Compositions de parfums masquant les mauvaises odeurs d'amines et procedes correspondants Download PDF

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Publication number
EP1161515B1
EP1161515B1 EP00914957A EP00914957A EP1161515B1 EP 1161515 B1 EP1161515 B1 EP 1161515B1 EP 00914957 A EP00914957 A EP 00914957A EP 00914957 A EP00914957 A EP 00914957A EP 1161515 B1 EP1161515 B1 EP 1161515B1
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Prior art keywords
composition
weight
compositions
present
perfume
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German (de)
English (en)
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EP1161515A1 (fr
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Carl Eric Kaiser
Alan Scott Goldstein
Mark Leslie Kacher
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes

Definitions

  • the present invention relates to detergent and cleaning compositions, particularly liquid or gel dishwashing compositions suitable for use in manual dishwashing operations.
  • These detergent compositions contain anionic surfactants, solvents and perfume compositions which are specially selected to cover the malodors generated by nitrogenous compounds like amines.
  • These components in the combinations disclosed herein, provide dishwashing detergent compositions which have preferred food soil cleaning, handling and sudsing characteristics without the odors typically associated with amines.
  • the present invention also relates to the perfume compositions themselves and methods for masking malodors.
  • Light-duty liquid (LDL) or gel detergent compositions useful for manual dishwashing are well known in the art. Such products are generally formulated to provide a number of widely diverse performance and aesthetics properties and characteristics. First and foremost, liquid or gel dishwashing products must be formulated with types and amounts of surfactants and other cleaning adjuvants that will provide acceptable solubilization and removal of food soils, especially greasy soils, from dishware being cleaned with, or in 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.
  • Diamines are a type of nitrogenous compound which can improve the cleaning performance of liquid dishwashing detergent compositions, in particular the cleaning of greasy, hydrophobic soils on dishware or other kitchen articles.
  • diamines can also cause extremely potent malodors, such as the unpleasant fragrance associated with permanent kits commonly used to curl hair.
  • nitrogen-containing surfactants and polymers can provide both cleaning and sudsing advantages, but frequently contain amine impurities as by-products in commercial materials.
  • amine impurities as by-products in commercial materials.
  • the resultant free amine can be malodors. Consequently, it has been difficult to formulate a malodor-free light duty liquid at pH higher than 8.5
  • a liquid dishwashing detergent which incorporates certain nitrogen-containing components (e.g. diamines) which are capable of providing excellent cleaning performance but which is free of the malodors generally associated with the use of these components.
  • the present invention also relates to a perfume compositions suitable for use in liquid dishwashing detergents,.
  • liquid dishwashing detergent containing nitrogenous compounds like amines can be prepared which provides excellent cleaning performance, particularly on greasy and hydrophobic soils, and includes a perfume composition which contains certain fragrance materials and odor neutralizers that are particularly effective at masking the malodors generated by nitrogenous compounds.
  • the detergent compositions according to the first aspect of the present invention comprise: (a) an anionic surfactant; (b) a solvent; (c) an amine having a pKa of greater than 8.0; and (d) a perfume composition comprising from 30 % to 100 % of an odor neutralizer which is capable of forming a Schiff base when reacted with an amine.
  • the pH of the detergent composition (as measured as 10% aqueous solution) is from 8.5 to 12 and, in preferred embodiments, the mole ratio of said anionic surfactant to any amphoteric surfactant present to any diamine present is from 100:40:1 to 9:0.5:1.
  • a detergent composition suitable for use in hand dishwashing comprising: (a) from 0.1% to 5%, by weight of a diamine having a molecular weight less than or equal to 400 g/mol; (b) from 5% to 50%, by weight, of an anionic surfactant; (c) from 0.5% to 10%, by weight, of an amphoteric surfactant; (d) from 0.1 % to 10.0 %, by weight, of a buffering agent; (e) from 0.1 % to 1.5 %, by weight, of an alkali metal inorganic salt; and (f) from about 0.75 % to 25.0 %, by weight, of a solvent.
  • the present detergent compositions comprise an "effective amount” or a "grease removal-improving amount” of individual components defined herein.
  • 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 cleaning composition against at least some of the target soils and stains.
  • the formulator will use sufficient diamine to at least directionally improve cleaning performance against such stains.
  • LDL light-duty liquid
  • kitchen articles it is meant cookware, flatware, dishes and dishware, silverware and other articles commonly found in 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.
  • nitrogenous compounds those compounds containing nitrogen and related to ammonia or ammonium.
  • Such compounds include amines, polyamines, amine oxide surfactants, amides, surfactants in which the hydrophilic, polar groups are neutralized by an ammounium cation, alkanolamine solvents (e.g. monoethanolamine, diethanolamine, and triethanolamine) and other similar compounds which are typically used in detergent or cleaning compositions.
  • malodor any detectable odor associated with an amine or other nitrogenous compounds related to ammonia or ammonium.
  • amine any derivative of ammonia or ammonium 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.
  • scent it is meant any detectable odor associated with and originating in a fragrance material.
  • ethylene oxide group it is meant the following structure:
  • the perfume compositions designed to mask these nitrogenous malodors comprise fragrance materials and odor neutralizers, which will now be set-forth in more detail below.
  • the present detergent composition will comprise from 0.01 % to 0.5 %, preferably from 0.02 % to 0.2 %, most preferably from 0.03 % to 0.08 %, by weight of the perfume composition.
  • the present perfume compositions contain fragrance materials which mask the presence of malodors emanating from amines and so allow the liquid dishwashing detergent to be free of amine malodors. These fragrance materials mask the amine malodors by providing scents which compete with the malodors for access to the nasal receptor sites.
  • fragrance materials contained in the present perfume compositions to mask malodors is related both to: 1) the amount of time that the scents emanating from the fragrances require to diffuse into the air and hence move from the detergent composition containers to the nasal receptor sites; and 2) the relative potency of a scent or malodor.
  • the rate at which a fragrance material diffuses into the air and hence escapes the detergent composition can also be related to its hydrophobicity, which is discussed in more detail below.
  • fragrance materials which constitute the perfume compositions of the present invention will be selected based on one or more of these three criteria: volatility, hydrophobicity and potency.
  • An essential component of the perfume compositions of the present invention is a highly volatile fragrance material.
  • Highly volatile fragrance materials have lower boiling points than other substances and so the scents from these materials quickly diffuse into the air, and compete with the malodors to bind 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 amine malodors do finally arrive the nasal receptor sites have already been occupied thus effectively masking the recognition of the amine malodors.
  • the present perfume compositions may comprise from 0.10 % to 4 %, preferably from 0.15 % to 2.5 %, most preferably from 0.20 % to 2.0 %, of the highly volatile fragrance materials.
  • Highly volatile fragrance material have a boiling point of below 180°C, preferably below 160°C , most preferably below 140°C under 1 atmosphere of pressure.
  • Suitable highly volatile fragrance materials include the following: Fragrance Material Boiling Point (°C) Methyl acetoacetate 172 Cyclohexyl alcohol 161 3-Methyl-1-pentanol 151 1,3-Dimethylbutyal acetate 148 Isopropyl 2-methylbutyrate 138 ethyl-2-methylbutyrate 131
  • volatile fragrance materials are less volatile than the highly volatile fragrance materials and have a boiling point of between 180°C and 260 °C, more preferably between 185°C and 240°C, most preferably between 190°C and 220°C under 1 atmosphere of pressure.
  • the perfume compositions of the present invention may comprise from 30 % to 50 %, preferably from 35 % to 50 %, most preferably from 40 % to 45 %, of volatile fragrance materials.
  • the perfume compositions of the present invention are more effective at masking amine malodors and other malodors originating in nitrogenous compounds when both highly volatile and volatile perfume compositions are present.
  • the present perfume compositions effectively mask these malodors because they include highly-volatile fragrance materials, which arrive at the nasal receptor sites before the malodors, therefore effectively masking the malodors.
  • 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.
  • fragrance materials in the perfume composition which are not as volatile as the highly volatile fragrance materials.
  • the scents from these fragrance materials should arrive 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.
  • Nonlimiting examples of suitable volatile fragrance materials and their respective boiling point values under 1 atmosphere of pressure include the following: Fragrance Material Boiling Point (°C) 3,7-dimethyl-1,6-octadien-3-ol 198 3,7-dimethyl-7-hydroxyoctan-1-al 241 n-decyl aldehyde 215 benzaldehyde 179 anisic aldehyde 248 benzyl acetate 215 allyl hexanoate 185 methyl-2-aminobenzoate 237 2-cis-3,7-dimethyl-2,6-octadien-1-ol 227 3,7-dimethyl-trans-2,6-octadien-1-ol 230 3,7-dimethyl-6-octen-1-ol 225 2,6-dimethyl-7-octen-2-ol 208 2-phenylethyl alcohol 220 1-methyl-4-iso-propyl-1-cyclohexen-8-o
  • 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 Boiling 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 Boiling 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.
  • the perfume compositions of the present invention may comprise from 20 % to 70 % , preferably from 30 % to 60 %, most preferably from 40 % to 55 % of fragrance materials which have ClogP values of greater than 2.5.
  • the logP of many perfume ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylog CIS), Irvine, Calif., contains many, 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 Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990).
  • the fragment approach is based on the chemical structure of each perfume ingredient, and takes into 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 in the present invention.
  • Nonlimiting examples of suitable fragrance materials and their respective ClogP values include the following: Perfume Material ClogP Benzyl acetate 2.0 Ethyl-2-methylbutyrate 2.2 Furfuryl valerate 2.7 Isobutyl benzyl carbinol 2.9 para-Ethyl-alpha, alpha-dimethylHydrocinnamaldehyde 3.4 Isobutyl caproate 3.8 4-tert.-butylcyclohexyl acetate 4.1
  • the fragrance materials used herein has a low-odor-detection threshold.
  • low-odor-threshold fragrance materials have a odor detection threshold of less than 4.0 mg/L, preferably less than 1.0, more preferably less than 0.10 mg/L when the fragrance material is dissolved in a water matrix.
  • the perfume composition of the present invention may comprise less than 20 %, preferably less than 8 %, most preferably less than 0.08 % of fragrance materials which have a low-odor-threshold.
  • odor detection threshold of fragrance materials are well-known and disclosed in available reference materials, e.g., "Compilation of Odor and Taste Threshold Values Data," F.A. Fazzalari, ed., American Society for Testing and Materials, 1978.
  • a gas chromatograph is characterized to determine the exact volume of material injected by the syringe, the precise split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution. The air-flow is accurately measured and, assuming the duration of a human inhalation to last 0.2 minutes, the sample volume is calculated. Since the precise concentration at the detector at any point in time is known, the mass per volume inhaled is known and hence the concentration of material. To determine whether a material has a threshold below 4 mg/L, solutions are delievered to the sniff port at the back-calculated concentration. A panelist sniffs the GC effluent and identifies the retention time when odor is noticed. The average over all panelists determines the threshold of detectability.
  • fragrance material is injected onto the column to achieve a 4 mg/L concentration at the detector.
  • Typical gas chromatograph parameters for determining odor detection thresholds are listed below.
  • a sufficient amount of fragrance material is injected onto the column to achieve a 1.0 mg/L or 0.1 mg/L concentration at the detector.
  • Odor neutralizers work differently than the fragrance materials discussed above. They mask the malodors by depriving the malodors of access to the nasal receptor sites, but by reducing the amount of the amines generating the malodor. Any chemical species that upon reacting with an amines yields products which generate little or significantly less malodor than amines is suitable as an odor neutralizer.
  • a preferred species of odor neutralizers are aldehydes; it is well known that aldehydes react with amines in a Schiff reaction to produce a Schiff base and water:
  • R a and R b are both aliphatic substituents.
  • the amine may be a diamine included 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 reacting an aldehyde with a amine they reduce the amount of the amine which is present to generate malodors.
  • aldehydes suitable for use in the present invention include: para-tertiary-Butyl-alpha-methly hydrocinnamic aldehyde, 4-(4-Methyl-4-hydroxyamyl)-3-cyclohexane-1-Carboxaldehyde, 4-(4-Hydroxy-4-Methyl Pentyl), hydroxycitronellal, alpha-methyl-beta-3,4-methylenedioxyphenylpropionaldehyde as well as most aldehydes.
  • Many odor neutralizers e.g. several different species of aldehydes, emit a characteristic scent and can also serve in the present invention as a fragrance material.
  • perfume compositions of the present invention will consist of an odor neutralizer which is capable of forming a Schiff base when reacted with an aldehyde.
  • diamines in combination with amphoteric 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 in the amount of divalent ions in the preferred embodiments of the present formula.
  • This improved cleaning is a result of diamines' 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 dishwashing detergents, especially compact formulations, at even significantly higher viscosities (e.g., 1,000 centipoise or higher) than conventional formulations while maintaining excellent dissolution and cleaning performance. This has significant potential advantages for making compact products with a higher viscosity while maintaining acceptable dissolution.
  • pKa1 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 diamines.
  • the diamines useful herein can be defined by the following structure: wherein R 2-5 are independently selected from H, methyl, -CH 3 CH 2 , and ethylene oxides; C x and C v are independently selected from methylene groups or branched alkyl groups where x+y is from about 3 to about 6; and A is optionally present and is selected from electron donating or withdrawing moieties chosen to adjust the diamine pKa's to the desired range. If A is present, then x and y must both be 1 or greater.
  • anionic surfactants useful in the present invention 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, sarcosinates, taurinates, and mixtures thereof.
  • An effective amount typically from 0.5% to 90%, preferably 5% to 50%, more preferably from 10 to 30%, by weight of anionic detersive surfactant can be used in the present invention.
  • anionic surfactants may be found in copending provisional patent application of Chandrika Kasturi et al., entitled “Liquid Detergent Compositions Comprising Polymeric Suds Enhancers", having P & G Case No. 6938P, serial no. 60/066,344 and filed on November 21, 1997. 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 in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23. Suitable anionic surfactants may further be found in U.S. Pat. No. 5,415,814 issued 16 May 1995, to Ofosu-Asante et al.
  • Semi-polar detergent surfactants include the amine oxide surfactants having the formula wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • amphoteric surfactants and amine oxides in particular, are disclosed in the copending provisional application of Joanna M. Clarke entitled “Diols and Polymeric Glycols for Improved Dishwashing Detergent Compositions", having P & G Case No. 7408P and application serial no. 60/119,044, which is hereby incorporated in its entirety, by reference.
  • amphoteric surfactant is present in the composition in an effective amount, more preferably from 0.1% to 20%, even more preferably 0.1% to 15%, even more preferably still from 0.5% to 10%,by weight.
  • Secondary Surfactants - Secondary detersive surfactant can be selected from the group consisting of nonionics, cationics, ampholytics, zwitterionics, and mixtures thereof.
  • the present detergent compositions can be formulated to be used in the context of laundry cleaning or in other different cleaning 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 in the copending provisional patent application of Chandrika Kasturi et al., entitled “Liquid Detergent Compositions Comprising Polymeric Suds Enhancers", having P & G Case No. 6938P, application serial no. 60/066,344.
  • the ratio of the anionic surfactant: amphoteric: diamine is from 100:40:1 to 9:0.5:1, by mole, preferably the ratio of the anionic surfactant: amphoteric: diamine is from 27:8:1 to 11:3:1, by mole. It has been found that detergent compositions containing anionic surfactant, amphoteric surfactant and diamine in this specific ratio range provide improved low temperature stability, deliver better grease removal and tough food cleaning benefits at pH less than 12.5, and improved hard water cleaning.
  • the mole ratio of anionic surfactant to diamine 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 cleaning.
  • Solvents A variety of water-miscible liquids such as lower alkanols, diols, polyols, ethers, amines and polymeric glycols which comprise ethylene oxide (EO) and propylene oxide (PO) groups and the like may be used in the present invention. Particularly preferred are the C1-C4 alkanols, diols and the above mentioned polymeric glycols.
  • the composition will preferably contain at least 0.01%, more preferably at least 0.5%, even more preferably still, at least 1% by weight of the composition of solvent.
  • the composition will also preferably contain no more than 20%, more preferably no more than 10%, even more preferably, no more than 8% by weight of the composition of solvent.
  • solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present.
  • Solvents are broadly defined as compounds that are liquid at temperatures of 20°C-25°C and which are not considered to be surfactants. One of the distinguishing features is that solvents tend to exist as discrete entities rather than as broad mixtures of compounds. Examples of suitable solvents for the present invention include ethanol, propanol, propylene glycol, polypropylene glycol and isopropanol, 2-methyl pyrrolidinone, benzyl alcohol and morpholine n-oxide. Preferred among these solvents are ethanol and isopropanol.
  • Preferred diols include propylene glycol, 1,2 hexanediol, 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
  • the present compositions will comprise at least 0.5 %, more preferably at least 1%, even more preferably still, at least 3% by weight of the composition of diols.
  • the composition will also preferably contain no more than 20%, more preferably no more than 10%, even more preferably, no more than 6% by weight of the composition of diols.
  • Polymeric glycols are also suitable for use in the present invention.
  • a preferred polymeric glycol is a polyproylene glycol having an average molecular weight of between about 1000 to about 5000, more preferably between about 2000 to about 4000, most preferably about 2000 to about 3000.
  • suitable polymeric glycols as well as their acceptable concentrations for use in a LDL compositions are disclosed in the copending provisional application of Joanna M. Clarke entitled “Diols and Polymeric Glycols for Improved Dishwashing Detergent Compositions", having P & G Case No. 7408P and application serial no. 60/119,044.
  • glycols according to the formula: HO-CR1R2-OH wherein R1 and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic are suitable and can be used herein.
  • R1 and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic are suitable and can be used herein.
  • One such suitable glycol is dodecaneglycol.
  • Suitable alkoxylated glycols which can be used herein are according to the formula R ⁇ (A) n -R 1 -OH wherein R is H, OH, a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein R 1 is H or a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated glycols to be used herein are methoxy octadecanol and/or ethoxyethoxyethanol.
  • Suitable aromatic alcohols which can be used herein are according to the formula R-OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
  • R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
  • a suitable aromatic alcohol to be used herein is benzyl alcohol.
  • the present invention may also include alkanolamine solvents (e.g. monoethanolamine, diethanolamine, and triethanolamine) which may also be included in the present invention as antioxidants.
  • alkanolamine solvents e.g. monoethanolamine, diethanolamine, and triethanolamine
  • Suitable aliphatic branched alcohols which can be used herein are according to the formula R-OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12.
  • Particularly suitable aliphatic branched alcohols to be used herein include 2-ethylbutanol and/or 2-methylbutanol.
  • Suitable alkoxylated aliphatic branched alcohols which can be used herein are according to the formula R (A)n-OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and/or 2-methylbutoxyethanol.
  • Dishwashing compositions of the present invention will thus contain from about 0.5% to 15%, preferably from 1% to 12%, most preferably from 2% to 10%, by weight, of a buffering agent.
  • the pKa value of this buffering agent should be 0.5 to 1.0 pH units below the desired pH value of the composition (determined as described above
  • the pKa of the buffering agent should be from 7 to 12. Under these conditions the buffering agent most effectively controls the pH while using the least amount thereof.
  • Preferred inorganic buffers/alkalinity 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 nitrogen-containing materials. Further examples of suitable buffering agents may be found in 7408P.
  • compositions of the present invention may optionally contain a polymeric suds stabilizer.
  • These polymeric suds stabilizers provide extended suds volume and suds duration without sacrificing the grease cutting ability of the liquid detergent compositions.
  • These polymeric suds stabilizers are selected from:
  • One preferred polymeric suds stabilizer is (N,N-dimethylamino)alkyl acrylate esters, namely When present in the compositions, the polymeric suds booster may be present in the composition from 0.01% to 15%, preferably from 0.05% to 10%, more preferably from 0.1% to 5%, by weight.
  • compositions according to the present invention may further comprise a builder system. Because builders such as citric acid and citrates impair the stability of enzymes in LDL compositions, it is desirable to include reduce the amounts or completely remove the builder salts normally utilized in LDL compositions incorporating propylene glycol as a builder. When a detergent composition includes propylene glycol solvent as a part or a whole of the detergent's carrier, enzymes are more stable and smaller amounts or no builder salts are needed.
  • any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylene-diamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylene-phosphonic acid.
  • aluminosilicate materials silicates, polycarboxylates and fatty acids
  • materials such as ethylene-diamine tetraacetate
  • metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylene-phosphonic acid.
  • phosphate builders can also be used herein.
  • polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
  • suitable fatty acid builders for use herein are saturated or unsaturated C 10-18 fatty acids, as well as the corresponding soaps.
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
  • Enzymes - Detergent compositions of the present invention 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, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases or mixtures thereof.
  • a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase. Enzymes when present in the compositions, at from 0.0001% to 5% of active enzyme by weight of the detergent composition.
  • Preferred proteolytic enzymes are selected from the group consisting of Alcalase ® (Novo Industri A/S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred.
  • Preferred amylase enzymes include TERMAMYL®, DURAMYL® and the amylase enzymes those described in WO 9418314 to Genencor International and WO 9402597 to Novo.
  • Hydrogen peroxide is often found as an impurity in surfactants and surfactant pastes.
  • the preferred level of hydrogen peroxide in the amine oxide or surfactant paste of amine oxide is 0-40 ppm, more preferably 0-15 ppm.
  • Amine impurities in amine oxide and betaines, if present, should be minimized to the levels referred above for hydrogen peroxide and preferably should be less than 1 ppm.
  • divalent ions be omitted from LDL compositions prepared according to the present invention
  • alternate embodiments of the present invention may include magnesium ions.
  • divalent ions may lead to slower dissolution as well as poor rinsing, and poor low temperature stability properties.
  • 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.
  • magnesium ions offer several benefits.
  • 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 in softened water that contains few divalent ions.
  • the magnesium ions are present at an active level of from 0.01 % to 1 %, preferably from 0.015 % to 0.5 %, more preferably from 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, including the amount of alkyl ethoxy carboxylates and polyhydroxy fatty acid amide.
  • the magnesium ions are added as a hydroxide, chloride, acetate, sulfate, formate, oxide or nitrate 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 in 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 in U.S. Pat. No. 5,739,092, issued April 14, 1998, to Ofosu-asante.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-tri-acetates, 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.
  • compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder.
  • MGDA water-soluble methyl glycine diacetic acid
  • so called "weak” builders such as citrate can also be used as chelating agents.
  • these chelating agents will generally comprise 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.
  • 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 comprise extremely complex mixtures of such ingredients.
  • perfume ingredients useful herein can be found in the copending provisional patent application: "Dishwashing Detergent Compositions Containing Organic Diamines for Improved Grease Cleaning, Sudsing, Low temperature stability and Dissolution", having P & G Case No. 7167P, application serial no. 60/087,693. It should be noted that these additional ingredients which come under the heading "Other Perfumes" are included in addition to the perfume composition formulations discussed above.
  • the detergent compositions will further preferably comprise one or more detersive adjuncts selected from the following: soil release polymers, polymeric dispersants, polysaccharides, abrasives, bactericides and other antimicrobials, tarnish inhibitors, builders, enzymes, dyes, buffers, antifungal or mildew control agents, insect repellents, perfumes, hydrotropes, thickeners, processing aids, suds boosters, brighteners, anti-corrosive aids, stabilizers antioxidants and chelants.
  • soil release polymers polymeric dispersants, polysaccharides, abrasives, bactericides and other antimicrobials, tarnish inhibitors, builders, enzymes, dyes, buffers, antifungal or mildew control agents, insect repellents, perfumes, hydrotropes, thickeners, processing aids, suds boosters, brighteners, anti-corrosive aids, stabilizers antioxidants and chelants.
  • compositions herein 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, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc.
  • suds boosters such as the C 10 -C 16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
  • the C 10 -C 14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • 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-di-tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolamine(MEA), diethanolamine, triethanolamine, etc. It is preferred that the antioxidant, when present, be present in the composition from 0.001% to 5% by weight.
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • MEA monoethanolamine
  • MEA diethanolamine
  • triethanolamine triethanolamine
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • these hand dishwashing detergent embodiments preferably further comprises a hydrotrope.
  • Suitable hydrotropes include sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluene sulfonic acid, naphthalene sulfonic acid, cumene sulfonic acid, xylene sulfonic acid.
  • liquid detergent compositions which comprise a non-aqueous carrier medium can be prepared according 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.
  • compositions can contain various particulate detersive ingredients stably suspended therein.
  • non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references.
  • compositions of this invention can be used to form aqueous washing solutions for use hand dishwashing.
  • 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.
  • BAL. BAL. BAL. BAL. BAL. BAL. Viscosity (cps @ 70F) 353 640 635 848 pH @ 10% 10.8 10.8 10.8 10.8 10.8 A light duty liquid dishwashing detergent of the present invention is as follows: Example 5 Example 6 Example 7 AE(1-3)S 31.0 34.0 31.0 Amine oxide 5.0 5.0 4.0 C 12-14 Glucose Amide 4.0 4.0 EO/PO Block Copolymer 0.4 0.3 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Sodium Chloride -- 4.0 -- Sodium Xylene Sulfonate 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Nonionic 1.0 1.0 1.0 Na 2 CO 3 -- 3.0 KCl 2.5 -- 2.5 K 2 CO 3 3.0 -- 2.5 Ethanol 5.0 7.0 5.0 Viscosity Thickener 1.0 -- -- Perfume Composition 0.05 0.05 0.05 Other Perfumes 0.2 0.2 0.2 Water and Misc
  • a light duty liquid dishwashing detergent of the present invention is as follows: Example 8 AE0.6S 26.1 Amine oxide 6.5 Citric acid 2.6 Suds boosting polymer 0.2 Sodium Cumene Sulfonate 3.50 propylene glycol 9.8 NonionicC11E9 3.0 Diamine 0.50 Perfume Composition 0.05 Water BAL.
  • 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 acetate 14.04 para-Ethyl-alpha, alpha-Dimethyl Hydrocinnamaldehyde 0.28 P. T. Bucinal 42.13 3-Cyclohexane-1-Carboxaldehyde, 4-(4-Hydroxy-4-Methyl Pentyl) 14.04 Watermint 0.70

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Claims (10)

  1. Composition détergente liquide pour le lavage de la vaisselle utilisable pour le lavage de la vaisselle à la main, ladite composition étant caractérisée par :
    a) un tensioactif anionique ;
    b) un solvant ;
    c) une amine ayant un pKa supérieur à 8,0 ; et
    d) une composition de parfum caractérisée par 30 % à 100 % en poids d'un agent neutralisant les odeurs qui est capable de former une base de Schiff quand il réagit avec une amine ;
    dans laquelle la composition a un pH de 8,5 à 12.
  2. Composition détergente liquide pour le lavage de la vaisselle selon la revendication 1, dans laquelle la composition de parfum est en outre caractérisée par 0,1 % à 4 % en poids d'un matériau odorant ayant un point d'ébullition inférieur à 180°C.
  3. Composition détergente liquide pour le lavage de la vaisselle selon la revendication 1 ou 2, dans laquelle la composition de parfum est en outre caractérisée par 30 % à 50 % en poids d'un matériau odorant ayant un point d'ébullition entre 180°C et 260°C.
  4. Composition détergente liquide pour le lavage de la vaisselle selon l'une quelconque des revendications 1 à 3, dans laquelle la composition de parfum est en outre caractérisée par 20 % à 70 % en poids d'un matériau odorant ayant une valeur de ClogP supérieure à 2,5.
  5. Composition détergente liquide pour le lavage de la vaisselle selon l'une quelconque des revendications 1 à 4, dans laquelle la composition de parfum est en outre caractérisée par moins de 20 % en poids d'un matériau odorant ayant un seuil de détection d'odeur inférieur à 4,0 mg/l dans une solution de matériau odorant et d'eau.
  6. Composition détergente liquide pour le lavage de la vaisselle selon l'une quelconque des revendications 1 à 5, dans laquelle la composition contient moins de 0,5 % en poids de peroxyde d'hydrogène.
  7. Procédé pour éviter la perception par le consommateur d'odeurs d'amines émanant d'une composition, ce procédé étant caractérisé par la préparation d'une composition de parfum comprenant :
    a) 0,1 % à 4 % en poids d'un matériau odorant ayant un point d'ébullition inférieur à 180°C ; et
    b) 30 % à 100 % en poids d'un agent neutralisant les odeurs qui est capable de former une base de Schiff quand il réagit avec une amine ;
    la préparation d'une seconde composition qui contient des amines générant de mauvaises odeurs ; et l'addition de la composition de parfum comme ingrédient dans la seconde composition.
  8. Procédé selon la revendication 7, dans lequel la composition de parfum est en outre caractérisée par 30 % à 50 % en poids d'un matériau odorant ayant un point d'ébullition entre 180°C et 260°C.
  9. Procédé selon l'une quelconque des revendications 7 et 8, dans lequel la composition de parfum comprend en outre 20 % à 70 % en poids d'un matériau odorant ayant une valeur de ClogP supérieure à 2,5.
  10. Procédé selon l'une quelconque des revendications 7 à 9, dans lequel la composition de parfum est en outre caractérisée par moins de 20 % en poids d'un matériau odorant ayant un seuil de détection d'odeur inférieur à 4,0 mg/l, quand on la teste dans une solution de matériau odorant et d'eau.
EP00914957A 1999-03-15 2000-03-14 Compositions de parfums masquant les mauvaises odeurs d'amines et procedes correspondants Expired - Lifetime EP1161515B1 (fr)

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EP1786891A1 (fr) * 2004-09-08 2007-05-23 The Procter and Gamble Company Compositions de traitement du linge a odeur amelioree
US8814861B2 (en) 2005-05-12 2014-08-26 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
CN100400633C (zh) * 2006-03-30 2008-07-09 中国日用化学工业研究院 一种手洗餐具洗涤剂及制备方法
DE102007012910A1 (de) 2007-03-19 2008-09-25 Momentive Performance Materials Gmbh Mit Duftstoffen modifizierte, verzweigte Polyorganosiloxane
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JP2002539322A (ja) 2002-11-19
ES2220436T3 (es) 2004-12-16
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DE60010443T2 (de) 2005-04-07
ATE266079T1 (de) 2004-05-15

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