WO2002005772A1 - Composition de parfum et compositions de nettoyage renfermant la composition de parfum - Google Patents

Composition de parfum et compositions de nettoyage renfermant la composition de parfum Download PDF

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Publication number
WO2002005772A1
WO2002005772A1 PCT/US2000/019078 US0019078W WO0205772A1 WO 2002005772 A1 WO2002005772 A1 WO 2002005772A1 US 0019078 W US0019078 W US 0019078W WO 0205772 A1 WO0205772 A1 WO 0205772A1
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Prior art keywords
perfume
composition
present
alkyl
compositions
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PCT/US2000/019078
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English (en)
Inventor
Peter Robert Foley
Carl Eric Kaiser
Zaigou Liu
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP00950327A priority Critical patent/EP1299077A1/fr
Priority to CA002414114A priority patent/CA2414114A1/fr
Priority to AU2000263444A priority patent/AU2000263444A1/en
Priority to MXPA03000330A priority patent/MXPA03000330A/es
Priority to PCT/US2000/019078 priority patent/WO2002005772A1/fr
Priority to JP2002511705A priority patent/JP2004503670A/ja
Priority to US09/904,227 priority patent/US20020032147A1/en
Priority to ARP010103338A priority patent/AR029720A1/es
Publication of WO2002005772A1 publication Critical patent/WO2002005772A1/fr
Priority to US10/684,903 priority patent/US20040077520A1/en

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    • 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

  • Perfume Composition and Cleaning Compositions comprising the Perfume Composition
  • the present application relates to a perfume composition comprising "blooming" perfume ingredients to provide a high intensity and long-lasting perfume aroma.
  • the present application also relates to a cleaning composition comprising such a perfume composition and the use of the cleaning composition in hand- dishwashing.
  • liquid detergent products are used for the hand washing of eating, dishware and cooking utensils. Since dishwashing operations using such products involve the close proximity of the dishwasher to the dishwashing operation and to the detergent products used therein, it is desirable and commercially beneficial to add perfume materials to such products.
  • Perfumes provide an olfactory aesthetic benefit that can not only provide the user with a pleasant aroma, but also serve as a signal of cleanliness. Such perfumes should therefore be readily noticeable to the user of the dishwashing products. Any perfumes that are used, however, should not leave residue or residual odor on surfaces that the washing solution formed from any such product has contacted.
  • Residual perfumes on such surfaces may be construed negatively by consumers as chemical residues, and may result in concerns around food contamination in subsequent uses.
  • a perfume composition which not only provides the user with a readily noticeable, pleasant and desirable odor during use, but which also impart a readily noticeable and desirable odor to the surrounding area during and after use. It is thus also an object of the present invention to provide a perfume which is capable of masking malodors generated during the cooking, eating and cleaning process.
  • a perfume composition comprising: a) at least 7.5% by weight of the composition of a first perfume ingredient having boiling point of 250°C or less and ClogP of 3.0 or less, and; b) at least 35% by weight of the composition of a second perfume ingredient having boiling point of 250°C or less and ClogP of 3.0 or more, the composition being further characterised in that at least one first or second perfume ingredient is present in an amount of at least 7% by weight of the composition.
  • a blooming perfume composition is one which comprises blooming perfume ingredients.
  • a blooming perfume ingredient may be characterized by its boiling point (B.P.) and its octanol/water partition coefficient (P).
  • B.P. according to the present invention is measured under normal standard pressure of 760 mmHg.
  • the boiling points of many perfume ingredients, at standard 760 mm Hg are given in, e.g., "Perfume and Flavor Chemicals (Aroma Chemicals),” Steffen Arctander, published by the author, 1969, incorporated herein by reference.
  • the octanol/water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentrations in octanol and in water.
  • the partition coefficients of the preferred perfume ingredients of the present invention may be more conveniently given in the form of their logarithm to the base 10, logP.
  • the logP values of many perfume ingredients have been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, contains many, along with citations to the original literature.
  • 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.
  • 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 preferably used instead of the experimental logP values in the selection of perfume ingredients which are useful in the present invention.
  • the perfume composition comprising at least two perfume ingredients.
  • the first perfume ingredient is characterised by having boiling point of 250 °C or less and ClogP of 3.0 or less. More preferably the first perfume ingredient has boiling point of 240°C or less, most preferably 235 °C or less. More preferably the first perfume ingredient has a ClogP value of less than 3.0, more preferably 2.5 or less.
  • the first perfume ingredient is present at a level of at least 7.5% by weight of the composition, more preferably at least 8.5 % and most preferably at least 9.5 % by weight of the composition.
  • the second perfume ingredient is characterised by having boiling point of 250 °C or less and ClogP of 3.0 or more.
  • the second perfume ingredient has boiling point of 240 °C or less, most preferably 235 °C or less. More preferably the second perfume ingredient has a ClogP value of greater than 3.0, even more preferably greater than 3.2.
  • the second perfume ingredient is present at a level of at least 35% by weight of the composition, more preferably at least 37.5 % and most preferably greater than 40 % by weight of the perfume composition.
  • the perfume composition of the present invention comprises at least one perfume from the first group of perfume ingredients and at least one perfume from the second group of perfume ingredients. More preferably the perfume composition comprises a plurality of ingredients chosen from the first group of perfume ingredients and a plurality of ingredients chosen from the second group of perfume ingredients.
  • the composition comprise at least one perfume ingredient selected from either first and/or second perfume ingredients which is present in an amount of at least 7% by weight of the perfume composition, preferably at least 8.5 % of the perfume composition, and most preferably, at least 10% of the perfume composition .
  • compositions of the present invention differ from those blooming perfume compositions previously described in that unusually high levels of particularly chosen perfume ingredients are used. Such high levels of perfume had not previously been used because of a phenomenon known as the odor detection threshold.
  • Perfume raw material generates an olfactory response in the individual smelling the perfume.
  • the minimum concentration of perfume ingredient which is consistently perceived to generate an olfactory response in an individual is known as the Odor Detection threshold (ODT).
  • ODT Odor Detection threshold
  • concentration of perfume is increased so is the odor intensity of the perfume, and the olfactory response of the individual. This is so until the concentration of the perfume reaches a maximum, at which point the odor intensity reaches a plateau beyond which there is no additional olfactory response by the individual.
  • This range of perfume concentration through which the individual consistently perceives an odor is known as the Odor Detection Range (ODR).
  • the Applicants have however found that it is in fact beneficial to exceed the ODR of the perfume ingredient.
  • the perfume is not only effusive and very noticeable when the product is used, but it has also been found that the perfume forms a reservoir in the headspace.
  • headspace it is meant the immediate atmosphere surrounding the perfume, hence the headspace may be the atmosphere in the container in which the composition is stored or the atmosphere between the washing-up basin and the user.
  • the reservoir of perfume serves to replace diffused perfume, thus maintaining perfume concentration in the headspace at or beyond the odor detection threshold of the perfume throughout use, and preferably, after use.
  • the perfume tends to linger for longer in the room in which the composition is used.
  • At least one perfume ingredient selected from the first and/or second perfume ingredients is preferably present at a level of 50% in excess of the ODR, more preferably 150% in excess of the ODR.
  • at least one perfume ingredient should be added at a level of more than 300% of the ODR.
  • Odor detection thresholds are determined using a gas chromatograph.
  • the gas chromatograph is calibrated 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 rate is accurately measured and, assuming the duration of a human inhalation to last 12 seconds, the sampled 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.
  • solutions are delivered 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 across all panelists determines the threshold of noticeability.
  • the first and second perfume ingredients of the present invention are preferably selected from the group consisting of esters, ketones, aldehydes, alcohols, derivatives thereof and mixtures thereof.
  • Table 1 provides some examples of preferred first perfume ingredients and table 2 provides some examples of preferred second perfume ingredients.
  • the preferred weight ratio of second perfume ingredients to first blooming perfume ingredient is typically at least 1 , preferably at least 1.3, more preferably 1.5, and even more preferably 2.
  • the perfume compositions comprises at least 42.5%, more preferably at least 50%, even more preferably at least 60% of the combined first and second perfume ingredients.
  • Octyl Alcohol (Octanol-2) 179 2.719 para-Cresol 202 1.000 para-Cresyl Methyl Ether 176 2.560 para-Methyl Acetophenone 228 2.080
  • Carvacrol 238 3.401 cis-3-Hexenyl Tiglate 101 3.700
  • Hexyl Tiglate 231 3.800 alpha-lonone 237 3.381 beta-lonone 239 3.960 gamma-lonone 240 3.780 alpha-lrone 250 3.820
  • Methyl Chavicol 216 3.074 alpha-iso "gamma” Methyl lonone 230 4.209
  • Phenyl Ethyl Isobutyrate 250 3.000 alpha-Pinene 157 4.122 beta-Pinene 166 4.182 alpha-Terpinene 176 4.412 gamma-Terpinene 183 4.232
  • Cinnamyl Cinnamate 370 5.480
  • Myristicin 276 3.200 delta-Nonalactone 280 2.760 Oxahexadecanolide-10 +300 4.336
  • Oxahexadecanolide-11 MP 35°C 4.336
  • Phantolide 288 5.977 Phenyl Ethyl Benzoate 300 4.058
  • Thibetolide 280 6.246 delta-Undecalactone 290 3.830 gamma-Undecalactone 297 4.140
  • M.P. is melting point; these ingredients have a B.P. higher than 275°C.
  • auxiliary materials having no odor, or a low odor are used, e.g., as solvents, diluents, extenders or fixatives.
  • these materials are ethyl alcohol, carbitol, diethylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, and benzyl benzoate. These materials are used for, e.g., solubilizing or diluting some solid or viscous perfume ingredients to, e.g., improve handling and/or formulating. These materials are useful in the blooming perfume compositions, but are not counted in the calculation of the limits for the definition/formulation of the blooming perfume compositions of the present invention.
  • Optional, including non-blooming perfume ingredients, which should be minimized in hand dish particulate cleaning compositions of the present invention, are those having a B.P. of more than 275°C.
  • Table 3 gives some non-limiting examples of optional perfume ingredients. It can be desirable to use blooming and delayed blooming perfume ingredients and even other ingredients, preferably in small amounts, in the blooming perfume compositions of the present invention, that have low odor detection threshold values.
  • the odor detection threshold of an odorous material is the lowest vapor concentration of that material which can be detected.
  • the odor detection threshold and some odor detection threshold values are discussed in, e.g., "Standardized Human Olfactory Thresholds", M.
  • Non-limiting examples of perfume ingredients that have low odor detection threshold values useful in the present invention include coumarin, vanillin, ethyl vanillin, methyl dihydro isojasmonate, 3- hexenyl salicylate, isoeugenol, lyral, gamma-undecalactone, gamma- dodecalactone, methyl beta naphthyl ketone, and mixtures thereof. These materials are preferably present at low levels in addition to the blooming and optionally delayed blooming ingredients, typically less than 5%, preferably less than 3%, more preferably less than 2%, by weight of the blooming perfume compositions of the present invention.
  • the perfumes suitable for use in the cleaning compositions herein can be formulated from known fragrance ingredients and for purposes of enhancing environmental compatibility, the perfume compositions used herein are preferably substantially free of halogenated fragrance materials and nitromusks.
  • perfume ingredients of the present invention or a portion thereof may be complexed with a complexing agent.
  • Complexing agents may include any compound which encapsulate or bind perfume raw materials in aqueous solution.
  • Binding can result from one or more of strong reversible chemical bonding, reversible weak chemical bonding, weak or strong physical absorption or adsorption and, for example, may take the form of encapsulation, partial encapsulation, or binding.
  • Complexes formed can be 1 :1 , 1 :2, 2:1 complexant:perfume ratios, or can be more complex combinations.
  • Key to effective complexation for controlled perfume release is an effective de-complexation mechanism, driven by use of the product for washing dishes or hard surfaces. Suitable de-complexation mechanisms can include dilution in water, increased or decreased temperature, increased or decreased ionic strength.
  • a coated perfume eg via reaction with enzyme, bleach or alkalinity, or via solubilization by surfactants or solvents.
  • Preferred complexing agents include cyclodextrin, zeolites, coacervates starch coatings, and mixtures thereof.
  • Cyclodextrin molecules are known for their ability to form complexes with perfume ingredients and have typically been taught as a perfume carrier.
  • cyclodextrin molecules also appear to be surprisingly effective at reducing malodors generated by nitrogenous compounds, such as amines.
  • the prior art teaches the use of drier-added fabric softener sheets containing high levels of cyclodextrin/perfume complexes wherein the fabrics treated with this solid cyclodextrin complex release perfume when the fabrics are rewetted and that these cyclodextrin/perfume complexes can be used in aqueous rinse-added fabric softener compositions without being protected.
  • cyclodextrin By “protected” it is meant that the cyclodextrin is encapsulated in a hydrophobic wax coating so the cyclodextrin/perfume complexes will not decompose due to the presence of water. See e.g. U.S. Pat. No. 5,578,563, issued Nov. 26, 1996, to Trinh et al., which is hereby incorporated by reference.
  • the cyclodextrin used in the present invention may either be “unprotected”, as discussed above, or “protected” by the hydrophobic-coating protection techniques discussed in the prior art; see e.g. U.S. Pat.No. 5,102,564 to Gardlik et al., issued Apr.
  • the cavity of a cyclodextrin molecule has a substantially conical shape. It is preferable in the present invention that the cone-shaped cavity of the cyclodextrins have a length (altitude) of 8 A and a base size of from 5 A to 8.5 A. Thus the preferred cavity volume for cyclodextrins of the present invention is from 65 A 3 to 210 A 3 .
  • Suitable cyclodextrin species include any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives and/or mixtures thereof.
  • the alpha-cyclodextrin consists of six glucose units
  • the beta-cyclodextrin consists of seven glucose units
  • the gamma-cyclodextrin consists of eight glucose units arranged in a donut-shaped ring.
  • the specific coupling and conformation of the glucose units give the cyclodextrins a rigid, conical molecular structure with a hollow interior of a specific volume.
  • the "lining" of the internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms, therefore this surface is fairly hydrophobic.
  • the unique shape and physical-chemical property of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity. Many perfume molecules can fit into the cavity.
  • the cyclodextrin molecules are preferably water-soluble.
  • the water-soluble cyclodextrins used herein preferably have a water solubility of at least 10 g in 100 ml water, more preferably at least 25 g in 100 ml of water at standard temperature and pressure.
  • Examples of preferred water-soluble cyclodextrin derivative species suitable for use herein are hydroxypropyl alpha-cyclodextrin, methylareal alpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethyl beta- cyclodextrin, and hydroxypropyl beta-cyclodextrin.
  • Hydroxyalkyl cyclodextrin derivatives preferably have a degree of substitution of from 1 to 14, more preferably from 1.5 to 7, wherein the total number of OR groups per cyclodextrin is defined as the degree of substitution.
  • Methylated cyclodextrin derivatives typically have a degree of substitution of from 1 to 18, preferably from 3 to 16.
  • a known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-.beta.- cyclodextrin, commonly known as DIMEB, in which each glucose unit has 2 methyl groups with a degree of substitution of 14.
  • a preferred, more commercially available methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin having a degree of substitution of 12.6.
  • the preferred cyclodextrins are available, e.g., from American Maize-Products Company and Wacker Chemicals (USA), Inc.
  • cyclodexrin species suitable for use in the present invention include alpha-cyclodextrin and derivatives thereof, gamma-cyclodextrin and derivatives thereof, derivatised beta-cyclodextrins, and/or mixtures thereof.
  • Other derivatives of cyclodextrin which are suitable for use in the present invention are discussed in U.S. Pat. No. 5,578,563, incorporated above. It should be noted that two or more different species of cyclodextrin may be used in the same liquid detergent composition.
  • the complexes may be formed in any of the ways known in the art. Typically, the complexes are formed either by bringing the fragrance materials and the cyclodextrin together in a suitable solvent e.g. water and ethanol mixtures, propylene glycol. Additional examples of suitable processes as well as further preferred processing parameters and conditions are disclosed in U.S. Pat. No. 5,234,610, to Gardlik et al., issued August 10, 1993, which is hereby incorporated by reference. After the cyclodextrin and fragrance materials are mixed together, this mixture is added to the liquid detergent composition.
  • a suitable solvent e.g. water and ethanol mixtures, propylene glycol.
  • fragrance materials mixed with the cyclodextrin will be encapsulated by the cyclodextrin and form part of the cyclodextrin/perfume complex; the remaining fragrance materials will be free of the cyclodextrin and when the cyclodextrin/perfume mixture is added to the detergent composition they will enter the detergent composition as free perfume molecules.
  • a portion of free cyclodextrin molecules which are not complexed with the fragrance materials may also be present.
  • the fragrance materials and cyclodextrins are added uncomplexed and separately to the liquid detergent compositions. Consequently, the cyclodextims and fragrance materials will come into the presence of each other in the composition, and a portion of each will combine to form the desired fragrance materials/cyclodextrin complex.
  • Suitable fragrance materials for use in the present invention are described in greater detail below.
  • perfume/cyclodextrin complexes have a molar ratio of perfume compound to cyclodextrin of 1 :1.
  • the molar ratio can be either higher or lower, depending on the size of the perfume compound and the identity of the cyclodextrin compound.
  • the molar ratio of fragrance materials to cyclodextrin is preferably from 4:1 to 1 :4, more preferably from 1.5:1 to 1 :2, most preferably from 1 :1 to 1 :1.5.
  • the molar ratio can be determined easily by forming a saturated solution of the cyclodextrin and adding the perfume to form the complex. In general the complex will precipitate readily. If not, the complex can usually be precipitated by the addition of electrolyte, change of pH, cooling, etc. The complex can then be analyzed to determine the ratio of perfume to cyclodextrin.
  • the actual complexes are determined by the size of the cavity in the cyclodextrin and the size of the perfume molecule.
  • the normal complex is one molecule of perfume in one molecule of cyclodextrin
  • complexes can be formed between one molecule of perfume and two molecules of cyclodextrin when the perfume molecule is large and contains two portions that can fit in the cyclodextrin.
  • Highly desirable complexes can be formed using mixtures of cyclodextrins since perfumes are normally mixtures of materials that vary widely in size. It is usually desirable that at least a majority of the material be beta- and/or gamma-cyclodextrin. It is highly desirable to use the reaction mixtures from the intermediate stages of the manufacture of the pure cyclodextrins as discussed hereinbefore. Examples
  • the present invention relates to a cleaning composition
  • a cleaning composition comprising the perfume composition described above.
  • the cleaning composition is preferably suitable for use in cleaning hard surfaces, for example any kind of surfaces typically found in houses like kitchens, bathrooms, or in car interiors or exteriors, e.g., floors, walls, tiles, windows, sinks, showers, shower plastified curtains, wash basins, WCs, dishes, fixtures and fittings and the like made of different materials like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, any plastics, plastified wood, metal or any painted or varnished or sealed surface and the like.
  • Hard-surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on. More preferably the cleaning composition according to the present invention is suitable for cleaning dishware including dishes, cups, cutlery, glasses, food storage containers, cutlery, cooking utensils, sinks and other kitchen surfaces.
  • the cleaning composition may be in any suitable form for example, particulate, gel, paste or liquid.
  • the cleaning composition is preferably in liquid form.
  • the cleaning composition is preferably in liquid aqueous form. Where present water is preferably present at a level of from 30 to 80% by weight of the cleaning composition, more preferably from 40 to 70% and most preferably from 45 to 65 %.
  • the cleaning composition comprises as an essential features thereof from 0.005 to 2% of perfume composition as described herein. More preferably, the cleaning composition comprises from 0.001 to 1 % of the perfume compositions, most preferably from 0.01 to 0.7 %.
  • compositions of the present invention may also comprise optional ingredients for example diamine, additional surfactants, solvents, polymeric suds stabiliser, enzymes, builder, perfume, chelating agent and mixtures thereof.
  • Solvent may preferably comprise a solvent.
  • Suitable solvents include diols polymeric glycols and mixtures of both diols and polymeric glycols.
  • Diols suitable for use in the present invention have the following formula:
  • 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 which comprise ethylene oxide (EO) and propylene oxide (PO) groups may also be included in the present invention. These materials are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains.
  • Polymeric gycols suitable for use in the present invention are of the following formula:
  • a preferred polymeric glycol is a polyproylene glycol (corresponding to when y « 0) having an average molecular weight of between 1000 to 5000, more preferably between 2000 to 4000, most preferably 2000 to 3000.
  • the present liquid detergent compositions will contain at least 0.25 %, more preferably at least 0.5 %, even more preferably still, at least 0.75 % by weight of the composition of polymeric glycols.
  • the composition will also preferably contain no more than 5 %, more preferably no more than 3 %, even more preferably, no more than 2 % by weight of the composition.
  • a diol and/or an alkali metal inorganic salt such as sodium chloride.
  • Suitable amounts of diols to provide physical stability are in the amounts in the ranges found above, while a suitable amount of an alkali metal inorganic salt is at least 0.1 % and less than 1.5 %, preferably less than 0.8 % by weight of the composition.
  • diols can improve the physical and enzymatic stability of a liquid dishwashing composition.
  • Suitable solvents include lower alkanols, diols, other polyols, ethers, amines, and the like may be used in the present invention. Particularly preferred are the C1-C4 alkanols.
  • Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms.
  • suitable solvents are glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-C16 glycol ethers and mixtures thereof.
  • glycols according to the formula: HO-CR1 R2-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
  • 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.
  • 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.
  • Suitable linear C1-C5 alcohols which can be used herein are according to the formula R-OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4.
  • -C 5 alcohols are methanol, ethanol, propanol or mixtures thereof.
  • Suitable solvents include, but are not limited to, butyl diglycol ether (BDGE), butyltriglycol ether, ter amilic alcohol and the like. Particularly preferred solvents which can be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
  • BDGE butyl diglycol ether
  • benzyl alcohol butoxypropanol
  • ethanol ethanol
  • methanol isopropanol and mixtures thereof.
  • Suitable solvents for use herein include propylene glycol derivatives such as n-butoxypropanol or n- butoxypropoxypropanol, water-soluble CARBITOL R solvents or water-soluble CELLOSOLVE R solvents; water-soluble CARBITOL R solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol.
  • Water-soluble CELLOSOLVE R solvents are compounds of the 2-alkoxyethoxy ethanol class, with 2-butoxyethoxyethanol being preferred.
  • solvents include benzyl alcohol, and diols such as 2-ethyl-1 , 3-hexanediol and 2,2,4-trimethyl-1 ,3- pentanediol and mixtures thereof.
  • Some preferred solvents for use herein are n- butoxypropoxypropanol, BUTYL CARBITOL O and mixtures thereof.
  • the solvents can also be selected from the group of compounds comprising ether derivatives of mono-, di- and tri-ethylene glycol, butylene glycol ethers, and mixtures thereof.
  • the molecular weights of these solvents are preferably less than 350, more preferably between 100 and 300, even more preferably between 115 and 250.
  • preferred solvents include, for example, mono- ethylene glycol n-hexyl ether, mono-propylene glycol n-butyl ether, and tri- propylene glycol methyl ether.
  • Ethylene glycol and propylene glycol ethers are commercially available from the Dow Chemical Company under the tradename "Dowanol” and from the Arco Chemical Company under the tradename "Arcosolv”.
  • Other preferred solvents including mono- and di-ethylene glycol n- hexyl ether are available from the Union Carbide company.
  • 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, isopropanol, 2-methyl pyrrolidinone, benzyl alcohol and morpholine n-oxide. Preferred among these solvents are ethanol and isopropanol.
  • Diamines Another optional although preferred ingredient of the compositions according to the present invention is a diamine.
  • usage levels of such diamine in the compositions herein can vary depending not only on the type and severity of the soils and stains, 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.
  • the composition will preferably contain at least 0.1 %, more preferably at least 0.2%, even more preferably, at least 0.25%, even more preferably still, at least 0.5% by weight of said composition of diamine.
  • the composition will also preferably contain no more than 15%, more preferably no more than 10%, even more preferably, no more than 6%, even more preferably, no more than 5%, even more preferably still, no more than abot 1.5% by weight of said composition of diamine.
  • the diamines used in the present invention are substantially free from impurities. That is, by “substantially free” it is meant that the diamines are over 95% pure, i.e., preferably 97%, more preferably 99%, still more preferably 99.5%, free of impurities.
  • impurities which may be present in commercially supplied diamines include 2-Methyl-1 ,3-diaminobutane and alkylhydropyrimidine. Further, it is believed that the diamines should be free of oxidation reactants to avoid diamine degradation and ammonia formation.
  • Preferred organic diamines are those in which pK1 and pK2 are in the range of 8.0 to 11.5, preferably in the range of 8.4 to 11 , even more preferably from 8.6 to 10.75.
  • 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 diamines.
  • the pKa of the diamines 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 equilibrium 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.
  • the relevant conditions and/or references used for pKa's of this invention are as defined herein or in "Critical Stability Constants: Volume 2, Amines”.
  • the diamines useful herein can be defined by the following structure: R 2 ⁇ . T ⁇ C X ⁇ C v R4
  • R3 S R 5 wherein R2-5 are independently selected from H, methyl, -CH3CH2, and ethylene oxides; C x and C v are independently selected from methylene groups or branched alkyl groups where x+y is from 3 to 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.
  • compositions according to the present invention may comprise a linear or cyclic carboxylic acid or salt thereof.
  • the acid or salt thereof is present and is linear, it preferably comprises from 1 to 6 carbon atoms whereas where the acid is cyclic, it preferably comprises greater than 3 carbon atoms.
  • the linear or cyclic carbon-containing chain of the carboxylic acid or salt thereof may be substituted with a substituent group selected from the group consisting of hydroxyl, ester, ether, aliphatic groups having from 1 to 6, more preferably 1 to 4 carbon atoms and mixtures thereof
  • the carboxylic acids or salts thereof preferably have a pKal of less than 7, more preferably from 1 to 3.
  • the carboxylic acid and salts thereof may comprise one or two or more carboxylic groups.
  • Suitable carboxylic acids or salts thereof are those having the general formula:
  • R ⁇ R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are selected from the group consisting of alkyl chain having from 1 to 3 carbon atoms, hydroxy group, hydrogen, ester group, carboxylic acid group with the proviso that no more than 3 carboxylic acid groups are present.
  • Preferred carboxylic acids are those selected from the group consisting of salicylic acid, maleic acid, acetyl salicylic acid, 3 methyl salicylic acid, 4 hydroxy isophthalic acid, dihydroxyfumaric acid, 1 ,2, 4 benzene tricarboxylic acid, pentanoic acid and salts thereof and mixtures thereof.
  • the carboxylic acid exists in the salt form, the cation of the salt is preferably selected from alkali metal, alkaline earth metal, monoethanolamine, diethanolamine or triethanolamine and mixtures thereof.
  • the carboxylic acid or salt thereof is preferably present at the level of from 0.1% to 5%, more preferably from 0.2% to 1 % and most preferably from 0.25% to 0.5%._
  • compositions herein are used to provide improved rinse feel as defined below.
  • the carboxylic acid provides this benefit.
  • formulating the composition with anionic surfactant the carbon chain of which is branched such that the anionic surfactant comprises on average greater than 30% branching, can also provide or improve the rinse feel.
  • rinse feel it is meant the feel of the hands of the user or the feel of the user hands on the dishware, especially when rinsing the dish with water.
  • the type of rinse feel provided by a composition can be described as either “slippery”, where it is perceived that composition and rinse water are more difficult to remove from the surface as opposed to “draggy” where it is perceived that the composition and rinse water are comparatively easier to remove. "Draggy" rinse feel can equally be detected as an increase in friction between skin of the user or between skin and dishware.
  • compositions of the present invention provide a comparatively more "draggy" rinse feel when compared with a composition not comprising either branched anionic surfactant or carboxylic acid as defined herein or mixtures thereof.
  • compositions of the present invention may optionally although preferably comprise a surfactant.
  • Surfactants may be selected from the group consisting of amphoteric, zwitterionic, nonionic other anionic, cationic surfactants and mixtures thereof.
  • Amphoteric surfactants are preferred additional surfactants.
  • the amphoteric surfactants useful in the present invention are preferably selected from amine oxide surfactants.
  • Amine oxides are semi-polar nonionic surfactants and include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
  • R is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from 8 to 22 carbon atoms;
  • R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixtures thereof;
  • x is from 0 to 3; and each R is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • the R5 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-
  • amine oxides such as propyl amine oxides, represented by the formula:
  • R is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2- hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms
  • R 2 and R 3 are each methyl, ethyl, propyl, isopropyl, 2- hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl and n is from 0 to 10.
  • a further suitable species of amine oxide semi-polar surface active agents comprise compounds and mixtures of compounds having the formula:
  • R. is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2- hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms
  • R 2 and R 3 are each methyl, ethyl, propyl, isopropyl, 2- hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl and n is from 0 to 10.
  • Particularly preferred are amine oxides of the formula: R 2
  • R3 wherein R 1 is a C 10 . 14 alkyl and R 2 and R 3 are methyl or ethyl. Because they are low-foaming it may also be desirable to use long chain amine oxide surfactants which are more fully described in U.S. Pat. Nos. 4,316,824 (Pancheri), 5,075,501 and 5,071 ,594, incorporated herein by reference.
  • amphoteric surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch), hereby incorporated by reference.
  • amphoteric surfactant where present 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.
  • Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference.
  • the condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 20 carbon atoms with from 2 to 18 moles of ethylene oxide per mole of alcohol.
  • nonionic surfactants of this type include Tergitol® 15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9 moles ethylene oxide), Tergitol® 24-L-6 NMW (the condensation product of C-12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol® 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol® 23- 6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol® 45-7 (the condensation product of C-14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (the condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell
  • alkyl ethoxylates This category of nonionic surfactant is referred to generally as "alkyl ethoxylates.”
  • the preferred alkylpolyglycosides have the formula R2 ⁇ (C n H 2 nO)t(glycosyl) ⁇ wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
  • the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
  • Fatty acid amide surfactants having the formula: O
  • R 6 CN(R 7 ) 2 wherein R ⁇ is an alkyl group containing from 7 to 21 (preferably from 9 to 17) carbon atoms and each R ⁇ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C 2 H4O) x H where x varies from 1 to 3.
  • Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
  • the nonionic surfactant when present in the composition, is present 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.
  • the detergent compositions hereof may also contain an effective amount of polyhydroxy fatty acid amide surfactant.
  • effective amount is meant that the formulator of the composition can select an amount of polyhydroxy fatty acid amide to be incorporated into the compositions that will improve the cleaning performance of the detergent composition. In general, for conventional levels, the incorporation of 1 %, by weight, polyhydroxy fatty acid amide will enhance cleaning performance.
  • the detergent compositions may comprise 1 % weight basis, polyhydroxy fatty acid amide surfactant, preferably from 3% to 30%, of the polyhydroxy fatty acid amide.
  • the polyhydroxy fatty acid amide surfactant component comprises compounds of the structural formula:
  • R 1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C-
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n .-i-CH2OH, -
  • n is an integer from 3 to 5, inclusive
  • R 1 is H or a cyclic or aliphatic monosaccharide.
  • glycityls wherein n is 4, particularly -CH2-
  • R' can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N- 2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R2-C0-N ⁇ can be, for example, cocamide, stearamide, oleamide, Iauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1- deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
  • Suitable anionic surfactants for use in the compositions herein include water- soluble salts or acids of the formula ROSO3M wherein R preferably is a C ⁇ -C20 linear or branched hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C-
  • C20 alkyl component more preferably a C10-C14 alkyl or hydroxyalkyl
  • M is
  • H or a cation e.g., an alkali metal cation or ammonium or substituted ammonium, but preferably sodium.
  • anionic surfactants for use herein are water-soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted linear or branched
  • C6-C20 alkyl or hydroxyalkyl group having a C10-C20 alkyl component, preferably a C12-C20 al ⁇ y' or hydroxyal yl, more preferably C12-C14 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 5, more preferably between 0.5 and 2, and M is H or a cation which can be, for example, a metal cation, ammonium or substituted-ammonium cation.
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Exemplary surfactants are C-10-C14 alkyl polyethoxylate (1.0) sulfate, C-10-C-14 polyethoxylate (1.0) sulfate, C10-C14 alkyl polyethoxylate (2.25) sulfate, C10-C14 polyethoxylate (2.25) sulfate, C10-C14 alkyl polyethoxylate (3.0) sulfate, C-
  • the anionic surfactant is a mixture of alkoxylated, preferably ethoxylated and non-alkoxylated sulfate surfactants.
  • the preferred average degree of alkoxylation is from 0.4 to 0.8.
  • alkyl sulphonates including water-soluble salts or acids of the formula RSO3M wherein R is a CQ-
  • M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl- ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkali metal cation e.g., sodium, potassium, lithium
  • ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl- ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from al
  • Suitable alkyl aryl sulphonates for use herein include water- soluble salts or acids of the formula RSO3M wherein R is an aryl, preferably a benzyl, substituted by a
  • M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium etc) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium etc
  • ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary
  • the carbon chain of the anionic surfactant comprises alkyl, preferably C1-4 alkyl branching units.
  • the average percentage branching of the anionic surfactant is greater than 30%, more preferably from 35% to 80% and most preferably from 40% to 60%.
  • Such average percentage of branching can be achieved by formulating the composition with one or more anionic surfactants all of which are preferably greater than 30% branched, more preferably from 35% to 80% and most preferably from 40% to 60%.
  • the composition may comprise a combination of branched anionic surfactant and linear anionic surfactant such that on average the percentage of branching of the total anionic surfactant combination is greater than 30%, more preferably from 35% to 80% and most preferably from 40% to 60%.
  • the anionic surfactant comprising on average less than 4 moles of alkoxy groups is preferably present at a level of at least 10%, more preferably from 15% to 40% and most preferably from 20% to 35% by weight of the total composition.
  • the anionic surfactant comprising on average at least 4 moles of alkoxy groups is preferably present at a level of at least 20%, more preferably from 25% to 35% by weight of the total composition.
  • anionic surfactants useful for detersive purposes can also be used herein. These can include salts (iancluding, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C14.I6 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12- 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolysaccharides such as the
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are 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 (herein incorporated by reference).
  • alkyl carboxylates and alkyl alkoxycarboxylates having from 4 to 24 carbon atoms in the alkyl chain, preferably from 8 to 18 and more preferably from 8 to 16, wherein the alkoxy is propoxy and/or ethoxy and preferably is ethoxy at an alkoxylation degree of from 0.5 to 20, preferably from 5 to 15.
  • 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: i) homopolymers of (N,N-dialkyIamino)alkyl acrylate esters having the formula:
  • each R is independently hydrogen, C-
  • R 1 is hydrogen, C1-C6 alkyl, and mixtures thereof, provided that the ratio of (ii) to (i) is from 2 to 1 to 1 to 2;
  • the molecular weight of the polymeric suds boosters determined via conventional gel permeation chromatography, is from 1 ,000 to 2,000,000, preferably from 5,000 to 1 ,000,000, more preferably from 10,000 to 750,000, more preferably from 20,000 to 500,000, even more preferably from 35,000 to 200,000.
  • the polymeric suds stabilizer can optionally be present in the form of a salt, either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
  • One preferred polymeric suds stabilizer is (N,N-dimethylamino)alkyl acrylate esters, namely
  • 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.
  • Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH 2 (COOH) wherein R is C 10 . 20 alkyl or alkenyl, preferably C 12-16 , or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
  • Specific examples include lauryl succinate, myristyl succinate, palmityl succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • 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.
  • detergency builder salts are included, they will be included 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.
  • 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, fi-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.
  • 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. Nonetheless, the presence of magnesium ions offers 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 1.5 %, preferably from 0.015 % to 1%, more preferably from 0.025 % to 0.5 %, 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, incorporated herein by reference.
  • 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 ethylenediaminetetrace-tates, N-hydroxyethylethylenediaminetriacetates, nitrilo- tri-acetates, ethylenediamine tetrapro-prionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldi-glycines, 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 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5-disulfobenzene.
  • a preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • EDDS ethylenediamine disuccinate
  • the 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
  • the so called "weak” builders such as citrate can also be used as chelating agents.
  • these chelating agents will generally comprise from 0.00015% to 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.0003% to 3.0% by weight of such compositions.
  • 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 C10-C16 alkanolamides can be incorporated into the compositions, typically at 1 %-10% levels.
  • the C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • 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.
  • Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C ⁇
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • 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.
  • 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.
  • 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.
  • the present invention also relates to a process for cleaning dishware.
  • the dishware is contacted with a composition as described above.
  • the composition may be applied to the dishware neat or in dilute form.
  • the dishware may be cleaned singly by applying the composition to the dishware and optionally but preferably subsequently rinsing before drying.
  • the composition can be mixed with water in a suitable vessel, for example a basin, sink or bowl and thus a number of dishes can be cleaned using the same composition and water (dishwater).
  • the product can be used in dilute form in a suitable vessel as a soaking medium for, typically extremely dirty, dishware.
  • the dishware can be optionally, although preferably, rinsed before allowing to dry. Drying make take place passively by allowing for the natural evaporation of water or actively using any suitable drying equipment, for example a cloth or towel.
  • Nonionic may be either C11 Alkyl ethoxylated surfactant containing 9 ethoxy groups or or C10 Alkyl ethoxylated surfactant containing 8 ethoxy groups.
  • the protease is selected from: Savinase®; Maxatase®; Maxacal®; Maxapem 15®; subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primase®; Durazym®; Opticlean®;and Optimase®; and Alcalase ®.
  • Viscosity (cps @ 353 640 635 848
  • Nonionic may be either C10 Alkyl ethoxylated surfactant containing 8 ethoxy groups or C10 Alkyl ethoxylated surfactant containing 8 ethoxy groups.

Abstract

L'invention concerne une composition de parfum, ainsi qu'une composition de nettoyage renfermant la composition de parfum. Celle-ci comprend au moins 7,5 % en poids de la composition d'un premier ingrédient de parfum possédant un point d'ébullition égal ou inférieur à 250 °C et un ClogP égal ou inférieur à 3,0, et au moins 35 % en poids de la composition d'un second ingrédient de parfum possédant un point d'ébullition égal ou inférieur à 250 °C et un ClogP égal ou supérieur à 3,0. La composition comprend également au moins un premier ou second ingrédient en une quantité égale à au moins 7 % en poids de la composition.
PCT/US2000/019078 2000-07-13 2000-07-13 Composition de parfum et compositions de nettoyage renfermant la composition de parfum WO2002005772A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP00950327A EP1299077A1 (fr) 2000-07-13 2000-07-13 Composition de parfum et compositions de nettoyage renfermant la composition de parfum
CA002414114A CA2414114A1 (fr) 2000-07-13 2000-07-13 Composition de parfum et compositions de nettoyage renfermant la composition de parfum
AU2000263444A AU2000263444A1 (en) 2000-07-13 2000-07-13 Perfume composition and cleaning compositions comprising the perfume composition
MXPA03000330A MXPA03000330A (es) 2000-07-13 2000-07-13 Composicion de perfume y composiciones limpiadoras que comprenden la composicion de perfume.
PCT/US2000/019078 WO2002005772A1 (fr) 2000-07-13 2000-07-13 Composition de parfum et compositions de nettoyage renfermant la composition de parfum
JP2002511705A JP2004503670A (ja) 2000-07-13 2000-07-13 香料組成物及びこの香料組成物を含む洗浄性組成物
US09/904,227 US20020032147A1 (en) 2000-07-13 2001-07-12 Perfume composition and cleaning compositions comprising the perfume composition
ARP010103338A AR029720A1 (es) 2000-07-13 2001-07-13 Composicion de perfume y composiciones limpiadoras que comprenden la composicion de perfume
US10/684,903 US20040077520A1 (en) 2000-07-13 2003-10-14 Perfume composition and cleaning compositions comprising the perfume composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2000/019078 WO2002005772A1 (fr) 2000-07-13 2000-07-13 Composition de parfum et compositions de nettoyage renfermant la composition de parfum

Publications (1)

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WO2002005772A1 true WO2002005772A1 (fr) 2002-01-24

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PCT/US2000/019078 WO2002005772A1 (fr) 2000-07-13 2000-07-13 Composition de parfum et compositions de nettoyage renfermant la composition de parfum

Country Status (7)

Country Link
EP (1) EP1299077A1 (fr)
JP (1) JP2004503670A (fr)
AR (1) AR029720A1 (fr)
AU (1) AU2000263444A1 (fr)
CA (1) CA2414114A1 (fr)
MX (1) MXPA03000330A (fr)
WO (1) WO2002005772A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006088446A1 (fr) * 2005-02-15 2006-08-24 Colgate-Palmolive Company Emploi de liquides de lavage de vaisselle pour la réduction des mauvaises odeurs
WO2006095200A1 (fr) * 2005-03-10 2006-09-14 Quest International Services B.V. Compositions de parfum
EP1875902A1 (fr) * 2005-04-13 2008-01-09 Shiseido Company, Ltd. Agent sedatif et composition sedative qui le contient liberant une fragrance
WO2010117865A2 (fr) 2009-04-06 2010-10-14 Multisorb Technologies, Inc. Carte comprenant des indicateurs d'humidité à base de bromure de cuivre
US20210301219A1 (en) * 2016-02-24 2021-09-30 Takasago International Corporation Stimulating agent

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7524809B2 (en) * 2004-02-27 2009-04-28 The Procter & Gamble Company Multiple use fabric conditioning composition with improved perfume
JP5328084B2 (ja) * 2005-08-05 2013-10-30 ライオン株式会社 液体柔軟剤組成物
WO2008018186A1 (fr) * 2006-08-07 2008-02-14 Lion Corporation Composition d'adoucissant liquide
JP6095952B2 (ja) * 2012-11-09 2017-03-15 花王株式会社 香料造粒物

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GB2311296A (en) * 1996-03-19 1997-09-24 Procter & Gamble Perfumed particulate detergent compositions for hand dishwashing
WO1997034987A1 (fr) * 1996-03-19 1997-09-25 The Procter & Gamble Company Composition parfumee pour lave-vaisselle
WO1997034988A1 (fr) * 1996-03-19 1997-09-25 The Procter & Gamble Company Compositions de nettoyage des verres contenant une composition nettoyante parfumee
US5714137A (en) * 1994-08-12 1998-02-03 The Procter & Gamble Company Uncomplexed cyclodextrin solutions for odor control on inanimate surfaces

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US5714137A (en) * 1994-08-12 1998-02-03 The Procter & Gamble Company Uncomplexed cyclodextrin solutions for odor control on inanimate surfaces
GB2311296A (en) * 1996-03-19 1997-09-24 Procter & Gamble Perfumed particulate detergent compositions for hand dishwashing
WO1997034987A1 (fr) * 1996-03-19 1997-09-25 The Procter & Gamble Company Composition parfumee pour lave-vaisselle
WO1997034988A1 (fr) * 1996-03-19 1997-09-25 The Procter & Gamble Company Compositions de nettoyage des verres contenant une composition nettoyante parfumee

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006088446A1 (fr) * 2005-02-15 2006-08-24 Colgate-Palmolive Company Emploi de liquides de lavage de vaisselle pour la réduction des mauvaises odeurs
WO2006095200A1 (fr) * 2005-03-10 2006-09-14 Quest International Services B.V. Compositions de parfum
EP1875902A1 (fr) * 2005-04-13 2008-01-09 Shiseido Company, Ltd. Agent sedatif et composition sedative qui le contient liberant une fragrance
EP1875902A4 (fr) * 2005-04-13 2010-10-06 Shiseido Co Ltd Agent sedatif et composition sedative qui le contient liberant une fragrance
WO2010117865A2 (fr) 2009-04-06 2010-10-14 Multisorb Technologies, Inc. Carte comprenant des indicateurs d'humidité à base de bromure de cuivre
US20210301219A1 (en) * 2016-02-24 2021-09-30 Takasago International Corporation Stimulating agent

Also Published As

Publication number Publication date
MXPA03000330A (es) 2004-01-26
AR029720A1 (es) 2003-07-10
AU2000263444A1 (en) 2002-01-30
EP1299077A1 (fr) 2003-04-09
CA2414114A1 (fr) 2002-01-24
JP2004503670A (ja) 2004-02-05

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