WO2011084569A1 - Dishwashing detergent composition having a malodor control component and methods of cleaning dishware - Google Patents

Dishwashing detergent composition having a malodor control component and methods of cleaning dishware Download PDF

Info

Publication number
WO2011084569A1
WO2011084569A1 PCT/US2010/060694 US2010060694W WO2011084569A1 WO 2011084569 A1 WO2011084569 A1 WO 2011084569A1 US 2010060694 W US2010060694 W US 2010060694W WO 2011084569 A1 WO2011084569 A1 WO 2011084569A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
weight
aldehyde
alternatively
volatile
Prior art date
Application number
PCT/US2010/060694
Other languages
French (fr)
Inventor
Ricky Ah-Man Woo
Steven Anthony Horenziak
Rhonda Jean Jackson
Zaiyou Liu
Michael-Vincent Nario Malanyaon
Jason John Olchovy
Christine Marie Readnour
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.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=43499978&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2011084569(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP10801497A priority Critical patent/EP2512531A1/en
Priority to JP2012544814A priority patent/JP5639661B2/en
Priority to CA2782479A priority patent/CA2782479C/en
Priority to MX2012007021A priority patent/MX2012007021A/en
Publication of WO2011084569A1 publication Critical patent/WO2011084569A1/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/01Deodorant compositions
    • AHUMAN NECESSITIES
    • A47FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47LDOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00Washing or rinsing machines for crockery or tableware
    • A47L15/0002Washing processes, i.e. machine working principles characterised by phases or operational steps
    • A47L15/0005Rinsing phases, e.g. pre-rinsing, intermediate rinsing, final rinsing
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0068Deodorant compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2072Aldehydes-ketones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2096Heterocyclic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/3481Organic compounds containing sulfur containing sulfur in a heterocyclic ring, e.g. sultones or sulfolanes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663Stabilised liquid enzyme compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes

Definitions

  • the present invention relates to dishwashing detergent compositions having a malodor control component, and methods of cleaning dishware.
  • Scented dishwashing detergent products for cleaning dishware are known.
  • dishwashing detergent manufacturers develop perfume technology that provides a pleasant scent and masks malodors associated with soiled dishware.
  • amine- based malodors such as fish malodors
  • sulfur-based malodors such as garlic and onion
  • the time required for a product to noticeably combat malodors may create consumer doubt as to a product's efficacy on malodors. For example, the consumer may finish washing a dish and leave the area before the product begins to noticeably reduce the malodor.
  • a dishwashing detergent composition comprising: (a) from about 0.1% to about 20% by weight of the total composition of a chelant; (b) from about 5% to about 80% by weight of the total composition of a surfactant selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwitterionic, semi-polar nonionic surfactants and mixtures thereof; and (c) a malodor control component comprising an effective amount of two or more volatile aldehydes for neutralizing a malodor, wherein said two or more volatile aldehydes are selected from the group consisting of 2-ethoxy benzylaldehyde, 2- isopropyl-5-methyl-2-hexenal, 5-methyl furfural, 5-methyl-thiophene-carboxaldehyde, adoxal, p- anisaldehyde, benzylaldehyde, strengenal, cinnamic aldehyde,
  • a dishwashing detergent composition comprising: (a) a chelant; (b) a surfactant selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwitterionic, semi-polar nonionic surfactants, and mixtures thereof; and (c) a malodor control component comprising: (i) at least one volatile aldehyde; and (ii) an acid catalyst having a vapor pressure of about 0.01 to about 13 at 25°C; and (b) about 1% to about 5%, by weight of said composition, of a low molecular weight monohydric alcohol.
  • a method of cleaning a dishware comprising the steps of: applying a composition according to claim 1 on said dishware; and rinsing said composition off of said dishware.
  • Fig. 1 is a graph showing butanethiol reduction by thiophene carboxaldehyde in combination with various acid catalysts.
  • the present invention relates to a dishwashing detergent composition that surprisingly provides excellent grease cleaning combined with superior shine and malodor control; and methods of cleaning dishware.
  • “Cleaning” means applying to a surface for the purpose of cleaning, and/or disinfecting.
  • “Dishware” means a surface such as dishes, glasses, pots, pans, baking dishes and flatware made from ceramic, china, metal, glass, plastic (polyethylene, polypropylene, polystyrene, etc.) and wood.
  • Dishwashing detergent composition refers to those compositions that are employed in manual (i.e. hand) dishwashing. Such compositions are generally high sudsing or foaming in nature.
  • “Grease” means materials comprising at least in part (i.e., at least 0.5 wt% by weight of the grease) saturated and unsaturated fats and oils, alternatively oils and fats derived from animal sources such as beef and/or chicken.
  • Malodor refers to compounds generally offensive or unpleasant to most people, such as the complex odors associated with bowel movements.
  • Negtralize or “neutralization” refers to the ability of a compound or product to reduce or eliminate malodorous compounds. Odor neutralization may be partial, affecting only some of the malodorous compounds in a given context, or affecting only part of a malodorous compound. A malodorous compound may be neutralized by chemical reaction resulting in a new chemical entity, by sequestration, by chelation, by association, or by any other interaction rendering the malodorous compound less malodorous or non- malodorous. Odor neutralization may be distinguished from odor masking or odor blocking by a change in the malodorous compound, as opposed to a change in the ability to perceive the malodor without any corresponding change in the condition of the malodorous compound.
  • Suds profile means the amount of sudsing (high or low) and the persistence of sudsing
  • high sudsing refers to liquid hand dishwashing detergent compositions which are both high sudsing (i.e. a level of sudsing considered acceptable to the consumer) and have sustained sudsing (i.e. a high level of sudsing maintained throughout the dishwashing operation). This is particularly important with respect to liquid dishwashing detergent compositions as the consumer uses high sudsing as an indicator of the performance of the detergent composition. Moreover, the consumer of a liquid dishwashing detergent composition also uses the sudsing profile as an indicator that the wash solution still contains active detergent ingredients. The consumer usually renews the wash solution when the sudsing subsides. Thus, a low sudsing liquid dishwashing detergent composition formulation will tend to be replaced by the consumer more frequently than is necessary because of the low sudsing level.
  • the dishwashing detergent composition generally contains from 30% to 95%, alternatively 40% to 80%, alternatively 50% to 75% of an aqueous liquid carrier, in which the other essential and optional compositions components are dissolved, dispersed or suspended.
  • composition of the present invention comprises a chelant at a level of from 0.1% to 20%, alternatively from 0.2% to 5%, alternatively from 0.2% to 3% by weight of total composition.
  • chelation means the binding or complexation of a bi- or multidentate ligand.
  • ligands which are often organic compounds, are called chelants, chelators, chelating agents, and/or sequestering agent.
  • Chelating agents form multiple bonds with a single metal ion.
  • Chelants are chemicals that form soluble, complex molecules with certain metal ions, inactivating the ions so that they cannot normally react with other elements or ions to produce precipitates or scale.
  • the ligand forms a chelate complex with the substrate. The term is reserved for complexes in which the metal ion is bound to two or more atoms of the chelant.
  • the chelants for use in the present invention are those having crystal growth inhibition properties, i.e. those that interact with the small calcium and magnesium carbonate particles preventing them from aggregating into hard scale deposit.
  • the particles repel each other and remain suspended in the water or form loose aggregates which may settle. These loose aggregates are easily rinsed away and do not form a deposit.
  • Suitable chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polufanctionally-substituted aromatic chelating agents and mixtures thereof.
  • Suitable chelants for use herein are also the amino acids based chelants, alternatively glutamic- ⁇ , ⁇ - diacetic acid and derivatives and/or phosphonate based chelants, alternatively diethylenetriamine penta methylphosphonic acid.
  • Amino carboxylates include ethylenediaminetetra- acetates, N- hydroxyethylethylenediaminetriacetates, nitrilo-triacetates, ethylenediamine tetrapro-prionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldi-glycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • MGDA methyl-glycine-diacetic acid
  • GLDA glutmic- N,N- diacetic acid
  • the composition comprises GLDA (salts and derivatives thereof).
  • the composition comprises tetrasodium salt.
  • suitable chelants include amino acid based compound or a succinate based compound.
  • succinate based compound and “succinic acid based compound” are used interchangeably herein.
  • Other suitable chelants are described in USP 6,426,229. Particular suitable chelants include; for example, aspartic acid-N-monoacetic acid (ASMA), aspartic acid- ⁇ , ⁇ -diacetic acid (ASDA), aspartic acid-N- monopropionic acid (ASMP) , iminodisuccinic acid (IDS), Imino diacetic acid (IDA), N- (2-sulfomethyl) aspartic acid (SMAS), N- (2-sulfoethyl) aspartic acid (SEAS), N- (2- sulfomethyl) glutamic acid (SMGL), N- (2- sulfoethyl) glutamic acid (SEGL), N- methyliminodiacetic acid (MID A), ⁇ - alanine-N,N-d
  • ethylenediamine disuccinate especially the [S,S] isomer as described in U.S. Patent 4,704,233.
  • EDDS ethylenediamine disuccinate
  • Hydroxyethyleneiminodiacetic acid, Hydroxyiminodisuccinic acid, Hydroxyethylene diaminetriacetic acid are also suitable.
  • chelants include homopolymers and copolymers of polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts.
  • Suitable salts of the abovementioned compounds are the ammonium and/or alkali metal salts, i.e. the lithium, sodium, and potassium salts.
  • Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, in which case they contain at least two carboxyl groups which are in each case separated from one another by, alternatively, no more than two carbon atoms.
  • Polycarboxylates which comprise two carboxyl groups include, for example, water-soluble salts of, malonic acid, (ethyl enedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid.
  • Polycarboxylates which contain three carboxyl groups include, for example, water-soluble citrate.
  • a suitable hydroxycarboxylic acid is, for example, citric acid.
  • Another suitable polycarboxylic acid is the homopolymer of acrylic acid.
  • the composition includes the polycarboxylates end capped with sulfonates.
  • Amino phosphonates are also suitable for use as chelating agents and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST.
  • the composition includes amino phosphonates that do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • compositions herein such as described in U.S. Patent 3,812,044.
  • the composition includes dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.
  • suitable polycarboxylates chelants for use herein include citric acid, lactic acid, acetic acid, succinic acid, formic acid; all alternatively in the form of a water-soluble salt.
  • Other suitable polycarboxylates are oxodisuccinates, carboxymethyloxysuccinate and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
  • composition of the present invention may comprise a surfactant selected from anionic, nonionic, cationic, amphoteric, zwitterionic, semi-polar nonionic surfactants, and mixtures thereof.
  • the surfactants of the composition will have an average branching of the alkyl chain(s) of more than 10%, alternatively more than 20%, alternatively more than 30%, alternatively more than 40%, by weight of the total surfactants.
  • the surfactants of the present invention will generally be present at a level of 5% to 80%, alternatively 10% to 60%, alternatively 12% to 45%, by weight of the total composition.
  • composition of the present invention will further comprise a nonionic surfactant at a weight ratio of total surfactant to nonionic surfactant of 2 to 10, alternatively of 2 to 7.5, alternatively of 2 to 6.
  • Nonionic Surfactants can be used in their linear and/or branched version.
  • nonionic surfactants alternatively of branched nonionic surfactants, will prevent efficiently the formation of crystalline films of the dish surface and will provide improved wetting and thereby providing superior shine.
  • Nonionic surfactants are present in a typical amount of from 2% to 40%, alternatively 3% to 30% by weight of the liquid detergent composition and alternatively from 3 to 20% by weight of the total composition.
  • Suitable nonionic surfactants include the condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms.
  • the composition includes the condensation products of alcohols having an alkyl group containing from 8 to 18 carbon atoms, alternatively from 9 to 15 carbon atoms with from 2 to 18 moles, alternatively 2 to 15, alternatively 5-12 of ethylene oxide per mole of alcohol.
  • alkylpolyglycosides having the formula R 2 0(C n H2 n O) t (glycosyl) x (formula (III)), wherein R 2 of formula (III) 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, alternatively from 12 to 14, carbon atoms; n of formula (III) is 2 or 3, alternatively 2; t of formula (III) is from 0 to 10, alternatively 0; and x of formula (III) is from 1.3 to 10, alternatively from 1.3 to 3, most alternatively from 1.3 to 2.7.
  • the glycosyl is alternatively derived from glucose.
  • alkyl glycerol ethers and sorbitan esters are also suitable.
  • fatty acid amide surfactants having the formula (IV):
  • R 6 of formula (IV) is an alkyl group containing from 7 to 21, alternatively from 9 to 17, carbon atoms and each R 7 of formula (IV) is selected from the group consisting of hydrogen, Ci- C 4 alkyl, Ci-C 4 hydroxyalkyl, and -(C2H 4 0) X H where x of formula (IV) varies from 1 to 3.
  • Suitable amides are C8-C2 0 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
  • Suitable nonionic surfactants for use in the present invention are the condensation products of aliphatic alcohols with ethylene oxide, such as the mixture of nonyl (C9), decyl (CIO) undecyl (Cl l) alcohol modified with on average 5 ethylene oxide (EO) units such as the commercially available Neodol 91-5 or the Neodol 91-8 that is modified with on average 8 EO units.
  • EO ethylene oxide
  • the longer alkyl chains ethoxylated nonionics such as C12, C13 modified with 5 EO (Neodol 23-5).
  • Neodol is a Shell tradename.
  • the C12, C14 alkyl chain with 7 EO commercially available under the trade name Novel 1412-7 (Sasol) or the Lutensol A 7 N (BASF)
  • Other branching also include oxo branched nonionic surfactants such as the Lutensol ON 50 (5 EO) and Lutensol ON70 (7 EO).
  • branched nonionics are the ones derived from the isotridecyl alcohol and modified with ethyleneoxyde such as the Lutensol T07 (7EO) from BASF and the Marlipal O 13/70 (7EO) from Sasol.
  • ethoxylated fatty alcohols originating from the Fisher & Troshp reaction comprising up to 50% branching (40% methyl (mono or bi) 10% cyclohexyl) such as those produced from the safolTM alcohols from Sasol; ethoxylated fatty alcohols originating from the oxo reaction wherein at least 50 weight % of the alcohol is C2 isomer (methyl to pentyl) such as those produced from the IsalchemTM alcohols or LialTM alcohols from Sasol; the ethoxylated fatty alcohols originating from the modified oxo reaction wherein at least 15 weight % of the alcohol is C2 isomer (methyl to pentyl) such as those produced from the Neodol
  • the amphoteric and zwitterionic surfactanta can be present at a level of from 0.01% to 20%, alternatively from 0.2% to 15%, alternatively 0.5% to 10%, by weight of the composition.
  • the compositions of the present invention may further comprise an amine oxide and/or a betaine.
  • the composition includes amine oxides are coco dimethyl amine oxide or coco amido propyl dimethyl amine oxide.
  • Amine oxide may have a linear or mid- branched alkyl moiety.
  • Typical linear amine oxides include water-soluble amine oxides containing one Rl C 8- i8 alkyl moiety and 2 R2 and R3 moieties selected from the group consisting of Ci_3 alkyl groups and Ci -3 hydroxyalkyl groups.
  • amine oxide is characterized by the formula Rl - N(R2)(R3) - ⁇ O wherein Ri is a C 8- i 8 alkyl and R 2 and R 3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2- hydroxypropyl and 3-hydroxypropyl.
  • the linear amine oxide surfactants in particular may include linear Cio-Ci 8 alkyl dimethyl amine oxides and linear C 8 -Ci 2 alkoxy ethyl dihydroxy ethyl amine oxides.
  • Suitable amine oxides include linear Cio, linear Cio-Ci 2 , and linear Ci 2 -Ci 4 alkyl dimethyl amine oxides.
  • mid-branched means that the amine oxide has one alkyl moiety having ni carbon atoms with one alkyl branch on the alkyl moiety having n 2 carbon atoms.
  • the alkyl branch is located on the a carbon from the nitrogen on t he alkyl moiety.
  • This type of branching for the amine oxide is also known in the art as an internal amine oxide.
  • the total sum of ni and n 2 is from 10 to 24 carbon atoms, alternatively from 12 to 20, and alternatively from 10 to 16.
  • the number of carbon atoms for the one alkyl moiety (ni) should be approximately the same number of carbon atoms as the one alkyl branch (n 2 ) such that the one alkyl moiety and the one alkyl branch are symmetric.
  • symmetric means that I ni - n 2 I is less than or equal to 5, alternatively 4, alternatively from 0 to 4 carbon atoms in at least 50 wt%, alternatively at least 75 wt% to 100 wt% of the mid-branched amine oxides for use herein.
  • the amine oxide further comprises two moieties, independently selected from a C1-3 alkyl, a Ci_3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups.
  • the two moieties are selected from a Ci -3 alkyl, alternatively both are selected as a Ci alkyl.
  • surfactants include betaines such alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as the Phosphobetaine and alternatively meets formula I:
  • R 1 is a saturated or unsaturated C6-22 alkyl residue, alternatively C8-18 alkyl residue, in particular a saturated ClO-16 alkyl residue, for example a saturated C12-14 alkyl residue;
  • X is NH, NR 4 with Cl-4 Alkyl residue R 4 , O or S,
  • n a number from 1 to 10, alternatively 2 to 5, in particular 3,
  • R 2 , R 3 are independently a CI -4 alkyl residue, potentially hydroxy substituted such as a hydroxyethyl, alternatively a methyl.
  • n a number from 1 to 4, in particular 1, 2 or 3,
  • Y is COO, S03, OPO(OR 5 )0 or P(0)(OR 5 )0, whereby R 5 is a hydrogen atom H or a Cl-
  • Suitable betaines are the alkyl betaines of the formula (la), the alkyl amido betaine of the formula (lb), the Sulfo betaines of the formula (Ic) and the Amido sulfobetaine of the formula (Id);
  • Suitable betaines are the Carbobetaine
  • betaines and sulfobetaine are the following [designated in accordance with INCI]: Almondamidopropyl of betaines, Apricotam idopropyl betaines, Avocadamidopropyl of betaines, Babassuamidopropyl of betaines, Behenam idopropyl betaines, Behenyl of betaines, betaines, Canolam idopropyl betaines, Capryl/Capram idopropyl betaines, Carnitine, Cetyl of betaines, Cocamidoethyl of betaines, Cocam idopropyl betaines, Cocam idopropyl Hydroxysultaine, Coco betaines, Coco Hydroxysultaine, Coco/Oleam idopropyl betaines, Coco Sultaine, Decyl of betaines, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl
  • Suitable anionic surfactants to be used in the compositions and methods of the present invention are sulfates, sulfosuccinates, sulfoacetates, and/or sulfonates; alternatively alkyl sulfate and/or alkyl ethoxy sulfates; alternatively a combination of alkyl sulfates and/or alkyl ethoxy sulfates with a combined ethoxylation degree less than 5, alternatively less than 3, alternatively less than 2.
  • Sulphate or sulphonate surfactant is typically present at a level of at least 5%, alternatively from 5% to 40%, alternatively from 15% to 30%, alternatively at 15% to 25%, by weight of the liquid detergent composition.
  • Suitable sulphate or sulphonate surfactants for use in the compositions herein include water-soluble salts or acids of Cio-Ci 4 alkyl or hydroxyalkyl, sulphate or sulphonates.
  • Suitable counterions include hydrogen, alkali metal cation or ammonium or substituted ammonium, but alternatively sodium.
  • the hydrocarbyl chain is branched, it alternatively comprises C alkyl branching units.
  • the average percentage branching of the sulphate or sulphonate surfactant is alternatively greater than 30%, alternatively from 35% to 80%, alternatively from 40% to 60% of the total hydrocarbyl chains.
  • the sulphate or sulphonate surfactants may be selected from Cn-Ci 8 alkyl benzene sulphonates (LAS), C8-C2 0 primary, branched-chain and random alkyl sulphates (AS); Cio-Ci 8 secondary (2,3) alkyl sulphates; Cio-Ci 8 alkyl alkoxy sulphates (AE X S) wherein alternatively x is from 1-30; Cio-Ci 8 alkyl alkoxy carboxylates alternatively comprising 1-5 ethoxy units; mid- chain branched alkyl sulphates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulphates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulphonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/0508
  • the paraffin sulphonates may be monosulphonates or disulphonates and usually are mixtures thereof, obtained by sulphonating paraffins of 10 to 20 carbon atoms. Suitable sulphonates are those of C12-18 carbon atoms chains and alternatively they are C14-17 chains. Paraffin sulphonates that have the sulphonate group(s) distributed along the paraffin chain are described in US2,503,280; US2,507,088; US3, 260,744; US 3,372 188 and in DE 735 096.
  • alkyl glyceryl sulphonate surfactants and/or alkyl glyceryl sulphate surfactants described in WO06/014740: A mixture of oligomeric alkyl glyceryl sulfonate and/or sulfate surfactant selected from dimers, trimers, tetramers, pentamers, hexamers, heptamers, and mixtures thereof; wherein the weight percentage of monomers is from 0 wt% to 60 wt% by weight of the alkyl glyceryl sulfonate and/or sulfate surfactant mixture.
  • alkyl alternatively dialkyl sulfosuccinates and/or sulfoacetate.
  • the dialkyl sulfosuccinates may be a C 6 -i5 linear or branched dialkyl sulfosuccinate.
  • the alkyl moieties may be symmetrical (i.e., the same alkyl moieties) or asymmetrical (i.e., different alkyl moiety.es). Alternatively, the alkyl moiety is symmetrical.
  • branched anionic alkyl ether sulphates are obtained via sulfation of a mixture of the branched alcohols and the branched alcohol ethoxylates.
  • the sulfated fatty alcohols originating from the Fisher & Troshp reaction comprising up to 50% branching (40% methyl (mono or bi) 10% cyclohexyl) such as those produced from the safolTM alcohols from Sasol; sulfated fatty alcohols originating from the oxo reaction wherein at least 50 weight % of the alcohol is C2 isomer (methyl to pentyl) such as those produced from the IsalchemTM alcohols or LialTM alcohols from Sasol; the sulfated fatty alcohols originating from the modified oxo reaction wherein at least 15 weight % of the alcohol is C2 isomer (methyl to pentyl) such as those produced from the NeodolTM alcohols from Shell.
  • Cationic surfactants when present in the composition, are present in an effective amount, alternatively from 0.1% to 20%, by weight of the composition.
  • Suitable cationic surfactants are quaternary ammonium surfactants. Suitable quaternary ammonium surfactants are selected from the group consisting of mono C 6 -Ci6, alternatively C6-C10 N-alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are substituted by methyl, hydroxyehthyl or hydroxypropyl groups.
  • Another suitable cationic surfactant is an C 6 -Ci8 alkyl or alkenyl ester of a quaternary ammonium alcohol, such as quaternary chlorine esters.
  • the cationic surfactants have the formula (V):
  • Rl of formula (V) is C$-Ci$ hydrocarbyl and mixtures thereof, alternatively, C 8- i 4 alkyl, alternatively, C 8 , Cio or Ci 2 alkyl, and X of formula (V) is an anion, alternatively, chloride or bromide.
  • the composition of the present invention can further comprise one or more alkoxylated polyethyleneimine polymer.
  • the composition may comprise from 0.01 wt% to 10 wt%, alternatively from 0.01 wt% to 2 wt%, alternatively from 0.1 wt% to 1.5 wt%, alternatively from 0.2% to 1.5%, by weight of the composition, of an alkoxylated polyethyleneimine polymer as described on page 2, line 33 to page 5, line 5 and exemplified in examples 1 to 4 at pages 5 to 7 of WO2007/135645.
  • the alkoxylated polyethyleneimine polymer of the present composition has a polyethyleneimine backbone having from 400 to 10000 weight average molecular weight, alternatively from 400 to 7000 weight average molecular weight, alternatively from 3000 to 7000 weight average molecular weight.
  • polyamines can be prepared for example, by polymerizing ethyleneimine in presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.
  • the alkoxylation of the polyethyleneimine backbone includes: (1) one or two alkoxylation modifications per nitrogen atom, dependent on whether the modification occurs at a internal nitrogen atom or at an terminal nitrogen atom, in the polyethyleneimine backbone, the alkoxylation modification consisting of the replacement of a hydrogen atom on a polyalkoxylene chain having an average of about 1 to about 40 alkoxy moieties per modification, wherein the terminal alkoxy moiety of the alkoxylation modification is capped with hydrogen, a Ci-C 4 alkyl or mixtures thereof; (2) a substitution of one Ci-C 4 alkyl moiety or benzyl moiety and one or two alkoxylation modifications per nitrogen atom, dependent on whether the substitution occurs at a internal nitrogen atom or at an terminal nitrogen atom, in the polyethyleneimine backbone, the alkoxylation modification consisting of the replacement of a hydrogen atom by a polyalkoxylene chain having an average of about 1 to about 40 alkoxy moieties per modification wherein the terminal alk
  • composition may further comprise the amphiphilic graft polymers based on water soluble polyalkylene oxides (A) as a graft base and sides chains formed by polymerization of a vinyl ester component (B), said polymers having an average of ⁇ 1 graft site per 50 alkylene oxide units and mean molar mass Mw of from 3,000 to 100,000 described in BASF patent application WO2007/138053 on pages 2 line 14 to page 10, line 34 and exemplified on pages 15-18.
  • A water soluble polyalkylene oxides
  • B vinyl ester component
  • Salts and solvents are generally used to ensure preferred product quality for dissolution, thickness and aesthetics and to ensure better processing.
  • the ions can be selected from magnesium, sodium, potassium, calcium, and/or magnesium and alternatively from sodium and magnesium, and are added as a hydroxide, chloride, acetate, sulphate, formate, oxide or nitrate salt to the compositions of the present invention.
  • Salts are generally present at an active level of from 0.01% to 5%, alternatively from 0.015% to 3%, alternatively from 0.025 % to 2.0%, by weight of the liquid detergent composition. In one embodiment, additional magnesium ions may be avoided.
  • Suitable solvents include C1-C5 alcohols are according to the formula R-OH wherein R is a linear saturated alkyl group of from 1 to 5 carbon atoms, alternatively from 2 to 4. Suitable alcohols are ethanol, propanol, isopropanol or mixtures thereof. Other suitable alcohols are alkoxylated Cl-8 alcohols according to the formula R (A0n-oh wherein R is a linear alkyl group of from 1 to 8 carbon atoms, alternatively from 3 to 6, wherein A is an alkoxy group alternatively propoxy and/or ethoxy and n is an integer of from 1 to 5, alternatively from 1 to 2.
  • Suitable alcohols are buthoxy propoxy propanol (n-BPP), buthoxy Propanol (n-BP) buthoxyethanol or mixtures thereof.
  • Suitable alkoxylated aromatic alcohols to be used herein are according to the formula R (B)n-OH whereinm R is an alkyl substituted or non alkyl substituted aryl group of from 1 to 20 carbon atoms ,, alternatively from 2 to 15 and alternatively from 2 to 10, wherein B is an alkoxy alternatively buthoxy, propoxy and/or ethoxy and n is an integer from of from 1 to 5, alternatively from 1 to 2.
  • Suitable alkoxylated aromatic alcohols are benzoyethanol and or benzoypropanol.
  • a suitable aromatic alcohol to be used herein is benzyl alcohol.
  • suitable solvents include butyl diglycolether , benzylalcohol, propoxyporpoxypropanol (EP 0 859 044) ethers and diethers, glycols, alkoxylated glycols, C 6 -Ci6 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.
  • the liquid detergent composition may contain from 0.01% to 20%, alternatively from 0.5% to 20%, alternatively from 1% to 10%, by weight of the composition, of a solvent.
  • a solvent such as water
  • the dishwashing detergent compositions of the present invention may optionally comprise a hydrotrope in an effective amount so that the liquid detergent compositions are appropriately compatible in water.
  • Suitable hydrotropes for use herein include anionic-type hydrotropes, particularly sodium, potassium, and ammonium xylene sulphonate, sodium, potassium and ammonium toluene sulphonate, sodium potassium and ammonium cumene sulphonate, and mixtures thereof, and related compounds, as disclosed in U.S. Patent 3,915,903.
  • compositions of the present invention typically comprise from 0% to 15% by weight of the liquid detergent composition of a hydro tropic, or mixtures thereof, alternatively from 1% to 10%, most alternatively from 3% to 6% by weight.
  • compositions of the present invention may optionally contain a polymeric suds stabilizer.
  • These polymeric suds stabilizers provide extended suds volume and suds duration of the liquid detergent compositions.
  • These polymeric suds stabilizers may be selected from homopolymers of (N,N-dialkylamino) alkyl esters and (N,N-dialkylamino) alkyl acrylate esters.
  • the weight average molecular weight of the polymeric suds boosters, determined via conventional gel permeation chromatography, is from 1,000 to 2,000,000, alternatively from 5,000 to 1,000,000, alternatively from 10,000 to 750,000, alternatively from 20,000 to 500,000, even alternatively 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, sulphate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
  • a salt either an inorganic or organic salt, for example the citrate, sulphate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
  • the composition includes a suds stabilizer that is (N,N- dimethylamino)alkyl acrylate esters namely the acrylate ester represented by the formula (VII):
  • suds boosting polymers are copolymers of hydroxypropylacrylate/dimethyl aminoethylmethacrylate (copolymer of HPA/DMAM), represented by the formulae VIII and IX
  • the polymeric suds booster/stabilizer may be present in the composition from 0.01% to 15%, alternatively from 0.05% to 10%, alternatively from 0.1% to 5%, by weight of the composition.
  • hydrophobic ally modified cellulosic polymers having a number average molecular weight (Mw) below 45,000; alternatively between 10,000 and 40,000; alternatively between 13,000 and 25,000.
  • the hydrophobic ally modified cellulosic polymers include water soluble cellulose ether derivatives, such as nonionic and cationic cellulose derivatives.
  • the composition includes methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, or mixtures thereof.
  • Another optional ingredient in the composition of the present invention is a diamine.
  • the composition will alternatively contain 0% to 15%, alternatively 0.1% to 15%, alternatively 0.2% to 10%, alternatively 0.25% to 6%, alternatively 0.5% to 1.5% by weight of said composition, of at least one diamine.
  • Suitabble organic diamines are those in which pKl and pK2 are in the range of 8.0 to
  • Other suitable materials include primary/primary diamines with alkylene spacers ranging from C 4 to C 8 .
  • pKa is used herein in the same manner as is commonly known to people skilled in the art of chemistry: in an all-aqueous solution at 25°C and for an ionic strength between 0.1 to 0.5 M. 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.
  • the dishwashing detergent compositions of the present invention may comprise a linear or cyclic carboxylic acid or salt thereof to improve the rinse feel of the composition.
  • Carboxylic acids useful herein include Ci_6 linear or at least 3 carbon containing cyclic acids.
  • 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, alternatively 1 to 4 carbon atoms, and mixtures thereof.
  • Suitable 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, citric acid and salts thereof, and mixtures thereof.
  • the carboxylic acid exists in the salt form, the cation of the salt is alternatively selected from alkali metal, alkaline earth metal, monoethanolamine, diethanolamine or triethanolamine and mixtures thereof.
  • the carboxylic acid or salt thereof when present, is present at the level of from 0.1% to 5%, alternatively from 0.2% to 1%, alternatively from 0.25% to 0.5%, by weight of the compositian.
  • the dishwashing detergent composition comprises a malodor control component.
  • the malodor control component may include at least one volatile aldehyde and an acid catalyst.
  • the malodor control component is designed to deliver genuine malodor neutralization and not function merely by covering up or masking odors.
  • a genuine malodor neutralization provides a sensory and analytically measurable (e.g. gas chromatograph) malodor reduction.
  • the composition will reduce malodors in the vapor and/or liquid phase.
  • the malodor control component includes a mixture of volatile aldehydes that neutralize malodors in vapor and/or liquid phase via chemical reactions. Such volatile aldehydes are also called reactive aldehydes (RA). Volatile aldehydes may react with amine-based odors, following the path of Schiff-base formation. Volatiles aldehydes may also react with sulfur-based odors, forming thiol acetals, hemi thiolacetals, and thiol esters in vapor and/or liquid phase. It may be desirable for these vapor and/or liquid phase volatile aldehydes to have virtually no negative impact on the desired perfume character of a product. Aldehydes that are partially volatile may be considered a volatile aldehyde as used herein.
  • Suitable volatile aldehydes may have a vapor pressure (VP) in the range of about 0.0001 torr to 100 torr, alternatively about 0.0001 torr to about 10 torr, alternatively about 0.001 torr to about 50 torr, alternatively about 0.001 torr to about 20 torr, alternatively about 0.001 torr to about 0.100 torr, alternatively about 0.001 torr to 0.06 torr, alternatively about 0.001 torr to 0.03 torr, alternatively about 0.005 torr to about 20 torr, alternatively about 0.01 torr to about 20 torr, alternatively about 0.01 torr to about 15 torr, alternatively about 0.01 torr to about 10 torr, alternatively about 0.05 torr to about 10 torr, measured at 25°C.
  • VP vapor pressure
  • the volatile aldehydes may also have a certain boiling point (B.P.) and octanol/water partition coefficient (P).
  • B.P. boiling point
  • P octanol/water partition coefficient
  • the boiling point referred to herein is measured under normal standard pressure of 760 mmHg.
  • the boiling points of many volatile aldehydes, at standard 760 mm Hg are given in, for example, "Perfume and Flavor Chemicals (Aroma Chemicals),” written and published by Steffen Arctander, 1969.
  • the octanol/water partition coefficient of a volatile aldehyde is the ratio between its equilibrium concentrations in octanol and in water.
  • the partition coefficients of the volatile aldehydes used in the malodor control component may be more conveniently given in the form of their logarithm to the base 10, logP.
  • the logP values of many volatile aldehydes have been reported. See, e.g., the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California. 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.
  • ClogP 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 volatile aldehyde, 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 alternatively used instead of the experimental logP values in the selection of volatile aldehydes for the malodor control component.
  • the ClogP values may be defined by four groups and the volatile aldehydes may be selected from one or more of these groups.
  • the first group comprises volatile aldehydes that have a B.P. of about 250 °C or less and ClogP of about 3 or less.
  • the second group comprises volatile aldehydes that have a B.P. of 250°C or less and ClogP of 3.0 or more.
  • the third group comprises volatile aldehydes that have a B.P. of 250°C or more and ClogP of 3.0 or less.
  • the fourth group comprises volatile aldehydes that have a B.P. of 250°C or more and ClogP of 3.0 or more.
  • the malodor control component may comprise any combination of volatile aldehydes from one or more of the ClogP groups.
  • the malodor control component of the present invention may comprise, by total weight of the malodor control component, from about 0% to about 30% of volatile aldehydes from group 1, alternatively about 25%; and/or about 0% to about 10% of volatile aldehydes from group 2, alternatively about 10%; and/or from about 10% to about 30% of volatile aldehydes from group 3, alternatively about 30%; and/or from about 35% to about 60% of volatile aldehydes from group 4, alternatively about 35%.
  • Exemplary volatile aldehydes which may be used in a malodor control component include, but are not limited to, Adoxal (2,6,10-Trimethyl-9-undecenal), Bourgeonal (4-t- butylbenzenepropionaldehyde), Lilestralis 33 (2-methyl-4-t-butylphenyl)propanal), Cinnamic aldehyde, cinnamaldehyde (phenyl propenal, 3-phenyl-2-propenal), Citral, Geranial, Neral (dimethyloctadienal, 3,7-dimethyl-2,6-octadien-l-al), Cyclal C (2,4-dimethyl-3-cyclohexen-l- carbaldehyde), Florhydral (3-(3-Isopropyl-phenyl)-butyraldehyde), Citronellal (3,7-dimethyl 6- octenal), Cymal, cyclamen aldehyde,
  • aldehydes include, but are not limited to, acetaldehyde (ethanal), pentanal, valeraldehyde, amylaldehyde, Scentenal (octahydro-5-methoxy-4,7-Methano-lH- indene-2-carboxaldehyde), propionaldehyde (propanal), Cyclocitral, beta-cyclocitral, (2,6,6- trimethyl-l-cyclohexene-l-acetaldehyde), Iso Cyclocitral (2,4,6-trimethyl-3-cyclohexene-l- carboxaldehyde), isobutyraldehyde, butyraldehyde, isovaleraldehyde (3-methyl butyraldehyde), methylbutyraldehyde (2-methyl butyraldehyde, 2-methyl butanal), Dihydrocitronellal (3,7- dimethyl o
  • the malodor control component includes a mixture of two or more volatile aldehydes selected from the group consisting of 2-ethoxy Benzylaldehyde, 2-isopropyl- 5-methyl-2-hexenal, 5-methyl Furfural, 5-methyl-thiophene-carboxaldehyde, Adoxal, p- anisaldehyde, Benzylaldehyde, Bourgenal, Cinnamic aldehyde, Cymal, Decyl aldehyde, Floral super, Florhydral, Helional, Why aldehyde, Ligustral, Lyral, Melonal, o-anisaldehyde, Pino acetaldehyde, P.T. Bucinal, Thiophene carboxaldehyde, trans-4-Decenal, trans trans 2,4- Nonadienal, Undecyl aldehyde, and mixtures thereof.
  • the malodor control component includes fast reacting volatile aldehydes.
  • Fast reacting volatile aldehydes refers to volatile aldehydes that either (1) reduce amine odors by 20% or more in less than 40 seconds; or (2) reduce thiol odors by 20% or more in less than 30 minutes.
  • the malodor control component includes a mixture of the volatile aldehydes listed in Table 1 and referred to herein as Accord A.
  • the malodor control component includes a mixture of the volatile aldehydes listed in Table 2 and referred to herein as Accord B.
  • Accord B a mixture of the volatile aldehydes listed in Table 2 and referred to herein as Accord B.
  • Table 2 - Accord B a mixture of the volatile aldehydes listed in Table 2 and referred to herein as Accord B.
  • the malodor control component includes a mixture of about 71.2% volatile aldehydes, the remainder being other an ester and an alcohol perfume raw material. This mixture is listed in Table 3 and referred to herein as Accord C.
  • Accords A, B, or C can be formulated in with other perfume raw materials in an amount, for example, of about 10% by weight of the malodor control component. Additionally, the individual volatile aldehydes or a various combination of the volatile aldehydes can be formulated into a malodor control component.
  • the volatile aldehydes may be present in an amount up to 100%, by weight of the malodor control component, alternatively from 1% to about 100%, alternatively from about 2% to about 100%, alternatively from about 3% to about 100%, alternatively about 50% to about 100%, alternatively about 70% to about 100%, alternatively about 80% to about 100%, alternatively from about 1% to about 20%, alternatively from about 1% to about 10%, alternatively from about 1% to about 5%, alternatively from about 1% to about 3%, alternatively from about 2% to about 20%, alternatively from about 3% to about 20%, alternatively from about 4% to about 20%, alternatively from about 5% to about 20%, by weight of the composition.
  • the present invention may include poly- aldehydes, for example, di-, tri-, tetra-aldehydes.
  • Such embodiments may include laundry detergents, additive, and the like for leave-on, through the wash, and rinse-off type of applications.
  • the malodor control component of the present invention may include an effective amount of an acid catalyst to neutralize sulfur-based malodors. It has been found that certain mild acids have an impact on aldehyde reactivity with thiols in the liquid and vapor phase. It has been found that the reaction between thiol and aldehyde is a catalytic reaction that follows the mechanism of hemiacetal and acetal formation path. When the present malodor control component contains an acid catalyst and contacts a sulfur-based malodor, the volatile aldehyde reacts with thiol. This reaction may form a thiol acetal compound, thus, neutralizing the sulfur- based odor. Without an acid catalyst, only hemi-thiol acetal is formed.
  • Suitable acid catalysts have a VP, as reported by Scifinder, in the range of about 0.001 torr to about 38 torr, measured at 25 °C, alternatively about 0.001 torr to about 14 torr, alternatively from about 0.001 to about 1, alternatively from about 0.001 to about 0.020, alternatively about 0.005 to about 0.020, alternatively about 0.010 to about 0.020.
  • VP as reported by Scifinder
  • the acid catalyst may be a weak acid.
  • a weak acid is characterized by an acid dissociation constant, K a> which is an equilibrium constant for the dissociation of a weak acid; the pKa being equal to minus the decimal logarithm of K a.
  • the acid catalyst may have a pKa from about 4.0 to about 6.0, alternatively from about 4.3 and 5.7, alternatively from about 4.5 to about 5, alternatively from about 4.7 to about 4.9.
  • Suitable acid catalyst include those listed in Table 4.
  • Such acid catalysts may have a VP of about 0.001 torr to about 0.020 torr, measured at 25 °C, alternatively about 0.005 torr to about 0.020 torr, alternatively about 0.010 torr to about 0.020 torr.
  • acid catalyst include 5-methyl thiophene carboxaldehyde with carboxylic acid impurity, succinic acid, or benzoic acid.
  • the malodor control component may include about 0.05% to about 5%, alternatively about 0.1% to about 1.0%, alternatively about 0.1% to about 0.5%, alternatively about 0.1% to about 0.4%, alternatively about 0.4% to about 1.5%, alternatively about 0.4% of an acid catalyst by weight of the malodor control component.
  • the present malodor control component may include about 0.4% of acetic acid (50:50 TC:DPM, 0.4% acetic acid).
  • the acid catalyst may increase the efficacy of the volatile aldehyde on malodors in comparison to the malodor efficacy of the volatile aldehyde on its own.
  • 1% volatile aldehyde and 1.5% benzoic acid provides malodor removal benefit equal to or better than 5% volatile aldehyde alone.
  • the malodor control component may have a pH from about 3 to about 8, alternatively from about 4 to about 7, alternatively from about, alternatively from about 4 to about 6.
  • the dishwashing detergent compositions herein can further comprise a number of other optional ingredients suitable for use in liquid detergent compositions such as diluents, including dipropylene glycol methyl ether, and 3-methoxy-3-methyl-l-butanol, and mixtures thereof; dyes; pearlescent agents; opacifiers; enzymes; thickening agents; preservatives; disinfecting agents; and pH buffering means so that the liquid detergent compositions herein generally have a pH of from 3 to 14, alternatively 6 to 13, alternatively 8 to 11.
  • the pH of the composition can be adjusted using pH modifying ingredients known in the art.
  • Odor-masking agents refer to known compounds (e.g. perfume raw materials) that mask or hide a malodorous compound. Odor-masking may include a compound with a non- offensive or pleasant smell that is dosed such it limits the ability to sense a malodorous compound. Odor-masking may involve the selection of compounds which coordinate with an anticipated malodor to change the perception of the overall scent provided by the combination of odorous compounds. “Odor blocking agents” refer to known compounds that dull the human sense of smell.
  • composition may also include perfume raw materials that solely provide a hedonic benefit (i.e. that do not neutralize malodors yet provide a pleasant fragrance). Suitable perfumes are disclosed in US 6,248,135, which is incorporated in its entirety by reference.
  • composition of the present invention may have viscosity from 50 to 2000 centipoises
  • Viscosity can be determined by conventional methods.
  • Viscosity according to the present invention is measured using an AR 550 rheometer from TA instruments using a plate steel spindle at 40 mm diameter and a gap size of 500 ⁇ .
  • the high shear viscosity at 20 s"1 and low shear viscosity at 0.05 s l can be obtained from a logarithmic shear rate sweep from 0.1 s l to 25 s l in 3 minutes time at 20°C.
  • the preferred rheology described therein may be achieved using internal existing structuring with detergent ingredients or by employing an external rheology modifier.
  • the composition comprises further a rheology modifier.
  • the method of the present invention comprises cleaning dishware with a dishwashing detergent composition comprising a cleaning agent and malodour control component.
  • the dishwashing operation comprises the steps of applying said composition onto said dishware, typically in diluted or neat form and rinsing said composition from said dishware or said surface, or leaving the composition to dry on said surface without rinsing said dishware or said surface. Instead of leaving said composition to dry on said surface on the air, it can also be hand-dried using a kitchen towel.
  • the hands and skin of the user may be exposed to the composition in diluted or neat form.
  • composition in its neat form, it is meant herein that the composition is applied directly onto the surface to be treated without undergoing any dilution by the user (immediately) prior to the application.
  • This direct application of that said composition onto the surface to be treated can be achieved through direct squeezing of that said composition out of the hand dishwashing liquid bottle onto the surface to be cleaned, or through squeezing that said composition out of the hand dishwashing liquid bottle on a pre-wetted or non pre-wetted cleaning article, such as without intending to be limiting a sponge, a cloth or a brush, prior to cleaning the targeted surface with said cleaning article.
  • diluted form it is meant herein that said composition is diluted by the user with an appropriate solvent, typically with water.
  • washing it is meant herein contacting the dishware cleaned with the process according to the present invention with substantial quantities of appropriate solvent, typically water, after the step of applying the composition herein onto said dishware.
  • substantial quantities it is meant usually 0.1 to 20 liters.
  • the composition herein can be applied in its diluted form.
  • Soiled dishes are contacted with an effective amount, typically from 0.5 ml to 20 ml (per 25 dishes being treated), alternatively from 3ml to 10 ml, of the liquid detergent composition of the present invention diluted in water.
  • the actual amount of liquid detergent composition used will be based on the judgment of user, and will typically depend upon factors such as the particular product formulation of the composition, including the concentration of active ingredients in the composition, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like.
  • the particular product formulation in turn, will depend upon a number of factors, such as the intended market (i.e., U.S., Europe, Japan, etc.) for the composition product. Typical light-duty detergent compositions are described in the examples section.
  • a detergent composition of the invention is combined with from 2000 ml to 20000 ml, more typically from 5000 ml to 15000 ml of water in a sink having a volumetric capacity in the range of from 1000 ml to 20000 ml, more typically from 5000 ml to 15000 ml.
  • the soiled dishes are immersed in the sink containing the diluted compositions then obtained, where contacting the soiled surface of the dish with a cloth, sponge, or similar article cleans them.
  • the cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranged from 1 to 10 seconds, although the actual time will vary with each application and user.
  • the contacting of cloth, sponge, or similar article to the dish surface is alternatively accompanied by a concurrent scrubbing of the dish surface.
  • Another method of the present invention will comprise immersing the soiled dishes into a water bath or held under running water without any liquid dishwashing detergent.
  • a device for absorbing liquid dishwashing detergent such as a sponge, is placed directly into a separate quantity of a concentrated pre-mix of diluted liquid dishwashing detergent, for a period of time typically ranging from 1 to 5 seconds.
  • the absorbing device, and consequently the diluted liquid dishwashing composition is then contacted individually to the surface of each of the soiled dishes to remove said soiling.
  • the absorbing device is typically contacted with each dish surface for a period of time range from 1 to 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish.
  • the step of contacting of the absorbing device to the dish surface is alternatively accompanied by concurrent scrubbing.
  • said concentrated pre-mix of diluted liquid dishwashing detergent is formed by combining 1ml to 200ml of neat dishwashing detergent with 50ml to 1500ml of water, more typically from 200ml to 1000ml of water.
  • the detergent compositions of the present invention may be packaged in any suitable packaging for delivering the liquid detergent composition for use.
  • the package is a clear package made of glass or plastic.
  • Malodor standards are prepared by pipeting 1 mL of butylamine (amine-based malodor) and butanethiol (sulfur-based malodor) into a 1.2 liter gas sampling bag. The bag is then filled to volume with nitrogen and allowed to sit for at least 12 hours to equilibrate.
  • 1.5 mL of the target malodor standard is injected into each 10 mL vial.
  • the vials containing a sample +malodor standard are held at room temperature for 30 minutes.
  • a 1 mL headspace syringe is then used to inject 250 ⁇ L of each sample/malodor into a GC/MS split/splitless inlet.
  • a 1 mL headspace syringe is used to inject 500 ⁇ L of each sample/malodor immediately into the GC/MS split/splitless inlet.
  • a GC pillow is used for the amine analysis to shorten the run times.
  • Samples are then analyzed using a GC/MS with a DB-5, 20 m, 1 ⁇ film thickness column with an MPS-2 autosampler equipment with static headspace function. Data is analyzed by ion extraction on each total ion current (56 for thiol and 30 for amine) and the area is used to calculate the percent reduction from the malodor standard for each sample.
  • Table 6 shows the effect of certain volatile aldehydes on neutralizing amine-based and sulfur based malodors at 40 seconds and 30 minutes, respectively.
  • Table 7 shows the percent reduction of butylamine and butaniethiol at 40 seconds and 30 minutes, respectively, for Accords A, B, and C.
  • Fig. 1 demonstrates that low vapor pressure acid catalysts provide up to 3 times better reduction of sulfur-based malodors in comparison to the control.
  • Analytical Test Effect of volatile aldehydes and acid catalyst on amine-based and sulfur-based malodors
  • Tables 8 and 9 show that a perfume mixture having as little as 1 % volatile aldehyde along with 1.5% acid catalyst performs better at reducing butylamine and butanethiol than the same perfume mixture having 5% volatile aldehyde.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)

Abstract

A dishwashing detergent composition comprising a malodor control component, and methods of cleaning dishware are provided. In some embodiments, the dishwashing detergent composition comprises at least one volatile aldehyde and an acid catalyst.

Description

DISHWASHING DETERGENT COMPOSITION HAVING A MALODOR CONTROL COMPONENT AND METHODS OF CLEANING DISHWARE FIELD OF THE INVENTION
The present invention relates to dishwashing detergent compositions having a malodor control component, and methods of cleaning dishware.
BACKGROUND OF THE INVENTION
Scented dishwashing detergent products for cleaning dishware are known. Typically, dishwashing detergent manufacturers develop perfume technology that provides a pleasant scent and masks malodors associated with soiled dishware.
However, not all odors are effectively controlled by products on the market as amine- based malodors such as fish malodors, and sulfur-based malodors such as garlic and onion are difficult to combat. Further, the time required for a product to noticeably combat malodors may create consumer doubt as to a product's efficacy on malodors. For example, the consumer may finish washing a dish and leave the area before the product begins to noticeably reduce the malodor.
The difficulty in overcoming a broad range of malodors has spawned a diverse assortment of products to neutralize, mask, or contain the malodors. There remains a need for a dishwashing detergent composition that cleans dishware and is effective on a broad range of malodors, including amine-based and sulfur-based malodors, while not overpowering malodors with an overwhelming perfume. SUMMARY OF THE INVENTION
In one embodiment, there is provided a dishwashing detergent composition comprising: (a) from about 0.1% to about 20% by weight of the total composition of a chelant; (b) from about 5% to about 80% by weight of the total composition of a surfactant selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwitterionic, semi-polar nonionic surfactants and mixtures thereof; and (c) a malodor control component comprising an effective amount of two or more volatile aldehydes for neutralizing a malodor, wherein said two or more volatile aldehydes are selected from the group consisting of 2-ethoxy benzylaldehyde, 2- isopropyl-5-methyl-2-hexenal, 5-methyl furfural, 5-methyl-thiophene-carboxaldehyde, adoxal, p- anisaldehyde, benzylaldehyde, bourgenal, cinnamic aldehyde, cymal, decyl aldehyde, floral super, florhydral, helional, lauric aldehyde, ligustral, lyral, melonal, o-anisaldehyde, pino acetaldehyde, P.T. bucinal, thiophene carboxaldehyde, trans-4-decenal, trans trans 2,4- nonadienal, undecyl aldehyde, and mixtures thereof.
In another embodiment, there is provided a dishwashing detergent composition comprising: (a) a chelant; (b) a surfactant selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwitterionic, semi-polar nonionic surfactants, and mixtures thereof; and (c) a malodor control component comprising: (i) at least one volatile aldehyde; and (ii) an acid catalyst having a vapor pressure of about 0.01 to about 13 at 25°C; and (b) about 1% to about 5%, by weight of said composition, of a low molecular weight monohydric alcohol.
In another embodiment, there is provided a method of cleaning a dishware comprising the steps of: applying a composition according to claim 1 on said dishware; and rinsing said composition off of said dishware.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a graph showing butanethiol reduction by thiophene carboxaldehyde in combination with various acid catalysts.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a dishwashing detergent composition that surprisingly provides excellent grease cleaning combined with superior shine and malodor control; and methods of cleaning dishware.
"Cleaning" means applying to a surface for the purpose of cleaning, and/or disinfecting. "Dishware" means a surface such as dishes, glasses, pots, pans, baking dishes and flatware made from ceramic, china, metal, glass, plastic (polyethylene, polypropylene, polystyrene, etc.) and wood.
"Dishwashing detergent composition" refers to those compositions that are employed in manual (i.e. hand) dishwashing. Such compositions are generally high sudsing or foaming in nature.
"Grease" means materials comprising at least in part (i.e., at least 0.5 wt% by weight of the grease) saturated and unsaturated fats and oils, alternatively oils and fats derived from animal sources such as beef and/or chicken.
"Malodor" refers to compounds generally offensive or unpleasant to most people, such as the complex odors associated with bowel movements. "Neutralize" or "neutralization" refers to the ability of a compound or product to reduce or eliminate malodorous compounds. Odor neutralization may be partial, affecting only some of the malodorous compounds in a given context, or affecting only part of a malodorous compound. A malodorous compound may be neutralized by chemical reaction resulting in a new chemical entity, by sequestration, by chelation, by association, or by any other interaction rendering the malodorous compound less malodorous or non- malodorous. Odor neutralization may be distinguished from odor masking or odor blocking by a change in the malodorous compound, as opposed to a change in the ability to perceive the malodor without any corresponding change in the condition of the malodorous compound.
"Suds profile" means the amount of sudsing (high or low) and the persistence of sudsing
(sustained sudsing) throughout the washing process resulting from the use of the liquid detergent composition of the present composition. As used herein "high sudsing" refers to liquid hand dishwashing detergent compositions which are both high sudsing (i.e. a level of sudsing considered acceptable to the consumer) and have sustained sudsing (i.e. a high level of sudsing maintained throughout the dishwashing operation). This is particularly important with respect to liquid dishwashing detergent compositions as the consumer uses high sudsing as an indicator of the performance of the detergent composition. Moreover, the consumer of a liquid dishwashing detergent composition also uses the sudsing profile as an indicator that the wash solution still contains active detergent ingredients. The consumer usually renews the wash solution when the sudsing subsides. Thus, a low sudsing liquid dishwashing detergent composition formulation will tend to be replaced by the consumer more frequently than is necessary because of the low sudsing level.
I. Dishwashing Detergent Composition
The dishwashing detergent composition generally contains from 30% to 95%, alternatively 40% to 80%, alternatively 50% to 75% of an aqueous liquid carrier, in which the other essential and optional compositions components are dissolved, dispersed or suspended. A. Chelant
The composition of the present invention comprises a chelant at a level of from 0.1% to 20%, alternatively from 0.2% to 5%, alternatively from 0.2% to 3% by weight of total composition.
As commonly understood in the detergent field, chelation herein means the binding or complexation of a bi- or multidentate ligand. These ligands, which are often organic compounds, are called chelants, chelators, chelating agents, and/or sequestering agent. Chelating agents form multiple bonds with a single metal ion. Chelants, are chemicals that form soluble, complex molecules with certain metal ions, inactivating the ions so that they cannot normally react with other elements or ions to produce precipitates or scale. The ligand forms a chelate complex with the substrate. The term is reserved for complexes in which the metal ion is bound to two or more atoms of the chelant. The chelants for use in the present invention are those having crystal growth inhibition properties, i.e. those that interact with the small calcium and magnesium carbonate particles preventing them from aggregating into hard scale deposit. The particles repel each other and remain suspended in the water or form loose aggregates which may settle. These loose aggregates are easily rinsed away and do not form a deposit.
Suitable chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polufanctionally-substituted aromatic chelating agents and mixtures thereof.
Suitable chelants for use herein are also the amino acids based chelants, alternatively glutamic-Ν,Ν- diacetic acid and derivatives and/or phosphonate based chelants, alternatively diethylenetriamine penta methylphosphonic acid.
Amino carboxylates include ethylenediaminetetra- acetates, N- hydroxyethylethylenediaminetriacetates, nitrilo-triacetates, ethylenediamine tetrapro-prionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldi-glycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein. As well as MGDA (methyl-glycine-diacetic acid), and salts and derivatives thereof and GLDA (glutamic- N,N- diacetic acid) and salts and derivatives thereof. In one embodiment, the composition comprises GLDA (salts and derivatives thereof). In another embodiment, the composition comprises tetrasodium salt.
Other suitable chelants include amino acid based compound or a succinate based compound. The term "succinate based compound" and "succinic acid based compound" are used interchangeably herein. Other suitable chelants are described in USP 6,426,229. Particular suitable chelants include; for example, aspartic acid-N-monoacetic acid (ASMA), aspartic acid- Ν,Ν-diacetic acid (ASDA), aspartic acid-N- monopropionic acid (ASMP) , iminodisuccinic acid (IDS), Imino diacetic acid (IDA), N- (2-sulfomethyl) aspartic acid (SMAS), N- (2-sulfoethyl) aspartic acid (SEAS), N- (2- sulfomethyl) glutamic acid (SMGL), N- (2- sulfoethyl) glutamic acid (SEGL), N- methyliminodiacetic acid (MID A),□- alanine-N,N-diacetic acid (□ -ALDA) , serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N- diacetic acid (PHD A) , anthranilic acid- N ,N - diacetic acid (AND A), sulfanilic acid-N, N- diacetic acid (SLDA) , taurine-N, N-diacetic acid (TUDA) and sulfomethyl-N,N-diacetic acid (SMDA) and alkali metal salts or ammonium salts thereof. Also suitable is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233. Furthermore, Hydroxyethyleneiminodiacetic acid, Hydroxyiminodisuccinic acid, Hydroxyethylene diaminetriacetic acid are also suitable.
Other chelants include homopolymers and copolymers of polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts. Suitable salts of the abovementioned compounds are the ammonium and/or alkali metal salts, i.e. the lithium, sodium, and potassium salts.
Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, in which case they contain at least two carboxyl groups which are in each case separated from one another by, alternatively, no more than two carbon atoms. Polycarboxylates which comprise two carboxyl groups include, for example, water-soluble salts of, malonic acid, (ethyl enedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid. Polycarboxylates which contain three carboxyl groups include, for example, water-soluble citrate. Correspondingly, a suitable hydroxycarboxylic acid is, for example, citric acid. Another suitable polycarboxylic acid is the homopolymer of acrylic acid. In one embodiment, the composition includes the polycarboxylates end capped with sulfonates.
Amino phosphonates are also suitable for use as chelating agents and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. In one embodiment, the composition includes amino phosphonates that do 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 such as described in U.S. Patent 3,812,044. In one embodiment, the composition includes dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.
Further suitable polycarboxylates chelants for use herein include citric acid, lactic acid, acetic acid, succinic acid, formic acid; all alternatively in the form of a water-soluble salt. Other suitable polycarboxylates are oxodisuccinates, carboxymethyloxysuccinate and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
B. Surfactants
The composition of the present invention may comprise a surfactant selected from anionic, nonionic, cationic, amphoteric, zwitterionic, semi-polar nonionic surfactants, and mixtures thereof. The surfactants of the composition will have an average branching of the alkyl chain(s) of more than 10%, alternatively more than 20%, alternatively more than 30%, alternatively more than 40%, by weight of the total surfactants.
The surfactants of the present invention will generally be present at a level of 5% to 80%, alternatively 10% to 60%, alternatively 12% to 45%, by weight of the total composition.
In one embodiment, the composition of the present invention will further comprise a nonionic surfactant at a weight ratio of total surfactant to nonionic surfactant of 2 to 10, alternatively of 2 to 7.5, alternatively of 2 to 6.
The surfactants described below can be used in their linear and/or branched version. 1. Nonionic Surfactants
It has been found that the addition of nonionic surfactants, alternatively of branched nonionic surfactants, will prevent efficiently the formation of crystalline films of the dish surface and will provide improved wetting and thereby providing superior shine.
Nonionic surfactants are present in a typical amount of from 2% to 40%, alternatively 3% to 30% by weight of the liquid detergent composition and alternatively from 3 to 20% by weight of the total composition. Suitable nonionic surfactants include the condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. In one embodiment, the composition includes the condensation products of alcohols having an alkyl group containing from 8 to 18 carbon atoms, alternatively from 9 to 15 carbon atoms with from 2 to 18 moles, alternatively 2 to 15, alternatively 5-12 of ethylene oxide per mole of alcohol.
Also suitable are alkylpolyglycosides having the formula R20(CnH2nO)t(glycosyl)x (formula (III)), wherein R2 of formula (III) 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, alternatively from 12 to 14, carbon atoms; n of formula (III) is 2 or 3, alternatively 2; t of formula (III) is from 0 to 10, alternatively 0; and x of formula (III) is from 1.3 to 10, alternatively from 1.3 to 3, most alternatively from 1.3 to 2.7. The glycosyl is alternatively derived from glucose. Also suitable are alkyl glycerol ethers and sorbitan esters.
Also suitable are fatty acid amide surfactants having the formula (IV):
O
61 1 7
R6CN(R7)2
(IV) wherein R6 of formula (IV) is an alkyl group containing from 7 to 21, alternatively from 9 to 17, carbon atoms and each R7 of formula (IV) is selected from the group consisting of hydrogen, Ci- C4 alkyl, Ci-C4 hydroxyalkyl, and -(C2H40)XH where x of formula (IV) varies from 1 to 3. Suitable amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
Suitable nonionic surfactants for use in the present invention are the condensation products of aliphatic alcohols with ethylene oxide, such as the mixture of nonyl (C9), decyl (CIO) undecyl (Cl l) alcohol modified with on average 5 ethylene oxide (EO) units such as the commercially available Neodol 91-5 or the Neodol 91-8 that is modified with on average 8 EO units. Also suitable are the longer alkyl chains ethoxylated nonionics such as C12, C13 modified with 5 EO (Neodol 23-5). Neodol is a Shell tradename. Also suitable is the C12, C14 alkyl chain with 7 EO, commercially available under the trade name Novel 1412-7 (Sasol) or the Lutensol A 7 N (BASF)
Suitable branched nonionic are the Guerbet CIO alcohol ethoxylates with 5 EO such as Ethylan 1005, Lutensol XP 50 and the Guerbet CIO alcohol alkoxylated nonionics (modified with EO and PO=propyleneoxyde) such as the commercially available Lutensol XL series (X150, XL70,...). Other branching also include oxo branched nonionic surfactants such as the Lutensol ON 50 (5 EO) and Lutensol ON70 (7 EO). Other suitable branched nonionics are the ones derived from the isotridecyl alcohol and modified with ethyleneoxyde such as the Lutensol T07 (7EO) from BASF and the Marlipal O 13/70 (7EO) from Sasol. Also suitable are the ethoxylated fatty alcohols originating from the Fisher & Troshp reaction comprising up to 50% branching (40% methyl (mono or bi) 10% cyclohexyl) such as those produced from the safol™ alcohols from Sasol; ethoxylated fatty alcohols originating from the oxo reaction wherein at least 50 weight % of the alcohol is C2 isomer (methyl to pentyl) such as those produced from the Isalchem™ alcohols or Lial™ alcohols from Sasol; the ethoxylated fatty alcohols originating from the modified oxo reaction wherein at least 15 weight % of the alcohol is C2 isomer (methyl to pentyl) such as those produced from the Neodol™ alcohols from Shell
2. Amphoteric/Zwitterionic Surfactants
The amphoteric and zwitterionic surfactanta can be present at a level of from 0.01% to 20%, alternatively from 0.2% to 15%, alternatively 0.5% to 10%, by weight of the composition. The compositions of the present invention may further comprise an amine oxide and/or a betaine.
In one embodiment, the composition includes amine oxides are coco dimethyl amine oxide or coco amido propyl dimethyl amine oxide. Amine oxide may have a linear or mid- branched alkyl moiety. Typical linear amine oxides include water-soluble amine oxides containing one Rl C8-i8 alkyl moiety and 2 R2 and R3 moieties selected from the group consisting of Ci_3 alkyl groups and Ci-3 hydroxyalkyl groups. Alternatively, amine oxide is characterized by the formula Rl - N(R2)(R3) -^O wherein Ri is a C8-i8 alkyl and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2- hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactants in particular may include linear Cio-Ci8 alkyl dimethyl amine oxides and linear C8-Ci2 alkoxy ethyl dihydroxy ethyl amine oxides. Suitable amine oxides include linear Cio, linear Cio-Ci2, and linear Ci2-Ci4 alkyl dimethyl amine oxides.
As used herein "mid-branched" means that the amine oxide has one alkyl moiety having ni carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms. The alkyl branch is located on the a carbon from the nitrogen on t he alkyl moiety. This type of branching for the amine oxide is also known in the art as an internal amine oxide. The total sum of ni and n2 is from 10 to 24 carbon atoms, alternatively from 12 to 20, and alternatively from 10 to 16. The number of carbon atoms for the one alkyl moiety (ni) should be approximately the same number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric. As used herein "symmetric" means that I ni - n2 I is less than or equal to 5, alternatively 4, alternatively from 0 to 4 carbon atoms in at least 50 wt%, alternatively at least 75 wt% to 100 wt% of the mid-branched amine oxides for use herein.
The amine oxide further comprises two moieties, independently selected from a C1-3 alkyl, a Ci_3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups. Alternatively, the two moieties are selected from a Ci-3 alkyl, alternatively both are selected as a Ci alkyl.
Other suitable surfactants include betaines such alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as the Phosphobetaine and alternatively meets formula I:
R'-fCO-X (CH2)n]x-N+(R2)(R3)-(CH2)m-[CH(OH)-CH2]y-Y- (I) wherein
R1 is a saturated or unsaturated C6-22 alkyl residue, alternatively C8-18 alkyl residue, in particular a saturated ClO-16 alkyl residue, for example a saturated C12-14 alkyl residue; X is NH, NR4 with Cl-4 Alkyl residue R4, O or S,
n a number from 1 to 10, alternatively 2 to 5, in particular 3,
x 0 or 1, alternatively 1, R2, R3 are independently a CI -4 alkyl residue, potentially hydroxy substituted such as a hydroxyethyl, alternatively a methyl.
m a number from 1 to 4, in particular 1, 2 or 3,
y 0 or 1 and
Y is COO, S03, OPO(OR5)0 or P(0)(OR5)0, whereby R5 is a hydrogen atom H or a Cl-
4 alkyl residue.
Suitable betaines are the alkyl betaines of the formula (la), the alkyl amido betaine of the formula (lb), the Sulfo betaines of the formula (Ic) and the Amido sulfobetaine of the formula (Id);
R1-N+(CH3)2-CH2COO" (la)
R1-CO-NH(CH2)3-N+(CH3)2-CH2COO" (lb)
R1-N+(CH3)2-CH2CH(OH)CH2S03- (Ic)
R1-CO-NH-(CH2)3-N+(CH3)2-CH2CH(OH)CH2S03- (Id) in which R1! as the same meaning as in formula I. Suitable betaines are the Carbobetaine
[wherein Y~=COO~], in particular the Carbobetaine of the formula (la) and (lb), alternatively the Alkylamidobetaine of the formula (lb). ]
Examples of suitable betaines and sulfobetaine are the following [designated in accordance with INCI]: Almondamidopropyl of betaines, Apricotam idopropyl betaines, Avocadamidopropyl of betaines, Babassuamidopropyl of betaines, Behenam idopropyl betaines, Behenyl of betaines, betaines, Canolam idopropyl betaines, Capryl/Capram idopropyl betaines, Carnitine, Cetyl of betaines, Cocamidoethyl of betaines, Cocam idopropyl betaines, Cocam idopropyl Hydroxysultaine, Coco betaines, Coco Hydroxysultaine, Coco/Oleam idopropyl betaines, Coco Sultaine, Decyl of betaines, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl of PG-betaines, Erucam idopropyl Hydroxysultaine, Hydrogenated Tallow of betaines, Isostearam idopropyl betaines, Lauram idopropyl betaines, Lauryl of betaines, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkam idopropyl betaines, Minkamidopropyl of betaines, Myristam idopropyl betaines, Myristyl of betaines, Oleam idopropyl betaines, Oleam idopropyl Hydroxysultaine, Oleyl of betaines, Olivamidopropyl of betaines, Palmam idopropyl betaines, Palm itam idopropyl betaines, Palmitoyl Carnitine, Palm Kernelam idopropyl betaines, Polytetrafluoroethylene Acetoxypropyl of betaines, Ricinoleam idopropyl betaines, Sesam idopropyl betaines, Soyam idopropyl betaines, Stearam idopropyl betaines, Stearyl of betaines, Tallowam idopropyl betaines, Tallowam idopropyl Hydroxysultaine, Tallow of betaines, Tallow Dihydroxyethyl of betaines, Undecylenam idopropyl betaines and Wheat Germam idopropyl betaines. In one embodiment, the composition includes Cocam idopropyl betaines (Cocoamidopropylbetain) .
3. Anionic surfactants
Suitable anionic surfactants to be used in the compositions and methods of the present invention are sulfates, sulfosuccinates, sulfoacetates, and/or sulfonates; alternatively alkyl sulfate and/or alkyl ethoxy sulfates; alternatively a combination of alkyl sulfates and/or alkyl ethoxy sulfates with a combined ethoxylation degree less than 5, alternatively less than 3, alternatively less than 2.
Sulphate or sulphonate surfactant is typically present at a level of at least 5%, alternatively from 5% to 40%, alternatively from 15% to 30%, alternatively at 15% to 25%, by weight of the liquid detergent composition.
Suitable sulphate or sulphonate surfactants for use in the compositions herein include water-soluble salts or acids of Cio-Ci4 alkyl or hydroxyalkyl, sulphate or sulphonates. Suitable counterions include hydrogen, alkali metal cation or ammonium or substituted ammonium, but alternatively sodium. Where the hydrocarbyl chain is branched, it alternatively comprises C alkyl branching units. The average percentage branching of the sulphate or sulphonate surfactant is alternatively greater than 30%, alternatively from 35% to 80%, alternatively from 40% to 60% of the total hydrocarbyl chains.
The sulphate or sulphonate surfactants may be selected from Cn-Ci8 alkyl benzene sulphonates (LAS), C8-C20 primary, branched-chain and random alkyl sulphates (AS); Cio-Ci8 secondary (2,3) alkyl sulphates; Cio-Ci8 alkyl alkoxy sulphates (AEXS) wherein alternatively x is from 1-30; Cio-Ci8 alkyl alkoxy carboxylates alternatively comprising 1-5 ethoxy units; mid- chain branched alkyl sulphates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulphates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulphonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; methyl ester sulphonate (MES); and alpha-olefin sulphonate (AOS).
The paraffin sulphonates may be monosulphonates or disulphonates and usually are mixtures thereof, obtained by sulphonating paraffins of 10 to 20 carbon atoms. Suitable sulphonates are those of C12-18 carbon atoms chains and alternatively they are C14-17 chains. Paraffin sulphonates that have the sulphonate group(s) distributed along the paraffin chain are described in US2,503,280; US2,507,088; US3, 260,744; US 3,372 188 and in DE 735 096. Also suitable are the alkyl glyceryl sulphonate surfactants and/or alkyl glyceryl sulphate surfactants described in WO06/014740: A mixture of oligomeric alkyl glyceryl sulfonate and/or sulfate surfactant selected from dimers, trimers, tetramers, pentamers, hexamers, heptamers, and mixtures thereof; wherein the weight percentage of monomers is from 0 wt% to 60 wt% by weight of the alkyl glyceryl sulfonate and/or sulfate surfactant mixture.
Other suitable anionic surfactants are alkyl, alternatively dialkyl sulfosuccinates and/or sulfoacetate. The dialkyl sulfosuccinates may be a C6-i5 linear or branched dialkyl sulfosuccinate. The alkyl moieties may be symmetrical (i.e., the same alkyl moieties) or asymmetrical (i.e., different alkyl moiety.es). Alternatively, the alkyl moiety is symmetrical.
Most common branched anionic alkyl ether sulphates are obtained via sulfation of a mixture of the branched alcohols and the branched alcohol ethoxylates. Also suitable are the sulfated fatty alcohols originating from the Fisher & Troshp reaction comprising up to 50% branching (40% methyl (mono or bi) 10% cyclohexyl) such as those produced from the safol™ alcohols from Sasol; sulfated fatty alcohols originating from the oxo reaction wherein at least 50 weight % of the alcohol is C2 isomer (methyl to pentyl) such as those produced from the Isalchem™ alcohols or Lial™ alcohols from Sasol; the sulfated fatty alcohols originating from the modified oxo reaction wherein at least 15 weight % of the alcohol is C2 isomer (methyl to pentyl) such as those produced from the Neodol™ alcohols from Shell.
4. Cationic Surfactants
Cationic surfactants, when present in the composition, are present in an effective amount, alternatively from 0.1% to 20%, by weight of the composition. Suitable cationic surfactants are quaternary ammonium surfactants. Suitable quaternary ammonium surfactants are selected from the group consisting of mono C6-Ci6, alternatively C6-C10 N-alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are substituted by methyl, hydroxyehthyl or hydroxypropyl groups. Another suitable cationic surfactant is an C6-Ci8 alkyl or alkenyl ester of a quaternary ammonium alcohol, such as quaternary chlorine esters. Alternatively, the cationic surfactants have the formula (V):
Figure imgf000013_0001
(V) wherein Rl of formula (V) is C$-Ci$ hydrocarbyl and mixtures thereof, alternatively, C8-i4 alkyl, alternatively, C8, Cio or Ci2 alkyl, and X of formula (V) is an anion, alternatively, chloride or bromide.
C. Cleaning polymer
The composition of the present invention can further comprise one or more alkoxylated polyethyleneimine polymer. The composition may comprise from 0.01 wt% to 10 wt%, alternatively from 0.01 wt% to 2 wt%, alternatively from 0.1 wt% to 1.5 wt%, alternatively from 0.2% to 1.5%, by weight of the composition, of an alkoxylated polyethyleneimine polymer as described on page 2, line 33 to page 5, line 5 and exemplified in examples 1 to 4 at pages 5 to 7 of WO2007/135645.
The alkoxylated polyethyleneimine polymer of the present composition has a polyethyleneimine backbone having from 400 to 10000 weight average molecular weight, alternatively from 400 to 7000 weight average molecular weight, alternatively from 3000 to 7000 weight average molecular weight.
These polyamines can be prepared for example, by polymerizing ethyleneimine in presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.
The alkoxylation of the polyethyleneimine backbone includes: (1) one or two alkoxylation modifications per nitrogen atom, dependent on whether the modification occurs at a internal nitrogen atom or at an terminal nitrogen atom, in the polyethyleneimine backbone, the alkoxylation modification consisting of the replacement of a hydrogen atom on a polyalkoxylene chain having an average of about 1 to about 40 alkoxy moieties per modification, wherein the terminal alkoxy moiety of the alkoxylation modification is capped with hydrogen, a Ci-C4 alkyl or mixtures thereof; (2) a substitution of one Ci-C4 alkyl moiety or benzyl moiety and one or two alkoxylation modifications per nitrogen atom, dependent on whether the substitution occurs at a internal nitrogen atom or at an terminal nitrogen atom, in the polyethyleneimine backbone, the alkoxylation modification consisting of the replacement of a hydrogen atom by a polyalkoxylene chain having an average of about 1 to about 40 alkoxy moieties per modification wherein the terminal alkoxy moiety is capped with hydrogen, a Ci-C4 alkyl or mixtures thereof; or (3) a combination thereof.
The composition may further comprise the amphiphilic graft polymers based on water soluble polyalkylene oxides (A) as a graft base and sides chains formed by polymerization of a vinyl ester component (B), said polymers having an average of <1 graft site per 50 alkylene oxide units and mean molar mass Mw of from 3,000 to 100,000 described in BASF patent application WO2007/138053 on pages 2 line 14 to page 10, line 34 and exemplified on pages 15-18.
D. Salts and solvents
Salts and solvents are generally used to ensure preferred product quality for dissolution, thickness and aesthetics and to ensure better processing. When salts are included, the ions can be selected from magnesium, sodium, potassium, calcium, and/or magnesium and alternatively from sodium and magnesium, and are added as a hydroxide, chloride, acetate, sulphate, formate, oxide or nitrate salt to the compositions of the present invention. Salts are generally present at an active level of from 0.01% to 5%, alternatively from 0.015% to 3%, alternatively from 0.025 % to 2.0%, by weight of the liquid detergent composition. In one embodiment, additional magnesium ions may be avoided.
Suitable solvents include C1-C5 alcohols are according to the formula R-OH wherein R is a linear saturated alkyl group of from 1 to 5 carbon atoms, alternatively from 2 to 4. Suitable alcohols are ethanol, propanol, isopropanol or mixtures thereof. Other suitable alcohols are alkoxylated Cl-8 alcohols according to the formula R (A0n-oh wherein R is a linear alkyl group of from 1 to 8 carbon atoms, alternatively from 3 to 6, wherein A is an alkoxy group alternatively propoxy and/or ethoxy and n is an integer of from 1 to 5, alternatively from 1 to 2. Suitable alcohols are buthoxy propoxy propanol (n-BPP), buthoxy Propanol (n-BP) buthoxyethanol or mixtures thereof. Suitable alkoxylated aromatic alcohols to be used herein are according to the formula R (B)n-OH whereinm R is an alkyl substituted or non alkyl substituted aryl group of from 1 to 20 carbon atoms ,, alternatively from 2 to 15 and alternatively from 2 to 10, wherein B is an alkoxy grup alternatively buthoxy, propoxy and/or ethoxy and n is an integer from of from 1 to 5, alternatively from 1 to 2. Suitable alkoxylated aromatic alcohols are benzoyethanol and or benzoypropanol. A suitable aromatic alcohol to be used herein is benzyl alcohol. Other suitable solvents include butyl diglycolether , benzylalcohol, propoxyporpoxypropanol (EP 0 859 044) ethers and diethers, glycols, alkoxylated glycols, C6-Ci6 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.
When present, the liquid detergent composition may contain from 0.01% to 20%, alternatively from 0.5% to 20%, alternatively from 1% to 10%, by weight of the composition, of a solvent. These 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. E. Hydrotrope
The dishwashing detergent compositions of the present invention may optionally comprise a hydrotrope in an effective amount so that the liquid detergent compositions are appropriately compatible in water. Suitable hydrotropes for use herein include anionic-type hydrotropes, particularly sodium, potassium, and ammonium xylene sulphonate, sodium, potassium and ammonium toluene sulphonate, sodium potassium and ammonium cumene sulphonate, and mixtures thereof, and related compounds, as disclosed in U.S. Patent 3,915,903.
The compositions of the present invention typically comprise from 0% to 15% by weight of the liquid detergent composition of a hydro tropic, or mixtures thereof, alternatively from 1% to 10%, most alternatively from 3% to 6% by weight.
F. Polymeric Suds Stabilizer
The compositions of the present invention may optionally contain a polymeric suds stabilizer. These polymeric suds stabilizers provide extended suds volume and suds duration of the liquid detergent compositions. These polymeric suds stabilizers may be selected from homopolymers of (N,N-dialkylamino) alkyl esters and (N,N-dialkylamino) alkyl acrylate esters. The weight average molecular weight of the polymeric suds boosters, determined via conventional gel permeation chromatography, is from 1,000 to 2,000,000, alternatively from 5,000 to 1,000,000, alternatively from 10,000 to 750,000, alternatively from 20,000 to 500,000, even alternatively 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, sulphate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
In one embodiment, the composition includes a suds stabilizer that is (N,N- dimethylamino)alkyl acrylate esters namely the acrylate ester represented by the formula (VII):
Figure imgf000016_0001
(VII)
Other suitable suds boosting polymers are copolymers of hydroxypropylacrylate/dimethyl aminoethylmethacrylate (copolymer of HPA/DMAM), represented by the formulae VIII and IX
Figure imgf000017_0001
(VIII) (IX)
When present in the compositions, the polymeric suds booster/stabilizer may be present in the composition from 0.01% to 15%, alternatively from 0.05% to 10%, alternatively from 0.1% to 5%, by weight of the composition.
Another suitable class of polymeric suds booster polymers are hydrophobic ally modified cellulosic polymers having a number average molecular weight (Mw) below 45,000; alternatively between 10,000 and 40,000; alternatively between 13,000 and 25,000. The hydrophobic ally modified cellulosic polymers include water soluble cellulose ether derivatives, such as nonionic and cationic cellulose derivatives. In one embodiment, the composition includes methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, or mixtures thereof.
G. Diamines
Another optional ingredient in the composition of the present invention is a diamine.
Since the habits and practices of the users of liquid detergent compositions show considerable variation, the composition will alternatively contain 0% to 15%, alternatively 0.1% to 15%, alternatively 0.2% to 10%, alternatively 0.25% to 6%, alternatively 0.5% to 1.5% by weight of said composition, of at least one diamine.
Suitabble organic diamines are those in which pKl and pK2 are in the range of 8.0 to
11.5, alternatively in the range of 8.4 to 11, even alternatively from 8.6 to 10.75. Suitable materials include l,3-bis(methylamine)-cyclohexane (pKa=10 to 10.5), 1,3 propane diamine (pKl=10.5; pK2=8.8), 1,6 hexane diamine (pKl=ll; pK2=10), 1,3 pentane diamine (DYTEK EP®) (pKl=10.5; pK2=8.9), 2-methyl 1,5 pentane diamine (DYTEK A®) (pKl=11.2; pK2=10.0). Other suitable materials include primary/primary diamines with alkylene spacers ranging from C4 to C8. In general, it is believed that primary diamines are preferred over secondary and tertiary diamines. pKa is used herein in the same manner as is commonly known to people skilled in the art of chemistry: in an all-aqueous solution at 25°C and for an ionic strength between 0.1 to 0.5 M. 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.
H. Carboxylic Acid
The dishwashing detergent compositions of the present invention may comprise a linear or cyclic carboxylic acid or salt thereof to improve the rinse feel of the composition. The presence of anionic surfactants, especially when present in higher amounts in the region of 15- 35% by weight of the composition, results in the composition imparting a slippery feel to the hands of the user and the dishware.
Carboxylic acids useful herein include Ci_6 linear or at least 3 carbon containing cyclic acids. 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, alternatively 1 to 4 carbon atoms, and mixtures thereof.
Suitable 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, citric acid and salts thereof, and mixtures thereof. Where the carboxylic acid exists in the salt form, the cation of the salt is alternatively selected from alkali metal, alkaline earth metal, monoethanolamine, diethanolamine or triethanolamine and mixtures thereof.
The carboxylic acid or salt thereof, when present, is present at the level of from 0.1% to 5%, alternatively from 0.2% to 1%, alternatively from 0.25% to 0.5%, by weight of the compositian.
I. Malodor control component
The dishwashing detergent composition comprises a malodor control component. The malodor control component may include at least one volatile aldehyde and an acid catalyst. The malodor control component is designed to deliver genuine malodor neutralization and not function merely by covering up or masking odors. A genuine malodor neutralization provides a sensory and analytically measurable (e.g. gas chromatograph) malodor reduction. Thus, if the malodor control component delivers a genuine malodor neutralization, the composition will reduce malodors in the vapor and/or liquid phase.
1. Volatile Aldehydes
The malodor control component includes a mixture of volatile aldehydes that neutralize malodors in vapor and/or liquid phase via chemical reactions. Such volatile aldehydes are also called reactive aldehydes (RA). Volatile aldehydes may react with amine-based odors, following the path of Schiff-base formation. Volatiles aldehydes may also react with sulfur-based odors, forming thiol acetals, hemi thiolacetals, and thiol esters in vapor and/or liquid phase. It may be desirable for these vapor and/or liquid phase volatile aldehydes to have virtually no negative impact on the desired perfume character of a product. Aldehydes that are partially volatile may be considered a volatile aldehyde as used herein.
Suitable volatile aldehydes may have a vapor pressure (VP) in the range of about 0.0001 torr to 100 torr, alternatively about 0.0001 torr to about 10 torr, alternatively about 0.001 torr to about 50 torr, alternatively about 0.001 torr to about 20 torr, alternatively about 0.001 torr to about 0.100 torr, alternatively about 0.001 torr to 0.06 torr, alternatively about 0.001 torr to 0.03 torr, alternatively about 0.005 torr to about 20 torr, alternatively about 0.01 torr to about 20 torr, alternatively about 0.01 torr to about 15 torr, alternatively about 0.01 torr to about 10 torr, alternatively about 0.05 torr to about 10 torr, measured at 25°C.
The volatile aldehydes may also have a certain boiling point (B.P.) and octanol/water partition coefficient (P). The boiling point referred to herein is measured under normal standard pressure of 760 mmHg. The boiling points of many volatile aldehydes, at standard 760 mm Hg are given in, for example, "Perfume and Flavor Chemicals (Aroma Chemicals)," written and published by Steffen Arctander, 1969.
The octanol/water partition coefficient of a volatile aldehyde is the ratio between its equilibrium concentrations in octanol and in water. The partition coefficients of the volatile aldehydes used in the malodor control component may be more conveniently given in the form of their logarithm to the base 10, logP. The logP values of many volatile aldehydes have been reported. See, e.g., the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California. 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 volatile aldehyde, 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 alternatively used instead of the experimental logP values in the selection of volatile aldehydes for the malodor control component. The ClogP values may be defined by four groups and the volatile aldehydes may be selected from one or more of these groups. The first group comprises volatile aldehydes that have a B.P. of about 250 °C or less and ClogP of about 3 or less. The second group comprises volatile aldehydes that have a B.P. of 250°C or less and ClogP of 3.0 or more. The third group comprises volatile aldehydes that have a B.P. of 250°C or more and ClogP of 3.0 or less. The fourth group comprises volatile aldehydes that have a B.P. of 250°C or more and ClogP of 3.0 or more. The malodor control component may comprise any combination of volatile aldehydes from one or more of the ClogP groups.
In some embodiments, the malodor control component of the present invention may comprise, by total weight of the malodor control component, from about 0% to about 30% of volatile aldehydes from group 1, alternatively about 25%; and/or about 0% to about 10% of volatile aldehydes from group 2, alternatively about 10%; and/or from about 10% to about 30% of volatile aldehydes from group 3, alternatively about 30%; and/or from about 35% to about 60% of volatile aldehydes from group 4, alternatively about 35%.
Exemplary volatile aldehydes which may be used in a malodor control component include, but are not limited to, Adoxal (2,6,10-Trimethyl-9-undecenal), Bourgeonal (4-t- butylbenzenepropionaldehyde), Lilestralis 33 (2-methyl-4-t-butylphenyl)propanal), Cinnamic aldehyde, cinnamaldehyde (phenyl propenal, 3-phenyl-2-propenal), Citral, Geranial, Neral (dimethyloctadienal, 3,7-dimethyl-2,6-octadien-l-al), Cyclal C (2,4-dimethyl-3-cyclohexen-l- carbaldehyde), Florhydral (3-(3-Isopropyl-phenyl)-butyraldehyde), Citronellal (3,7-dimethyl 6- octenal), Cymal, cyclamen aldehyde, Cyclosal, Lime aldehyde (Alpha-methyl-p-isopropyl phenyl propyl aldehyde), Methyl Nonyl Acetaldehyde, aldehyde C12 MNA (2-methyl-l-undecanal), Hydroxycitronellal, citronellal hydrate (7-hydroxy-3,7-dimethyl octan-l-al), Helional (alpha- methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde, hydrocinnamaldehyde (3-phenylpropanal, 3-phenylpropionaldehyde), Intreleven aldehyde (undec-10-en-l-al), Ligustral, Trivertal (2,4- dimethyl-3-cyclohexene-l-carboxaldehyde), Jasmorange, satinaldehyde (2-methyl-3- tolylproionaldehyde, 4-dimethylbenzenepropanal), Lyral (4-(4-hydroxy-4-methyl pentyl)-3- cyclohexene-l-carboxaldehyde), Melonal (2,6-Dimethyl-5-Heptenal), Methoxy Melonal (6- methoxy-2,6-dimethylheptanal), methoxycinnamaldehyde (trans-4-methoxycinnamaldehyde), Myrac aldehyde isohexenyl cyclohexenyl-carboxaldehyde, trifernal ((3-methyl-4-phenyl propanal, 3-phenyl butanal), lilial, P.T. Bucinal, lysmeral, benzenepropanal (4-tert-butyl-alpha- methyl-hydrocinnamaldehyde), Dupical, tricyclodecylidenebutanal (4-Tricyclo5210- 2,6decylidene-8butanal), Melafleur (1,2,3,4,5,6,7, 8-octahydro-8,8-dimethyl-2-naphthaldehyde), Methyl Octyl Acetaldehyde, aldehyde C-l l MOA (2-mehtyl deca-l-al), Onicidal (2,6,10- trimethyl-5,9-undecadien-l-al), Citronellyl oxyacetaldehyde, Muguet aldehyde 50 (3,7-dimethyl- 6-octenyl) oxyacetaldehyde), phenylacetaldehyde, Mefranal (3-methyl-5-phenyl pentanal), Triplal, Vertocitral dimethyl tetrahydrobenzene aldehyde (2,4-dimethyl-3-cyclohexene-l- carboxaldehyde), 2-phenylproprionaldehyde, Hydrotropaldehyde, Canthoxal, anisylpropanal 4- methoxy-alpha-methyl benzenepropanal (2-anisylidene propanal), Cylcemone A (1,2,3,4,5,6,7,8- octahydro-8,8-dimethyl-2-naphthaldehyde), and Precylcemone B (1-cyclohexene-l- carboxaldehyde) .
Still other exemplary aldehydes include, but are not limited to, acetaldehyde (ethanal), pentanal, valeraldehyde, amylaldehyde, Scentenal (octahydro-5-methoxy-4,7-Methano-lH- indene-2-carboxaldehyde), propionaldehyde (propanal), Cyclocitral, beta-cyclocitral, (2,6,6- trimethyl-l-cyclohexene-l-acetaldehyde), Iso Cyclocitral (2,4,6-trimethyl-3-cyclohexene-l- carboxaldehyde), isobutyraldehyde, butyraldehyde, isovaleraldehyde (3-methyl butyraldehyde), methylbutyraldehyde (2-methyl butyraldehyde, 2-methyl butanal), Dihydrocitronellal (3,7- dimethyl octan-l-al), 2-Ethylbutyraldehyde, 3-Methyl-2-butenal, 2-Methylpentanal, 2-Methyl Valeraldehyde, Hexenal (2-hexenal, trans-2-hexenal), Heptanal, Octanal, Nonanal, Decanal, Laurie aldehyde, Tridecanal, 2-Dodecanal, Methylthiobutanal, Glutaraldehyde, Pentanedial, Glutaric aldehyde, Heptenal, cis or trans-Heptenal, Undecenal (2-, 10-), 2,4-octadienal, Nonenal (2-, 6-), Decenal (2-, 4-), 2,4-hexadienal, 2,4-Decadienal, 2,6-Nonadienal, Octenal, 2,6-dimethyl 5-heptenal, 2-isopropyl-5-methyl-2-hexenal, Trifernal, beta methyl Benzenepropanal, 2,6,6- Trimethyl-l-cyclohexene-1 -acetaldehyde, phenyl Butenal (2-phenyl 2-butenal), 2.Methyl-3(p- isopropylphenyl)-propionaldehyde, 3-(p-isopropylphenyl)-propionaldehyde, p-Tolylacetaldehyde (4-methylphenylacetaldehyde), Anisaldehyde (p-methoxybenzene aldehyde), Benzaldehyde, Vernaldehyde (l-Methyl-4-(4-methylpentyl)-3-cyclohexenecarbaldehyde), Heliotropin (piperonal) 3,4-Methylene dioxy benzaldehyde, alpha-Amylcinnamic aldehyde, 2-pentyl-3- phenylpropenoic aldehyde, Vanillin (4-methoxy 3-hydroxy benzaldehyde), Ethyl vanillin (3- ethoxy 4-hydroxybenzaldehyde), Hexyl Cinnamic aldehyde, Jasmonal H (alpha-n-hexyl- cinnamaldehyde), Floralozone, (para-ethyl-alpha,alpha-dimethyl Hydrocinnamaldehyde), Acalea (p-methyl-alpha-pentylcinnamaldehyde), methylcinnamaldehyde, alpha-Methylcinnamaldehyde (2-methyl 3-pheny propenal), alpha-hexylcinnamaldehyde (2 -hexyl 3 -phenyl propenal), Salicylaldehyde (2-hydroxy benzaldehyde), 4-ethyl benzaldehyde, Cuminaldehyde (4-isopropyl benzaldehyde), Ethoxybenzaldehyde, 2,4-dimethylbenzaldehyde, Veratraldehyde (3,4- dimethoxybenzaldehyde), Syringaldehyde (3,5-dimethoxy 4-hydroxybenzaldehyde), Catechaldehyde (3,4-dihydroxybenzaldehyde), Safranal (2,6,6-trimethyl-l,3-diene methanal), Myrtenal (pin-2-ene-l-carbaldehyde), Perillaldehyde L-4(l-methylethenyl)-l-cyclohexene-l- carboxaldehyde), 2,4-Dimethyl-3-cyclohexene carboxaldehyde, 2-Methyl-2-pentenal, 2- methylpentenal, pyruvaldehyde, formyl Tricyclodecan, Mandarin aldehyde, Cyclemax, Pino acetaldehyde, Corps Iris, Maceal, and Corps 4322.
In one embodiment, the malodor control component includes a mixture of two or more volatile aldehydes selected from the group consisting of 2-ethoxy Benzylaldehyde, 2-isopropyl- 5-methyl-2-hexenal, 5-methyl Furfural, 5-methyl-thiophene-carboxaldehyde, Adoxal, p- anisaldehyde, Benzylaldehyde, Bourgenal, Cinnamic aldehyde, Cymal, Decyl aldehyde, Floral super, Florhydral, Helional, Laurie aldehyde, Ligustral, Lyral, Melonal, o-anisaldehyde, Pino acetaldehyde, P.T. Bucinal, Thiophene carboxaldehyde, trans-4-Decenal, trans trans 2,4- Nonadienal, Undecyl aldehyde, and mixtures thereof.
In some embodiments, the malodor control component includes fast reacting volatile aldehydes. "Fast reacting volatile aldehydes" refers to volatile aldehydes that either (1) reduce amine odors by 20% or more in less than 40 seconds; or (2) reduce thiol odors by 20% or more in less than 30 minutes.
In one embodiment, the malodor control component includes a mixture of the volatile aldehydes listed in Table 1 and referred to herein as Accord A.
Table 1 - Accord A
Figure imgf000022_0001
In another embodiment, the malodor control component includes a mixture of the volatile aldehydes listed in Table 2 and referred to herein as Accord B. Table 2 - Accord B
Figure imgf000023_0001
In another embodiment, the malodor control component includes a mixture of about 71.2% volatile aldehydes, the remainder being other an ester and an alcohol perfume raw material. This mixture is listed in Table 3 and referred to herein as Accord C.
Table 3 - Accord C
Material Wt. % CAS Number ClogP VP (torr)
Group @25°C
Intreleven Aldehyde 2.000 112-45-8 3 0.060
Florhydral 10.000 125109-85-5 4 0.008
Floral Super 5.000 71077-31-1 3 0.030
Scentenal 2.000 86803-90-9 2 0.010
Cymal 15.000 103-95-7 4 0.007
Floralozone 12.000 67634-14-4 4 0.005
Adoxal 1.000 141-13-9 4 0.007
Methyl Nonyl
Acetaldehyde 1.000 110-41-8 3 0.030
Melonal 1.000 106-72-9 3 0.670
Flor Acetate 11.800 5413-60-5 1 0.060 Frutene 7.000 17511-60-3 4 0.020
Helional 5.000 1205-17-0 2 0.0005
Bourgeonal 2.000 18127-01-0 4 0.004
Linalool 10.000 78-70-6 3 0.050
Benzaldehyde 0.200 100-52-7 1 1.110
o-anisaldehyde 15.000 135-02-4 1 0.320
Accords A, B, or C can be formulated in with other perfume raw materials in an amount, for example, of about 10% by weight of the malodor control component. Additionally, the individual volatile aldehydes or a various combination of the volatile aldehydes can be formulated into a malodor control component. In certain embodiments, the volatile aldehydes may be present in an amount up to 100%, by weight of the malodor control component, alternatively from 1% to about 100%, alternatively from about 2% to about 100%, alternatively from about 3% to about 100%, alternatively about 50% to about 100%, alternatively about 70% to about 100%, alternatively about 80% to about 100%, alternatively from about 1% to about 20%, alternatively from about 1% to about 10%, alternatively from about 1% to about 5%, alternatively from about 1% to about 3%, alternatively from about 2% to about 20%, alternatively from about 3% to about 20%, alternatively from about 4% to about 20%, alternatively from about 5% to about 20%, by weight of the composition.
In some embodiments where volatility is not important for neutralizing a malodor, the present invention may include poly- aldehydes, for example, di-, tri-, tetra-aldehydes. Such embodiments may include laundry detergents, additive, and the like for leave-on, through the wash, and rinse-off type of applications.
2. Acid Catalyst
The malodor control component of the present invention may include an effective amount of an acid catalyst to neutralize sulfur-based malodors. It has been found that certain mild acids have an impact on aldehyde reactivity with thiols in the liquid and vapor phase. It has been found that the reaction between thiol and aldehyde is a catalytic reaction that follows the mechanism of hemiacetal and acetal formation path. When the present malodor control component contains an acid catalyst and contacts a sulfur-based malodor, the volatile aldehyde reacts with thiol. This reaction may form a thiol acetal compound, thus, neutralizing the sulfur- based odor. Without an acid catalyst, only hemi-thiol acetal is formed. Suitable acid catalysts have a VP, as reported by Scifinder, in the range of about 0.001 torr to about 38 torr, measured at 25 °C, alternatively about 0.001 torr to about 14 torr, alternatively from about 0.001 to about 1, alternatively from about 0.001 to about 0.020, alternatively about 0.005 to about 0.020, alternatively about 0.010 to about 0.020.
The acid catalyst may be a weak acid. A weak acid is characterized by an acid dissociation constant, Ka> which is an equilibrium constant for the dissociation of a weak acid; the pKa being equal to minus the decimal logarithm of Ka. The acid catalyst may have a pKa from about 4.0 to about 6.0, alternatively from about 4.3 and 5.7, alternatively from about 4.5 to about 5, alternatively from about 4.7 to about 4.9. Suitable acid catalyst include those listed in Table 4.
Table 4
Figure imgf000025_0001
Depending on the desired use of the malodor control component, one may consider the scent character or the affect on the scent of the malodor control component when selecting an acid catalyst. In some embodiments of the malodor control component, it may be desirable to select an acid catalyst that provides a neutral to pleasant scent. Such acid catalysts may have a VP of about 0.001 torr to about 0.020 torr, measured at 25 °C, alternatively about 0.005 torr to about 0.020 torr, alternatively about 0.010 torr to about 0.020 torr. Non-limiting examples of such acid catalyst include 5-methyl thiophene carboxaldehyde with carboxylic acid impurity, succinic acid, or benzoic acid. The malodor control component may include about 0.05% to about 5%, alternatively about 0.1% to about 1.0%, alternatively about 0.1% to about 0.5%, alternatively about 0.1% to about 0.4%, alternatively about 0.4% to about 1.5%, alternatively about 0.4% of an acid catalyst by weight of the malodor control component.
In an acetic acid system, the present malodor control component may include about 0.4% of acetic acid (50:50 TC:DPM, 0.4% acetic acid).
Table 5
Figure imgf000026_0001
When an acid catalyst is present with a volatile aldehyde (or RA), the acid catalyst may increase the efficacy of the volatile aldehyde on malodors in comparison to the malodor efficacy of the volatile aldehyde on its own. For example, 1% volatile aldehyde and 1.5% benzoic acid provides malodor removal benefit equal to or better than 5% volatile aldehyde alone.
The malodor control component may have a pH from about 3 to about 8, alternatively from about 4 to about 7, alternatively from about, alternatively from about 4 to about 6.
J. Other Optional Components:
The dishwashing detergent compositions herein can further comprise a number of other optional ingredients suitable for use in liquid detergent compositions such as diluents, including dipropylene glycol methyl ether, and 3-methoxy-3-methyl-l-butanol, and mixtures thereof; dyes; pearlescent agents; opacifiers; enzymes; thickening agents; preservatives; disinfecting agents; and pH buffering means so that the liquid detergent compositions herein generally have a pH of from 3 to 14, alternatively 6 to 13, alternatively 8 to 11. The pH of the composition can be adjusted using pH modifying ingredients known in the art.
The malodor control component may also include odor masking agents, odor blocking agents, and/or diluents. For example, the composition may include a chelant, surfactant, and malodor control components comprising a mixture of volatile aldehydes for neutralizing a malodor, perfume ionones, and a diluent. Alternatively, the malodor control component may include 100% volatile aldehydes.
"Odor-masking agents" refer to known compounds (e.g. perfume raw materials) that mask or hide a malodorous compound. Odor-masking may include a compound with a non- offensive or pleasant smell that is dosed such it limits the ability to sense a malodorous compound. Odor-masking may involve the selection of compounds which coordinate with an anticipated malodor to change the perception of the overall scent provided by the combination of odorous compounds. "Odor blocking agents" refer to known compounds that dull the human sense of smell.
The composition may also include perfume raw materials that solely provide a hedonic benefit (i.e. that do not neutralize malodors yet provide a pleasant fragrance). Suitable perfumes are disclosed in US 6,248,135, which is incorporated in its entirety by reference.
K. Viscosity
The composition of the present invention may have viscosity from 50 to 2000 centipoises
(50-2000 mPa*s), alternatively from 100 to 1500 centipoises (100-1500 mPa*s), alternatively from 500 to 1300 centipoises (500-1300 mPa*s) at 20 s"1 and 20°C. Viscosity can be determined by conventional methods.
Viscosity according to the present invention is measured using an AR 550 rheometer from TA instruments using a plate steel spindle at 40 mm diameter and a gap size of 500 μιη. The high shear viscosity at 20s"1 and low shear viscosity at 0.05 s l can be obtained from a logarithmic shear rate sweep from 0.1 s l to 25 s l in 3 minutes time at 20°C. The preferred rheology described therein may be achieved using internal existing structuring with detergent ingredients or by employing an external rheology modifier. Hence, in one embodiment of the present invention, the composition comprises further a rheology modifier.
II. Method of cleaning/treating a dishware
The method of the present invention comprises cleaning dishware with a dishwashing detergent composition comprising a cleaning agent and malodour control component. The dishwashing operation comprises the steps of applying said composition onto said dishware, typically in diluted or neat form and rinsing said composition from said dishware or said surface, or leaving the composition to dry on said surface without rinsing said dishware or said surface. Instead of leaving said composition to dry on said surface on the air, it can also be hand-dried using a kitchen towel. During the dishwashing operation, particularly during the application of the composition to the dishware and/or rinsing away of said composition from the dishware, the hands and skin of the user may be exposed to the composition in diluted or neat form.
By "in its neat form", it is meant herein that the composition is applied directly onto the surface to be treated without undergoing any dilution by the user (immediately) prior to the application. This direct application of that said composition onto the surface to be treated can be achieved through direct squeezing of that said composition out of the hand dishwashing liquid bottle onto the surface to be cleaned, or through squeezing that said composition out of the hand dishwashing liquid bottle on a pre-wetted or non pre-wetted cleaning article, such as without intending to be limiting a sponge, a cloth or a brush, prior to cleaning the targeted surface with said cleaning article. By "diluted form", it is meant herein that said composition is diluted by the user with an appropriate solvent, typically with water. By "rinsing", it is meant herein contacting the dishware cleaned with the process according to the present invention with substantial quantities of appropriate solvent, typically water, after the step of applying the composition herein onto said dishware. By "substantial quantities", it is meant usually 0.1 to 20 liters.
In one embodiment of the present invention, the composition herein can be applied in its diluted form. Soiled dishes are contacted with an effective amount, typically from 0.5 ml to 20 ml (per 25 dishes being treated), alternatively from 3ml to 10 ml, of the liquid detergent composition of the present invention diluted in water. The actual amount of liquid detergent composition used will be based on the judgment of user, and will typically depend upon factors such as the particular product formulation of the composition, including the concentration of active ingredients in the composition, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like. The particular product formulation, in turn, will depend upon a number of factors, such as the intended market (i.e., U.S., Europe, Japan, etc.) for the composition product. Typical light-duty detergent compositions are described in the examples section.
Generally, from 0.01 ml to 150 ml, alternatively from 3ml to 40ml, alternatively from 3ml to 10ml of a detergent composition of the invention is combined with from 2000 ml to 20000 ml, more typically from 5000 ml to 15000 ml of water in a sink having a volumetric capacity in the range of from 1000 ml to 20000 ml, more typically from 5000 ml to 15000 ml. The soiled dishes are immersed in the sink containing the diluted compositions then obtained, where contacting the soiled surface of the dish with a cloth, sponge, or similar article cleans them. The cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranged from 1 to 10 seconds, although the actual time will vary with each application and user. The contacting of cloth, sponge, or similar article to the dish surface is alternatively accompanied by a concurrent scrubbing of the dish surface.
Another method of the present invention will comprise immersing the soiled dishes into a water bath or held under running water without any liquid dishwashing detergent. A device for absorbing liquid dishwashing detergent, such as a sponge, is placed directly into a separate quantity of a concentrated pre-mix of diluted liquid dishwashing detergent, for a period of time typically ranging from 1 to 5 seconds. The absorbing device, and consequently the diluted liquid dishwashing composition, is then contacted individually to the surface of each of the soiled dishes to remove said soiling. The absorbing device is typically contacted with each dish surface for a period of time range from 1 to 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish. The step of contacting of the absorbing device to the dish surface is alternatively accompanied by concurrent scrubbing. Typically, said concentrated pre-mix of diluted liquid dishwashing detergent is formed by combining 1ml to 200ml of neat dishwashing detergent with 50ml to 1500ml of water, more typically from 200ml to 1000ml of water.
III. Packaging
The detergent compositions of the present invention may be packaged in any suitable packaging for delivering the liquid detergent composition for use. Alternatively the package is a clear package made of glass or plastic.
EXAMPLES
The examples herein are meant to exemplify the present invention but are not necessarily used to limit or otherwise define the scope of the present invention. All numerical values in the below examples are weight %, by total weight of the composition unless otherwise stated.
Ex.1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex.7
Alkyl Ethoxy Sulfate AExS* 22.5 25.0 25.0 27.0 20.0 22.5 22.5 w% linear in alkyl chain 45 84 70 50 76 76 40 w% branching in alkyl chain 55 16 30 50 24 24 60
Amine oxide 8.0 6.0 7.0 5.0 5.0 8.0 7.0
Figure imgf000030_0001
Balance of Minors (**), Ma odor Control Component, and water up to 100%
Figure imgf000030_0002
Average branching weight % in total 17.3 14.9 12.4 36.0 surfactant mixture
Total surfactant/Nonionic weight ratio 5.4 6.4 5.6 5.0
Balance of Minors (**), Malodor Control Component, and water up to
100%
Figure imgf000031_0001
Ex.17 Ex.18 Ex.19 Ex.20 Ex.21
Alkyl Ethoxy Sulfate AExS* 17.0 12.0 24.5 18.0 29.0 w% linear in alkyl chain 40 76 84 70 70 w% branching in alkyl chain 60 24 16 30 30
CI 2- 14 alpha olefin sulfonate - - 1.0 - -
Figure imgf000032_0001
(*) Alkyl chain between CIO and C14, alternatively between C12-13 and x=between 0 and 4, alternatively between 0.5 and 2
(**) Minors: dyes, opacifiers, perfumes, preservatives, hydrotropes, processing aids, salts, stabilizers....
(1) Glutamic acid
(2) Diethylenetriamine penta methylphosphonic acid
(3) Diethylenetriamine pentaacetic acid
(4) Methyl glycinediacetic acid
Analytical Test - Effect of volatile aldehydes on amine-based and sulfur-based malodors
Malodor standards are prepared by pipeting 1 mL of butylamine (amine-based malodor) and butanethiol (sulfur-based malodor) into a 1.2 liter gas sampling bag. The bag is then filled to volume with nitrogen and allowed to sit for at least 12 hours to equilibrate.
A l μΐ^ sample of each volatile aldehyde listed in Table 6 and of each Accord (A, B, and
C) listed in Tables 1 to 3 is pipeted into individual 10 mL silanized headspace vials. The vials are sealed and allowed to equilibrate for at least 12 hours. Repeat 4 times for each sample (2 for butylamine analysis and 2 for butanethiol analysis).
After the equilibration period, 1.5 mL of the target malodor standard is injected into each 10 mL vial. For thiol analysis, the vials containing a sample +malodor standard are held at room temperature for 30 minutes. Then, a 1 mL headspace syringe is then used to inject 250 μL of each sample/malodor into a GC/MS split/splitless inlet. For amine analysis, a 1 mL headspace syringe is used to inject 500 μL of each sample/malodor immediately into the GC/MS split/splitless inlet. A GC pillow is used for the amine analysis to shorten the run times.
Samples are then analyzed using a GC/MS with a DB-5, 20 m, 1 μιη film thickness column with an MPS-2 autosampler equipment with static headspace function. Data is analyzed by ion extraction on each total ion current (56 for thiol and 30 for amine) and the area is used to calculate the percent reduction from the malodor standard for each sample.
Table 6 shows the effect of certain volatile aldehydes on neutralizing amine-based and sulfur based malodors at 40 seconds and 30 minutes, respectively.
Table 6
Perfume Raw Material (R-CHO) At least 20% At least 20%
butylamine butanethiol reduction at 40 reduction at 30
sees.? mins.?
2,4,5 Trimethoxy Benzaldehyde No No
2,4, 6-Trimethoxy-benzylaldehyde No No
2-ethoxy benzylaldehyde Yes Yes
2-isopropyl-5-methyl-2-hexenal Yes Yes
2-methyl-3-(2-furyl)-propenal No No
3,4,5 Trimethoxy Benzaldehyde No No
3 ,4-Trimethoxy-benzylaldehyde No No
4-tertbutyl benzylaldehyde Yes No
5 -methyl furfural Yes Yes
5-methyl-thiophene-carboxaldehyde No Yes
Adoxal Yes No
Amyl cinnamic aldehyde No No
Benzylaldehyde Yes No Bourgenal No Yes
Cinnamic aldehyde Yes Yes
Citronelyl Oxyacetaldehyde No No
Cymal Yes No
Decyl aldehyde Yes No
Floral Super Yes Yes
Florhydral Yes Yes
Floralozone No No
Helional Yes No
Hydroxycitronellal No No
Laurie aldehyde Yes No
Ligustral Yes No
Lyral Yes No
Melonal Yes No
Methyl nonyl acetaldehyde No No o-anisaldehyde Yes Yes p-anisaldehyde Yes No
Pino acetaldehyde Yes Yes
P.T. Bucinal Yes No
Thiophene Carboxaldehyde Yes No
Trans-4-decenal Yes Yes
Trans Trans 2,4-Nonadienal Yes No
Undecyl aldehyde Yes No
Table 7 shows the percent reduction of butylamine and butaniethiol at 40 seconds and 30 minutes, respectively, for Accords A, B, and C. Table 7
Figure imgf000035_0001
Analytical Test - Effect of acid catalysts on sulfur-based malodors
The above analytical test is repeated using samples containing an acid catalyst to test their effect on sulfur-based malodors. Specifically, a 1 μΐ aliquot of each of the following controls and acid catalyst samples are pipeted into individual 10 mL silanized headspace vials in duplicate: thiophene carboxyaldehyde as a control; a 50/50 mixture of thiophene carboxaldehyde and each of the following acid catalysts at 0.04%, 0.10%, 0.43% in DPM, 1.02% in DPM, and 2.04% in DPM: phenol, mesitylenic acid, caprylic acid, succinic acid, pivalic acid, tiglic acid, and benzoic acid.
Fig. 1 demonstrates that low vapor pressure acid catalysts provide up to 3 times better reduction of sulfur-based malodors in comparison to the control. Analytical Test - Effect of volatile aldehydes and acid catalyst on amine-based and sulfur-based malodors
The above analytical test is repeated using sample formulations containing volatile aldehydes (or RA) and an acid catalyst, as outlined in Tables 8 and 9.
Tables 8 and 9 show that a perfume mixture having as little as 1 % volatile aldehyde along with 1.5% acid catalyst performs better at reducing butylamine and butanethiol than the same perfume mixture having 5% volatile aldehyde.
Table 8
Formulation % butylamine reduction at % butanethiol
40 sees. reduction at 30 mins.
Perfume Mixture w/ 5% RA 34.21 2.40
(Control) Perfume Mixture w/ 1% RA and 41.63 +7.42 11.9 +9.55 w/ 1.5% Benzoic Acid 5
Perfume Mixture w/ 3% RA and 36.19 +1.98 13.5 +11.16 w/ 1.5% Benzoic Acid 6
Perfume A Mixture w/ 5% RA and 41.26 +7.05 9.56 +5.02 w/ 1.5% Benzoic Acid
Table 9
Formulation % butylamine % butanethiol reduction at
Reduction at 40 sees. 30 mins.
Perfume mixture w/ 5% RA 4.94 10.52
(Control)
Perfume mixture w/ 1% RA and 11.61 +6.67 18.82 +8.30 w/ 1.5% Benzoic Acid
Perfume mixture w/ 3% RA and 26.89 +21.95 14.85 +4.33 w/ 1.5% Benzoic Acid
Perfume mixture w/ 5% RA and 20.27 +15.33 16.84 +6.32 w/ 1.5% Benzoic Acid
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."
Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests, or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern. While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is, therefore, intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

CLAIMS What is claimed is:
1. A dishwashing detergent composition comprising:
(a) from about 0.1% to about 20% by weight of the total composition of a chelant;
(b) from about 5% to about 80% by weight of the total composition of a surfactant selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwitterionic, semi- polar nonionic surfactants and mixtures thereof; and
(c) a malodor control component comprising an effective amount of two or more volatile aldehydes for neutralizing a malodor, wherein said two or more volatile aldehydes are selected from the group consisting of 2-ethoxy benzylaldehyde, 2- isopropyl-5-methyl-2-hexenal, 5-methyl furfural, 5-methyl-thiophene-carboxaldehyde, adoxal, p-anisaldehyde, benzylaldehyde, bourgenal, cinnamic aldehyde, cymal, decyl aldehyde, floral super, florhydral, helional, lauric aldehyde, ligustral, lyral, melonal, o- anisaldehyde, pino acetaldehyde, P.T. bucinal, thiophene carboxaldehyde, trans-4- decenal, trans trans 2,4-nonadienal, undecyl aldehyde, and mixtures thereof.
2. The composition of Claim 1 wherein said two or more volatile aldehydes are selected from the group consisting of 2-ethoxy benzylaldehyde, 2-isopropyl-5-methyl-2-hexenal, 5- methyl furfural, cinnamic aldehyde, floral super, florhydral, o-anisaldehyde, pino acetaldehyde, trans-4-decenal, and mixtures thereof.
3. The composition of Claim 1 wherein said two or more volatile aldehydes comprise flor super and o-anisaldehyde.
4. The composition of Claim 1 wherein said two or more volatile aldehydes have a VP from about 0.001 torr to about 0.100 torr.
5. The composition of Claim 1 wherein said two or more volatile aldehydes comprise about 25% of quad I volatile aldehydes, by weight of said malodor control component.
6. The composition of Claim 1 wherein said mixture of two or more volatile aldehydes comprise about 10% of quad II volatile aldehydes, by weight of said malodor control component.
7. The composition of Claim 1 wherein said mixture of two or more volatile aldehydes comprise from about 10% to about 30% of quad III volatile aldehydes, by weight of said malodor control component.
8. The composition of Claim 1 wherein said mixture of two or more volatile aldehydes comprise from about 35% to about 60% of quad IV volatile aldehydes, by weight of said malodor control component.
9. The composition of Claim 1 wherein said two or more volatile aldehydes is selected from the group consisting of: Accord A, Accord B, Accord C, and mixtures thereof.
10. The composition of Claim 1 wherein said two or more volatile aldehydes comprise about 1% to about 10% of Accord A, by weight of said malodor control component.
11. The composition of Claim 1 wherein said composition has a pH of about 4 to about 6.5.
12. The composition of Claim 1 wherein said two or more volatile aldehydes comprise three or more volatile aldehydes having a VP of about 0.001 torr to about 0.100 torr.
13. The composition of Claim 1 wherein said two or more volatile aldehydes are present in an amount from about 0.015% to about 1%, by weight of said dishwashing detergent composition.
14. The composition of Claim 1 wherein said malodor control component further comprises an acid catalyst having a vapor pressure of about 0.01 to about 13 at 25°C.
15. The composition of Claim 1 wherein said surfactant is present in an amount from about 10% to about 60% by weight of said composition.
16. The composition of Claim 1 wherein said surfactant is present in an amount from about 12% to about 45% by weight of said composition.
17. The composition of Claim 1 wherein said surfactant is selected from the group consisting of amine oxide surfactants, betaines surfactants, and mixture thereof.
18. The composition of Claim 17 wherein said surfactant is a coco dimethyl amine oxide.
19. The composition of Claim 1 wherein the average alkyl chain branching is at least about 40% by weight of the total surfactants.
20. The composition of Claim 1 wherein the average alkyl chain branching is provided by a branched nonionic surfactant selected from the group consisting of Guerbet alcohol ethoxylates, Guerbet alcohol alkoxylated EO/PO nonionics, oxo branched nonionic surfactants; derivatives from the isotridecyl alcohol and modified with ethyleneoxyde, and mixtures thereof.
21. The composition of Claim 1 further comprising a nonionic surfactant present in an amount from about 3% to about 20%, by weight of said composition.
22. The composition of Claim 21 wherein the weight ratio of total surfactant to nonionic surfactant is from about 2 to about 6.
23. The composition of Claim 1 wherein said chelant is present in an amount from about 0.1% to about 20% by weight of said composition.
24. The composition of Claim 1 wherein said chelant is selected from the group consisting of Glutamic acid, Diethylenetriamine penta methylphosphonic acid; Diethylenetriamine pentaacetic acid, Methyl glycinediacetic acid and mixtures thereof.
25. The composition of Claim 1 wherein said composition further comprises uncomplexed cyclodextrin.
26. The composition of Claim 1 wherein said composition further comprises a water-soluble metallic salt selected from the group consisting of: zinc salts, copper salts, and mixtures thereof.
27. A dishwashing detergent composition comprising:
(a) a chelant;
(b) a surfactant selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwitterionic, semi-polar nonionic surfactants, and mixtures thereof; and
(c) a malodor control component comprising:
(i) at least one volatile aldehyde; and
(ii) an acid catalyst having a vapor pressure of about 0.01 to about 13 at 25°C; and
(b) about 1% to about 5%, by weight of said composition, of a low molecular weight monohydric alcohol.
28. The composition of Claim 27 wherein said at least one volatile aldehyde has a VP of about 0.001 to about 50 torr .
29. The composition of Claim 27 wherein said at least one volatile aldehyde has a VP of about 0.001 torr to about 15 torr.
30. The composition of Claim 27 wherein said at least one volatile aldehyde is selected from the group consisting of 2-ethoxy benzylaldehyde, 2-isopropyl-5-methyl-2-hexenal, 5-methyl furfural, 5-methyl-thiophene-carboxaldehyde, adoxal, p-anisaldehyde, benzylaldehyde, bourgenal, cinnamic aldehyde, cymal, decyl aldehyde, floral super, florhydral, helional, lauric aldehyde, ligustral, lyral, melonal, o-anisaldehyde, pino acetaldehyde, P.T. bucinal, thiophene carboxaldehyde, trans-4-decenal, trans trans 2,4-nonadienal, undecyl aldehyde, and mixtures thereof.
31. The composition of Claim 27 wherein said at least one volatile aldehyde is selected from the group consisting of flor super, o-anisaldehyde, and mixtures thereof.
32. The composition of Claim 27 wherein said at least one volatile aldehyde is present in an amount from about 1% to about 10%, by weight of said malodor control component.
33. The composition of Claim 27 wherein said at least one volatile aldehyde is present in an amount from about 0.015% to about 1%, by weight of said dishwashing detergent composition.
34. The composition of Claim 27 wherein said at least one volatile aldehyde comprises a mixture of volatile aldehydes selected from the group consisting of Accord A, Accord B, Accord C, and mixtures thereof.
35. The composition of Claim 27 wherein said at least one volatile aldehyde is present in an amount from about 1% to about 5%, by weight of said malodor control component, and said acid catalyst is present in an amount of about 0.4% to about 1.5%, by weight of said malodor control component.
36. The composition of Claim 27 wherein said acid catalyst is present in an amount from about 0.1% to about 0.4%, by weight of said malodor control composition.
37. The composition of Claim 27 wherein said acid catalyst has a vapor pressure of about 0.01 to about 2 torr at 25°C.
38. The composition of Claim 27 wherein said acid catalyst is a carboxylic acid.
39. The composition of Claim 27 wherein said acid catalyst is 5-methyl thiophene carboxylic acid.
40. A method of cleaning a dishware comprising the steps of:
(a) applying a composition according to claim 1 on said dishware; and
(b) rinsing said composition off of said dishware.
PCT/US2010/060694 2009-12-17 2010-12-16 Dishwashing detergent composition having a malodor control component and methods of cleaning dishware WO2011084569A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP10801497A EP2512531A1 (en) 2009-12-17 2010-12-16 Dishwashing detergent composition having a malodor control component and methods of cleaning dishware
JP2012544814A JP5639661B2 (en) 2009-12-17 2010-12-16 Dishwashing detergent composition having malodor control component, and dishwashing method
CA2782479A CA2782479C (en) 2009-12-17 2010-12-16 Dishwashing detergent composition having a malodor control component and methods of cleaning dishware
MX2012007021A MX2012007021A (en) 2009-12-17 2010-12-16 Dishwashing detergent composition having a malodor control component and methods of cleaning dishware.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US28734809P 2009-12-17 2009-12-17
US28736909P 2009-12-17 2009-12-17
US28738309P 2009-12-17 2009-12-17
US61/287,369 2009-12-17
US61/287,383 2009-12-17
US61/287,348 2009-12-17

Publications (1)

Publication Number Publication Date
WO2011084569A1 true WO2011084569A1 (en) 2011-07-14

Family

ID=43499978

Family Applications (3)

Application Number Title Priority Date Filing Date
PCT/US2010/060694 WO2011084569A1 (en) 2009-12-17 2010-12-16 Dishwashing detergent composition having a malodor control component and methods of cleaning dishware
PCT/US2010/060717 WO2011084577A1 (en) 2009-12-17 2010-12-16 Hard surface cleaning composition having a malodor control component and methods of cleaning hard surfaces
PCT/US2010/060705 WO2011084574A1 (en) 2009-12-17 2010-12-16 Laundry detergent composition having a malodor control component and methods of laundering fabrics

Family Applications After (2)

Application Number Title Priority Date Filing Date
PCT/US2010/060717 WO2011084577A1 (en) 2009-12-17 2010-12-16 Hard surface cleaning composition having a malodor control component and methods of cleaning hard surfaces
PCT/US2010/060705 WO2011084574A1 (en) 2009-12-17 2010-12-16 Laundry detergent composition having a malodor control component and methods of laundering fabrics

Country Status (10)

Country Link
US (6) US20110150817A1 (en)
EP (3) EP2512528B1 (en)
JP (2) JP5639661B2 (en)
CN (1) CN102655886A (en)
BR (1) BR112012014692A2 (en)
CA (4) CA2780656A1 (en)
MX (2) MX2012007022A (en)
RU (2) RU2557989C2 (en)
WO (3) WO2011084569A1 (en)
ZA (1) ZA201203443B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014530930A (en) * 2011-10-19 2014-11-20 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Composition, method of use thereof for producing dishwashing detergent and method of production thereof
JP2015520619A (en) * 2012-04-10 2015-07-23 ザ プロクター アンド ギャンブルカンパニー Odor reducing composition
US11938242B2 (en) 2017-11-03 2024-03-26 The Procter & Gamble Plaza Apparatus and method for reducing malodor on surfaces

Families Citing this family (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8178078B2 (en) 2008-06-13 2012-05-15 S.C. Johnson & Son, Inc. Compositions containing a solvated active agent suitable for dispensing as a compressed gas aerosol
US20110150817A1 (en) * 2009-12-17 2011-06-23 Ricky Ah-Man Woo Freshening compositions comprising malodor binding polymers and malodor control components
DK2365055T3 (en) 2010-03-01 2018-03-05 Procter & Gamble COMPOSITION INCLUDING SUBSTITUTED CELLULOSE POLYMES AND AMYLASE
US8889612B2 (en) * 2010-04-19 2014-11-18 The Procter & Gamble Company Method of laundering fabric using a compacted liquid laundry detergent composition
CN102234810A (en) * 2010-04-20 2011-11-09 深圳富泰宏精密工业有限公司 Cleaning agent for etched stainless steel and using method thereof
ES2565192T3 (en) * 2010-04-23 2016-04-01 The Procter & Gamble Company Method to perfume
CA2806265C (en) * 2010-08-17 2016-10-18 The Procter & Gamble Company Method for hand washing dishes having long lasting suds
UA111166C2 (en) * 2010-08-27 2016-04-11 Анітокс Корпорейшн COMPOSITION AGAINST SALMONELLA TYPHIMURIUM AND METHOD OF ANIMAL FEED PROCESSING
US8653015B2 (en) * 2011-04-13 2014-02-18 American Sterilizer Company Environmentally friendly, multi-purpose refluxing cleaner
CN103889464B (en) 2011-10-20 2018-10-26 阿尼托克斯公司 Anti-microbial agents with n-nonanoic acid
AR092788A1 (en) * 2012-01-18 2015-05-06 Procter & Gamble DETERGENT COMPOSITIONS ACIDED FOR LAUNDRY
JP6004515B2 (en) * 2012-02-20 2016-10-12 国立研究開発法人海洋研究開発機構 Method for measuring enzyme activity
US8859478B2 (en) * 2012-03-09 2014-10-14 Process Cleaning Solutions Ltd. Cleaning composition/solutions and use thereof
US8927474B2 (en) 2012-03-16 2015-01-06 S.C. Johnson & Son, Inc. Compressed gas aerosol composition in steel can
US9790456B2 (en) * 2012-12-20 2017-10-17 Ecolab Usa Inc. Citrate salt bathroom cleaners
US9534190B2 (en) * 2012-12-20 2017-01-03 Ecolab Usa Inc. Citrate salt bathroom cleaners
US10301576B2 (en) * 2013-02-28 2019-05-28 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
CA2910881C (en) 2013-05-24 2018-06-26 The Procter & Gamble Company Concentrated surfactant composition
CN105209587A (en) 2013-05-24 2015-12-30 宝洁公司 Low PH detergent composition comprising nonionic surfactants
CA2910875C (en) 2013-05-24 2018-11-06 The Procter & Gamble Company Low ph detergent composition
JP6257102B2 (en) * 2013-06-12 2018-01-10 ライオン株式会社 Cleaning composition
US9309485B2 (en) * 2013-06-26 2016-04-12 Ecolab USA, Inc. Use of nonionics as rheology modifiers in liquid cleaning solutions
KR102115548B1 (en) 2013-12-16 2020-05-26 삼성전자주식회사 Organic material-cleaning composition and method of forming a semiconductor device using the composition
US9611449B2 (en) * 2014-02-11 2017-04-04 Gregory E Robinson Multi-purpose cleaning composition
US20150252310A1 (en) 2014-03-07 2015-09-10 Ecolab Usa Inc. Alkyl amides for enhanced food soil removal and asphalt dissolution
JP6809906B2 (en) * 2014-05-28 2021-01-06 ノボザイムス アクティーゼルスカブ Use of polypeptides
US9957469B2 (en) 2014-07-14 2018-05-01 Versum Materials Us, Llc Copper corrosion inhibition system
JP6521507B2 (en) * 2014-12-29 2019-05-29 ライオン株式会社 Liquid cleaning agents for textiles
EP3247782A1 (en) * 2015-01-21 2017-11-29 Basf Se Cleaning composition and method of forming the same
HUE036591T2 (en) * 2015-06-05 2018-08-28 Procter & Gamble Compacted liquid laundry detergent composition
US10549888B2 (en) * 2015-07-08 2020-02-04 The Glad Products Company Thermoplastic films and bags with enhanced odor control and methods of making the same
KR102537436B1 (en) * 2015-07-17 2023-05-25 아질렉스 플레이버스 앤드 프레이그런시스, 인크. Composition for reducing malodor and use thereof
US10358625B2 (en) * 2015-07-17 2019-07-23 S. C. Johnson & Son, Inc. Non-corrosive cleaning composition
JP6767471B2 (en) * 2015-07-20 2020-10-14 エス.シー. ジョンソン アンド サン、インコーポレイテッド Water-based fragrance compositions, fragrance delivery devices, and methods for providing long-lasting scents
WO2017099932A1 (en) 2015-12-07 2017-06-15 S.C. Johnson & Son, Inc. Acidic hard surface cleaner with glycine betaine amide
US11339353B2 (en) 2015-12-07 2022-05-24 S.C. Johnson & Son, Inc. Acidic hard surface cleaner with glycine betaine ester
FR3047488B1 (en) * 2016-02-05 2020-02-28 Laboratoires Anios DETERGENT COMPOSITIONS FOR CLEANING IN THE COSMETIC AND PHARMACEUTICAL INDUSTRY.
US10676621B2 (en) 2016-03-04 2020-06-09 S. C. Johnson & Son, Inc. Multi-purpose floor finish composition
US11096877B2 (en) 2016-03-29 2021-08-24 Lg Household & Health Care Ltd. Perfume composition capable of masking odor of formulation containing amine
BR112018073598B1 (en) * 2016-05-17 2022-09-27 Unilever Ip Holdings B.V LIQUID COMPOSITION FOR WASHING CLOTHES AND USE OF A LIQUID COMPOSITION DETERGENT FOR WASHING CLOTHES
EP3458561B1 (en) * 2016-05-17 2020-10-14 Unilever PLC Liquid laundry detergent compositions
CN106520396A (en) * 2016-10-29 2017-03-22 袁春华 Preparation method of strong decontamination grapefruit oil abrasive cleaner
EP3541355B1 (en) 2016-11-21 2023-06-07 Bell Flavors And Fragrances, Inc. Malodor counteractant composition and methods
JP7001344B2 (en) 2016-12-28 2022-01-19 小林製薬株式会社 Fragrance composition
EP3399012A1 (en) * 2017-05-05 2018-11-07 The Procter & Gamble Company Liquid detergent compositions with improved rheology
EP3399013B1 (en) 2017-05-05 2022-08-03 The Procter & Gamble Company Laundry detergent compositions with improved grease removal
EP3561033A1 (en) * 2018-04-27 2019-10-30 The Procter & Gamble Company Acidic hard surface cleaners comprising alkylpyrrolidones
EP3569681A1 (en) 2018-05-15 2019-11-20 The Procter & Gamble Company Improved prevention of water marks and splash marks
EP3569683B1 (en) 2018-05-15 2020-10-14 The Procter & Gamble Company Liquid acidic hard surface cleaning compositions providing improved maintenance of surface shine, and prevention of water marks and splash marks
US11008536B2 (en) * 2019-03-13 2021-05-18 American Sterilizer Company Liquid product for stainless-steel corrosion remediation
CA3057217A1 (en) * 2019-10-02 2021-04-02 Fluid Energy Group Ltd. Composition useful in metal sulfide scale removal
CN111393553B (en) * 2019-11-27 2021-12-17 浙江工业大学 Preparation method of organic oligomer, organic composite heat stabilizer containing organic oligomer and application of organic composite heat stabilizer
WO2021223222A1 (en) * 2020-05-08 2021-11-11 The Procter & Gamble Company Liquid laundry detergent composition
US11667871B2 (en) * 2020-09-18 2023-06-06 Henkel Ag & Co. Kgaa Use of alkyl dialkylamine oxide and surfactant blend to increase mildness of unit dose or liquid laundry detergent
EP4174159A1 (en) * 2021-11-02 2023-05-03 The Procter & Gamble Company Acidic liquid fabric care compositions
EP4257663A1 (en) * 2022-04-05 2023-10-11 The Procter & Gamble Company Food contact surface sanitizing liquid
WO2024126317A1 (en) 2022-12-12 2024-06-20 Clariant International Ltd Liquid laundry detergent compositions containing cucurbiturils

Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE735096C (en) 1940-12-09 1943-05-06 Ig Farbenindustrie Ag Process for the production of sulphonic acids
US2503280A (en) 1947-10-24 1950-04-11 Du Pont Azo catalysts in preparation of sulfonic acids
US2507088A (en) 1948-01-08 1950-05-09 Du Pont Sulfoxidation process
US3260744A (en) 1958-09-28 1966-07-12 Ajinomoto Kk Method of optically resolving racemic amino acids
US3372188A (en) 1965-03-12 1968-03-05 Union Oil Co Sulfoxidation process in the presence of sulfur trioxide
US3812044A (en) 1970-12-28 1974-05-21 Procter & Gamble Detergent composition containing a polyfunctionally-substituted aromatic acid sequestering agent
US3915903A (en) 1972-07-03 1975-10-28 Procter & Gamble Sulfated alkyl ethoxylate-containing detergent composition
US4663071A (en) 1986-01-30 1987-05-05 The Procter & Gamble Company Ether carboxylate detergent builders and process for their preparation
US4704233A (en) 1986-11-10 1987-11-03 The Procter & Gamble Company Detergent compositions containing ethylenediamine-N,N'-disuccinic acid
EP0859044A1 (en) 1997-02-14 1998-08-19 THE PROCTER &amp; GAMBLE COMPANY Liquid hard-surface cleaning compositions
WO1999005243A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Detergent compositions containing mixtures of crystallinity-disrupted surfactants
WO1999005242A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved alkylbenzenesulfonate surfactants
WO1999005244A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved alkyl aryl sulfonate surfactants
WO1999005084A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Process for making alkylbenzenesulfonate surfactants from alcohols and products thereof
WO1999005241A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof
WO1999005082A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved processes for making alkylbenzenesulfonate surfactants and products thereof
WO1999007656A2 (en) 1997-08-08 1999-02-18 The Procter & Gamble Company Improved processes for making surfactants via adsorptive separation and products thereof
US6008181A (en) 1996-04-16 1999-12-28 The Procter & Gamble Company Mid-Chain branched Alkoxylated Sulfate Surfactants
US6020303A (en) 1996-04-16 2000-02-01 The Procter & Gamble Company Mid-chain branched surfactants
WO2000023548A1 (en) 1998-10-20 2000-04-27 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
WO2000023549A1 (en) 1998-10-20 2000-04-27 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
US6060443A (en) 1996-04-16 2000-05-09 The Procter & Gamble Company Mid-chain branched alkyl sulfate surfactants
WO2001023516A1 (en) * 1999-09-30 2001-04-05 The Procter & Gamble Company Detergent compositions with perfume complexes to mask malodors
US6248135B1 (en) 1994-08-12 2001-06-19 The Procter & Gamble Company Composition for reducing malodor impression on inanimate surfaces
EP1111034A1 (en) * 1999-12-22 2001-06-27 The Procter & Gamble Company Laundry and cleaning and/or fabric care compositions
US6362147B1 (en) * 1997-08-29 2002-03-26 The Procter & Gamble Company Thickened liquid dishwashing detergent compositions containing organic diamines
US6426229B1 (en) 1995-12-22 2002-07-30 Mitsubishi Rayon Co., Ltd. Chelating agent and detergent comprising the same
WO2006014740A1 (en) 2004-07-21 2006-02-09 Magna International Inc. Assembly aid for running boards
WO2007135645A2 (en) 2006-05-22 2007-11-29 The Procter & Gamble Company Liquid detergent composition for improved grease cleaning
WO2007138053A1 (en) 2006-05-31 2007-12-06 Basf Se Amphiphilic graft polymers based on polyalkylene oxides and vinyl esters
WO2008100625A1 (en) * 2007-02-15 2008-08-21 The Procter & Gamble Company Benefit agent delivery compositions

Family Cites Families (86)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2702279A (en) 1955-02-15 Detergent compositions having
US2082275A (en) 1934-04-26 1937-06-01 Gen Aniline Works Inc Substituted betaines
US2255082A (en) 1938-01-17 1941-09-09 Gen Aniline & Film Corp Capillary active compounds and process of preparing them
US2438091A (en) 1943-09-06 1948-03-16 American Cyanamid Co Aspartic acid esters and their preparation
US2528378A (en) 1947-09-20 1950-10-31 John J Mccabe Jr Metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same
US2658072A (en) 1951-05-17 1953-11-03 Monsanto Chemicals Process of preparing amine sulfonates and products obtained thereof
GB1082179A (en) 1965-07-19 1967-09-06 Citrique Belge Nv Unsaturated carboxylic salt materials and derivatives thereof
DE2437090A1 (en) 1974-08-01 1976-02-19 Hoechst Ag CLEANING SUPPLIES
US4228044A (en) 1978-06-26 1980-10-14 The Procter & Gamble Company Laundry detergent compositions having enhanced particulate soil removal and antiredeposition performance
JPS60136506A (en) * 1983-12-23 1985-07-20 Takasago Corp Deodorant
GB8618635D0 (en) 1986-07-30 1986-09-10 Unilever Plc Detergent composition
US4954292A (en) 1986-10-01 1990-09-04 Lever Brothers Co. Detergent composition containing PVP and process of using same
JPS6392698A (en) * 1986-10-08 1988-04-23 花王株式会社 Detergent composition for kitchen
US6033679A (en) * 1998-04-27 2000-03-07 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
US5942217A (en) * 1997-06-09 1999-08-24 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
DD272608A1 (en) 1988-05-30 1989-10-18 Akad Wissenschaften Ddr CROSS POWER FILTER MODULE
US5795566A (en) 1989-05-29 1998-08-18 Robertet S.A. Deodorant compositions containing at least two aldehydes and the deodorant products containing them
US5321074A (en) 1993-07-26 1994-06-14 Eastman Chemical Company Process for preparing hydrolytically stable poly (ethylene-2,6-naphthalene dicarboxylate) polymers
JP3691061B2 (en) 1993-11-30 2005-08-31 クエスト・インターナショナル・ビー・ブイ Anti-smoke perfume and composition
HU218030B (en) 1994-08-12 2000-05-28 The Procter & Gamble Co. Uncomplexed cyclodextrin solutions for odor control on inanimate surfaces and use thereof
JP4489190B2 (en) * 1997-03-07 2010-06-23 ザ、プロクター、エンド、ギャンブル、カンパニー Bleach composition containing metal bleach catalyst and bleach activator and / or organic percarboxylic acid
US5955093A (en) * 1997-06-09 1999-09-21 The Procter & Gamble Company Uncomplexed cyclodextrin compositions for odor control
JP2002507133A (en) * 1997-06-09 2002-03-05 ザ、プロクター、エンド、ギャンブル、カンパニー Improved uncomplexed cyclodextrin composition for odor control
WO1999019444A1 (en) * 1997-10-10 1999-04-22 The Procter & Gamble Company A detergent composition
CA2305330A1 (en) * 1997-10-10 1999-04-22 Susumu Murata Mid-chain branched surfactants with cellulose derivatives
ATE293673T1 (en) * 1998-05-15 2005-05-15 Procter & Gamble LIQUID, ACIDIC CLEANING COMPOSITION FOR HARD SURFACES
US6511948B1 (en) 1998-07-10 2003-01-28 The Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
EP0971025A1 (en) 1998-07-10 2000-01-12 The Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
GB2346900A (en) 1999-02-18 2000-08-23 Reckitt & Colman Inc Deodorizing compositions for fibrous substrates
AU3627200A (en) * 1999-03-15 2000-10-04 Procter & Gamble Company, The Perfume compositions and methods to mask amine malodors
US6979667B1 (en) 1999-03-15 2005-12-27 The Procter & Gamble Company Perfume compositions and methods to mask amine malodors
US6903064B1 (en) * 1999-05-26 2005-06-07 Procter & Gamble Company Detergent composition comprising polymeric suds volume and suds duration enhancers
US6740713B1 (en) * 1999-07-08 2004-05-25 Procter & Gamble Company Process for producing particles of amine reaction products
US6972276B1 (en) * 1999-07-09 2005-12-06 Procter & Gamble Company Process for making amine compounds
FR2796392B1 (en) 1999-07-15 2003-09-19 Rhodia Chimie Sa CLEANING COMPOSITION COMPRISING A WATER-SOLUBLE OR HYDRODISPERSABLE POLYMER
FR2796390B1 (en) 1999-07-15 2001-10-26 Rhodia Chimie Sa USING AN AMPHOTERIC POLYMER TO TREAT A HARD SURFACE
US20040018955A1 (en) * 2000-01-12 2004-01-29 Jean Wevers Pro-perfume composition
EP1116788A1 (en) * 2000-01-12 2001-07-18 The Procter & Gamble Company Pro-perfume composition
US6890894B2 (en) * 2000-02-22 2005-05-10 The Procter & Gamble Company Fatty acids, soaps surfactant systems, and consumer products based thereon
US6753305B2 (en) * 2000-04-14 2004-06-22 The Procter & Gamble Company Process for disinfecting a hard-surface with a composition comprising cinnamon oil and/or an active thereof
US7799966B2 (en) 2000-04-14 2010-09-21 Playtex Products, Inc. Fibrous absorbent articles having malodor counteractant ability and method of making same
MXPA03003739A (en) 2000-10-27 2003-07-28 Procter & Gamble Stabilized liquid compositions.
US20020169091A1 (en) * 2001-02-14 2002-11-14 Clare Jonathan Richard Automatic dishwashing compositions comprising blooming perfume and base masking ingredients
ES2261662T3 (en) 2001-04-16 2006-11-16 Johnsondiversey, Inc. COMPOSITION AND METHOD TO REDUCE ODOR AND DISINFECT.
US20030073607A1 (en) * 2001-05-11 2003-04-17 The Procter & Gamble Company Pro-perfume compositions
US20030158079A1 (en) * 2001-10-19 2003-08-21 The Procter & Gamble Company Controlled benefit agent delivery system
US20030134772A1 (en) * 2001-10-19 2003-07-17 Dykstra Robert Richard Benefit agent delivery systems
US20040144406A1 (en) * 2003-01-16 2004-07-29 Aram Garabedian Dry aerosol carpet cleaning process
FR2851572B1 (en) 2003-02-20 2007-04-06 Rhodia Chimie Sa CLEANING OR RINSING COMPOSITION FOR HARD SURFACES
US20040223943A1 (en) 2003-05-05 2004-11-11 The Procter & Gamble Company Air freshener
US7998403B2 (en) * 2003-05-05 2011-08-16 The Proctor & Gamble Company Method of freshening air
EP1502944B1 (en) * 2003-08-01 2007-02-28 The Procter & Gamble Company Aqueous liquid laundry detergent compositions with visible beads
JP2007517933A (en) * 2003-12-19 2007-07-05 ザ プロクター アンド ギャンブル カンパニー Cleaning composition comprising a surfactant-enhancing polymer
US20050155628A1 (en) * 2004-01-16 2005-07-21 Andrew Kilkenny Cleaning composition for disposable cleaning head
US7393521B2 (en) 2004-02-18 2008-07-01 Bionutratech, Inc. In situ remediation of waste in farm animal bedding substrates
US7135449B2 (en) 2004-02-20 2006-11-14 Milliken & Company Composition for removal of odors and contaminants from textiles and method
ES2333597T3 (en) 2004-03-25 2010-02-24 THE PROCTER &amp; GAMBLE COMPANY ACID LIQUID COMPOSITION FOR CLEANING HARD SURFACES.
CA2560587C (en) * 2004-04-16 2011-09-13 The Procter & Gamble Company Liquid laundry detergent compositions with silicone blends as fabric care agents
US20050245424A1 (en) * 2004-04-30 2005-11-03 Naymesh Patel High fragrance cleaners
US7378382B2 (en) * 2004-05-05 2008-05-27 The Clorox Company Rheologically stabilized silicone dispersions comprising a polydimethylsiloxane mixture
JP2006020526A (en) * 2004-07-06 2006-01-26 Kiyomitsu Kawasaki Coffee flavor composition, and food and drink containing the same
US20060128585A1 (en) * 2004-12-15 2006-06-15 Martha Adair Antimicrobial composition for cleaning substrate
JP2006176675A (en) * 2004-12-22 2006-07-06 Riken Koryo Kogyo Kk Detergent deodorizing compounding agent and detergent composition
US20060165740A1 (en) * 2005-01-24 2006-07-27 Goldschmidt Chemical Corporation Perfume delivery system
DE602006008466D1 (en) * 2005-06-07 2009-09-24 Reckitt Benckiser Inc ACID CLEANSING AGENT FOR SOLID SURFACES
DE102005043188A1 (en) * 2005-09-09 2007-03-22 Henkel Kgaa Consumable products with changing odor images
CN101299987B (en) * 2005-11-01 2014-05-07 宝洁公司 Multi-phase personal care composition comprising a stabilizing perfume composition
GB0603914D0 (en) * 2006-02-28 2006-04-05 Reckitt Benckiser Uk Ltd Improvement in or relating to compositions
JP2009542896A (en) * 2006-06-19 2009-12-03 ザ プロクター アンド ギャンブル カンパニー Liquid detergent composition having low polydispersity polyacrylic acid polymer
EP1886698B1 (en) 2006-08-09 2011-02-16 The Procter & Gamble Company Absorbent articles including an improved odour control system
US20080045426A1 (en) 2006-08-17 2008-02-21 George Kavin Morgan Dryer-added fabric care articles imparting malodor absorption benefits
EP2102325B1 (en) * 2006-12-06 2011-04-20 Reckitt Benckiser LLC Aqueous highly acidic hard surface cleaning compositions
MX2009008576A (en) * 2007-02-09 2009-08-18 Procter & Gamble Perfume systems.
DE102007022069A1 (en) * 2007-05-08 2008-11-13 Henkel Ag & Co. Kgaa Discoloration inhibition of detergents and cleaners and / or cosmetic products
WO2008155683A1 (en) 2007-06-18 2008-12-24 Firmenich Sa Malodor counteracting compositions and method for their use
ES2556127T3 (en) 2007-08-31 2016-01-13 The Procter & Gamble Company Liquid acid hard surface cleaning composition
EP2100947A1 (en) * 2008-03-14 2009-09-16 The Procter and Gamble Company Automatic dishwashing detergent composition
CN102224233A (en) 2008-09-25 2011-10-19 荷兰联合利华有限公司 Liquid detergents
EP2328999A1 (en) * 2008-09-30 2011-06-08 The Procter & Gamble Company Liquid hard surface cleaning composition
WO2010053891A1 (en) * 2008-11-04 2010-05-14 The Procter & Gamble Company Malodor control system
EP2206766B1 (en) 2008-12-23 2015-11-11 The Procter and Gamble Company Liquid acidic hard surface cleaning composition
US20110305659A1 (en) * 2009-09-18 2011-12-15 Ricky Ah-Man Woo Freshening compositions comprising malodor binding polymers and malodor control components
US20110150817A1 (en) 2009-12-17 2011-06-23 Ricky Ah-Man Woo Freshening compositions comprising malodor binding polymers and malodor control components
US8357359B2 (en) * 2009-12-17 2013-01-22 The Procter & Gamble Company Malodor control composition having an acid catalyst and methods thereof
ES2413094T3 (en) * 2009-12-17 2013-07-15 The Procter & Gamble Company Method to neutralize bad odors
US20110150814A1 (en) * 2009-12-17 2011-06-23 Ricky Ah-Man Woo Malodor control composition having a mixture of volatile aldehydes and methods thereof

Patent Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE735096C (en) 1940-12-09 1943-05-06 Ig Farbenindustrie Ag Process for the production of sulphonic acids
US2503280A (en) 1947-10-24 1950-04-11 Du Pont Azo catalysts in preparation of sulfonic acids
US2507088A (en) 1948-01-08 1950-05-09 Du Pont Sulfoxidation process
US3260744A (en) 1958-09-28 1966-07-12 Ajinomoto Kk Method of optically resolving racemic amino acids
US3372188A (en) 1965-03-12 1968-03-05 Union Oil Co Sulfoxidation process in the presence of sulfur trioxide
US3812044A (en) 1970-12-28 1974-05-21 Procter & Gamble Detergent composition containing a polyfunctionally-substituted aromatic acid sequestering agent
US3915903A (en) 1972-07-03 1975-10-28 Procter & Gamble Sulfated alkyl ethoxylate-containing detergent composition
US4663071A (en) 1986-01-30 1987-05-05 The Procter & Gamble Company Ether carboxylate detergent builders and process for their preparation
US4663071B1 (en) 1986-01-30 1992-04-07 Procter & Gamble
US4704233A (en) 1986-11-10 1987-11-03 The Procter & Gamble Company Detergent compositions containing ethylenediamine-N,N'-disuccinic acid
US6248135B1 (en) 1994-08-12 2001-06-19 The Procter & Gamble Company Composition for reducing malodor impression on inanimate surfaces
US6426229B1 (en) 1995-12-22 2002-07-30 Mitsubishi Rayon Co., Ltd. Chelating agent and detergent comprising the same
US6008181A (en) 1996-04-16 1999-12-28 The Procter & Gamble Company Mid-Chain branched Alkoxylated Sulfate Surfactants
US6020303A (en) 1996-04-16 2000-02-01 The Procter & Gamble Company Mid-chain branched surfactants
US6060443A (en) 1996-04-16 2000-05-09 The Procter & Gamble Company Mid-chain branched alkyl sulfate surfactants
EP0859044A1 (en) 1997-02-14 1998-08-19 THE PROCTER &amp; GAMBLE COMPANY Liquid hard-surface cleaning compositions
WO1999005242A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved alkylbenzenesulfonate surfactants
WO1999005244A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved alkyl aryl sulfonate surfactants
WO1999005084A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Process for making alkylbenzenesulfonate surfactants from alcohols and products thereof
WO1999005241A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof
WO1999005082A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Improved processes for making alkylbenzenesulfonate surfactants and products thereof
WO1999005243A1 (en) 1997-07-21 1999-02-04 The Procter & Gamble Company Detergent compositions containing mixtures of crystallinity-disrupted surfactants
WO1999007656A2 (en) 1997-08-08 1999-02-18 The Procter & Gamble Company Improved processes for making surfactants via adsorptive separation and products thereof
US6362147B1 (en) * 1997-08-29 2002-03-26 The Procter & Gamble Company Thickened liquid dishwashing detergent compositions containing organic diamines
WO2000023549A1 (en) 1998-10-20 2000-04-27 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
WO2000023548A1 (en) 1998-10-20 2000-04-27 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
WO2001023516A1 (en) * 1999-09-30 2001-04-05 The Procter & Gamble Company Detergent compositions with perfume complexes to mask malodors
EP1111034A1 (en) * 1999-12-22 2001-06-27 The Procter & Gamble Company Laundry and cleaning and/or fabric care compositions
WO2006014740A1 (en) 2004-07-21 2006-02-09 Magna International Inc. Assembly aid for running boards
WO2007135645A2 (en) 2006-05-22 2007-11-29 The Procter & Gamble Company Liquid detergent composition for improved grease cleaning
WO2007138053A1 (en) 2006-05-31 2007-12-06 Basf Se Amphiphilic graft polymers based on polyalkylene oxides and vinyl esters
WO2008100625A1 (en) * 2007-02-15 2008-08-21 The Procter & Gamble Company Benefit agent delivery compositions

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A. LEO: "Comprehensive Medicinal Chemistry", vol. 4, 1990, PERGAMON PRESS, pages: 295
See also references of EP2512531A1
SMITH; MARTEL: "Critical Stability Constants: Volume 2, Amines", 1975, PLENUM PRESS
STEFFEN ARCTANDER: "Perfume and Flavor Chemicals (Aroma Chemicals)", 1969

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014530930A (en) * 2011-10-19 2014-11-20 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Composition, method of use thereof for producing dishwashing detergent and method of production thereof
JP2015520619A (en) * 2012-04-10 2015-07-23 ザ プロクター アンド ギャンブルカンパニー Odor reducing composition
US11938242B2 (en) 2017-11-03 2024-03-26 The Procter & Gamble Plaza Apparatus and method for reducing malodor on surfaces

Also Published As

Publication number Publication date
EP2512530A1 (en) 2012-10-24
US20110146001A1 (en) 2011-06-23
CA2865839A1 (en) 2011-07-14
BR112012014692A2 (en) 2015-10-27
CA2865839C (en) 2017-05-16
US20110146725A1 (en) 2011-06-23
EP2512531A1 (en) 2012-10-24
US9055849B2 (en) 2015-06-16
RU2012119342A (en) 2014-01-27
MX2012007022A (en) 2012-07-04
RU2012119348A (en) 2014-01-27
EP2512528A1 (en) 2012-10-24
RU2557989C2 (en) 2015-07-27
US20130247941A1 (en) 2013-09-26
WO2011084574A1 (en) 2011-07-14
EP2512528B1 (en) 2018-06-06
CA2782479A1 (en) 2011-07-14
US9226641B2 (en) 2016-01-05
MX2012007021A (en) 2012-07-04
CA2782418A1 (en) 2011-07-14
CA2782418C (en) 2014-12-09
CA2782479C (en) 2015-01-27
US20110150817A1 (en) 2011-06-23
US8629092B2 (en) 2014-01-14
WO2011084577A1 (en) 2011-07-14
JP2013513721A (en) 2013-04-22
JP5639661B2 (en) 2014-12-10
US20140090663A1 (en) 2014-04-03
US8461089B2 (en) 2013-06-11
JP2013513722A (en) 2013-04-22
US20110152157A1 (en) 2011-06-23
CN102655886A (en) 2012-09-05
ZA201203443B (en) 2013-01-31
CA2780656A1 (en) 2011-07-14

Similar Documents

Publication Publication Date Title
US9055849B2 (en) Dishwashing detergent composition having a malodor control component and methods of cleaning dishware
ES2365739T3 (en) COMBINATION OF AROMATIC SUBSTANCES CONTAINING 3,7-DIMETILOCT-6-ENO-NITRILE (CITRONELIL NITRILE) AS A SUBSTITUTE FOR GERANONITRILE.
RU2527423C2 (en) Liquid detergent composition for manual dish-washing
RU2608735C1 (en) Liquid detergent composition for hand dish washing
EP2162525A1 (en) Perfumed household products and methods for preserving perfume integrity and extending fragrance life
JP2004501273A (en) Rinse-added fabric treatment compositions, kits containing them and methods of using them
JP2007014749A (en) Deodorant composition
US20040077520A1 (en) Perfume composition and cleaning compositions comprising the perfume composition
JP2002525418A (en) Antibacterial detergent composition
EP1161515B1 (en) Perfume compositions and methods to mask amine malodors
JP2009185094A (en) Detergent composition for toilet
US6979667B1 (en) Perfume compositions and methods to mask amine malodors
JP2004503670A (en) Perfume composition and detersive composition containing this perfume composition
US20090000979A1 (en) Perfumed household products and methods for preserving perfume integrity and extending fragrance life
EP1230336A1 (en) Detergent compositions with perfume complexes to mask malodors
JPH09313582A (en) Deodorant composition
JP2010004971A (en) Method for suppressing malodor generated from waste, drain outlet and the like
KR0180489B1 (en) Detergent for cleaning and deodorizing of dish-washer
JP2003129086A (en) Liquid detergent composition and method for deodorization

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10801497

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2782479

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2010801497

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2012544814

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: MX/A/2012/007021

Country of ref document: MX

NENP Non-entry into the national phase

Ref country code: DE