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EP0709451A1 - Stable liquid detergent compositions - Google Patents

Stable liquid detergent compositions Download PDF

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Publication number
EP0709451A1
EP0709451A1 EP94307979A EP94307979A EP0709451A1 EP 0709451 A1 EP0709451 A1 EP 0709451A1 EP 94307979 A EP94307979 A EP 94307979A EP 94307979 A EP94307979 A EP 94307979A EP 0709451 A1 EP0709451 A1 EP 0709451A1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
alkyl
composition according
detergent composition
silicone
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP94307979A
Other languages
German (de)
French (fr)
Inventor
Roger Jefferey Jones
Peter Johannes Marie Baets
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP94307979A priority Critical patent/EP0709451A1/en
Priority to JP8514620A priority patent/JPH10508060A/en
Priority to CN 95196870 priority patent/CN1170428A/en
Priority to PCT/US1995/013213 priority patent/WO1996013566A1/en
Priority to CA 2203399 priority patent/CA2203399A1/en
Priority to BR9509534A priority patent/BR9509534A/en
Publication of EP0709451A1 publication Critical patent/EP0709451A1/en
Priority to MXPA/A/1997/003106A priority patent/MXPA97003106A/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/36Organic compounds, e.g. vitamins containing silicon
    • 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
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/047Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on cationic surface-active compounds and soap
    • 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
    • C11D3/37Polymers
    • 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
    • C11D9/00Compositions of detergents based essentially on soap
    • C11D9/04Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22Organic compounds, e.g. vitamins
    • C11D9/225Polymers
    • 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
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest

Definitions

  • the present invention relates to stable homogeneous liquid detergent compositions. More in particular, the present invention relates to liquid detergent compositions comprising a suds supressing system, said suds supressing system comprising a silicone antifoam agent and a specific fatty acid mixture.
  • Silicone antifoam agents are included in detergent compositions to control the amount of foam produced during a washing cycle in a washing machine. Silicone antifoam agents in finely dispersed form have been found to be particularly effective species. However, it is particularly difficult to homogeneously disperse antifoam formulations into concentrated liquid detergents.
  • a suds suppressing system comprising silicone-antifoam agent in combination with a specific mixture of fatty acids.
  • the present invention relates to concentrated liquid detergents, in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. Th elevel of water in the concentrated liquid detergents of the present invention is less than 50%, preferably less than 40%, more preferably less than 30% of water by weight of the total detergent compositions.
  • fatty acids suitable for use in the fatty acid mixture of the present invention include palmitoleic, safflower, sunflower, soyabean, oleic, linoleic, linolenic, ricinoleic, rapeseed oil or mixtures thereof. Mixtures of saturated and unsaturated fatty acids can also be used herein. Preferred mixtures include mixtures of palmkernel fatty acid and rapeseed fatty acid in a ratio of from 9:1 to 1:9, preferably from 3:1 to 1:9. Suitable sources of fatty acids are well known. For example see Bailey's Industrial Oil and fat Products, Third edition, Swern, published by Interscience Publisher, 1964.
  • the amount of fatty acid will vary depending on the particular characteristics desired in the final detergent composition.
  • the weight ratio of the fatty acid mixture to the silicone from 1:1 to 400:1, more preferably from 10:1 to 200:1.
  • the specific selected fatty acids according to the present invention synergistically enhance the suds suppressing activity of the silicone suds suppressor.
  • the silicone/fatty acid combination according to the present invention gives a statistically significant better suds suppressing activity which is better than the sum of the individual suds suppressing activity of both ingredients.
  • silicone suds suppressor has become a generic term which emcompasses a variety of relatively high-molecular-weight polymers containing siloxane units and hydrocarbyl groups of various types.
  • silicone sudscontrollers can be described as siloxanes having the general structure : wherein n is from 20 to 2.000, and where each R independently can be an alkyl or an aryl radical. Examples of such substituents are methyl, ethyl, propyl, isobutyl, and phenyl.
  • Preferred polydiorganosiloxanes are polydimethylsiloxanes having trimethylsilyl endblocking units and having a viscosity at 25°C of from 5 x 10 ⁇ 5 m2/s to 0.1 m2/s i.e. a value of n in the range 40 to 1500. These are preferred because of their ready availability and their relatively low cost.
  • Suitable silicone oils that can be used for the present invention are functional silicone oils.
  • Preferred functional silicone oils are anionic or cationic type of silicone oils.
  • silicone include combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well-known in the art and are, for example, disclosed in U.S. Patent 4,265,779, and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M.S.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of :
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the preferred primary silicone suds suppressor is branched/crosslinked.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5 weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant, and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight % and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorganosiloxan
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol copolymer of polyethylene-polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PURONIC L101.
  • Silicone suds suppressors are typically utilized in amounts up to about 2.0% by weight of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs mimimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.05% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. In terms of processing, the silicone/fatty acid mixture can be added to the liquid detergent composition as a premix as such or as a mixture with other detergent ingredients.
  • the detergent compositions according to the present invention comprise a surfactant system which is free of linear alkylbenzene sulfonate surfactant (Nil-Las).
  • the surfactant is preferably selected from anionic surfactants selected from the group of alkylalkoxy sulfates and alkyl sulfates.
  • Preferred anionic surfactants include the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C18 alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C18 alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium
  • methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C18 alkyl or hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12-C15 alkyl polyethoxylate (1.0) sulfate (C12-C15E(1.0)M), C12-C15 alkyl polyethoxylate (2.25) sulfate (C12-C15E(2.25)M), C12-C15 alkyl polyethoxylate (3.0) sulfate (C12-C15E(3.0)M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (C12-C15E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula : wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R3 is C10-C16 alkyl
  • R4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R3 is C10-C16 alkyl.
  • anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention.
  • These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, C8-C22 primary of secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants.
  • One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
  • Nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula wherein R1 is H, or R1 is C1 ⁇ 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5 ⁇ 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R1 is methyl
  • R2 is a straight C11 ⁇ 15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • the detergent compositions herein may also contain additional suds suppressors.
  • additional suds suppressors include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g. K, Na and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • the term "paraffin", as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • suds suppressors useful herein comprise the secondary alcohols (e.g. 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150 872.
  • the secondary alcohols include the C6-C16 alkyl alcohols having a C1-C16 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 20:1.
  • monocarboxylic fatty acids, and salts therein When utilized mainly as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 15% by weight of the detergent composition. Preferably from about 5% to about 15% of fatty monocarboxylate suds suppressor is utilized. In addition, the compositions herein will generally comprise from 0% to about 5% of suds suppressor.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • compositions according to the present invention may further comprise a builder system.
  • a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
  • phosphate builders can also be used herein.
  • Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
  • Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
  • suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • Another preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
  • Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
  • detergent compositions may be employed, such as enzymes and stabilizers or activators therefore, soil-suspending agents, abrasives, bactericides, tarnish inhibitors, coloring agents, corrosion inhibitors and perfumes.
  • enzymes and stabilizers or activators therefore, soil-suspending agents, abrasives, bactericides, tarnish inhibitors, coloring agents, corrosion inhibitors and perfumes.
  • combinations with enzyme technologies which also provide a type of color care benefit. Examples are cellulase for color maintenance/rejuvenation.
  • Other examples are the polymers disclosed in EP 92870017.8 filed January 31, 1992 and enzyme oxidation scavengers disclosed in EP 92870018.6 filed January 31, 1992.
  • the detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • the detergent compositions according to the present invention include compositions which are to be used for cleaning of substrates, such as fabrics, fibers, hard surfaces, etc., for example laundry detergent compositions and automatic and non-automatic dishwashing compositions, hard surface cleaners.
  • liquid detergent compositions (I-IV) were found to be very efficient in controlling suds while remaining stable upon prolonged periods of storage.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Detergent Compositions (AREA)
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Abstract

A concentrated Nil-Las containing liquid detergent comprising a silicone oil and a fatty acid mixture characterized in that said fatty acid mixture comprises
  • i) at least 20% of unsaturated fatty acid;
  • ii) at least 30% of fatty acid having 16 or more carbon atoms.

Description

    FIELD OF THE INVENTION
  • The present invention relates to stable homogeneous liquid detergent compositions. More in particular, the present invention relates to liquid detergent compositions comprising a suds supressing system, said suds supressing system comprising a silicone antifoam agent and a specific fatty acid mixture.
  • BACKGROUND OF THE INVENTION
  • One of the overriding trends in today's liquid detergent business is the move toward more concentrated liquid detergents. This shift offers the inherent efficiency of manufacture and use of liquid formulas, such as pumpability and easy measuring of liquids, while reducing the burden of packaging and shipping costs. This trend is occurring in both the consumer market products and in industrial formulations. The move toward concentrated liquids usually entails the reduction of water content in a formulated liquid. This results in an increase in electrolyte and solids levels in these liquid detergent formulas. Another change is the dependence on non-aqueous solvents to aid in the solubilization of detergent components such as surfactants. Both of these changes make stabilization of certain detergent ingredients against physical separation and/or aggregation phenomena more difficult.
    One of these ingredients include silicone antifoam agents. Said silicone antifoam agents are included in detergent compositions to control the amount of foam produced during a washing cycle in a washing machine. Silicone antifoam agents in finely dispersed form have been found to be particularly effective species. However, it is particularly difficult to homogeneously disperse antifoam formulations into concentrated liquid detergents.
  • It is therefore an object of the present invention to provide a suds suppressor system which is capable of providing a suds controlling profile for concentrated liquid detergents
  • It is another object of this invention to provide homogeneous liquid detergent compositions which will remain stable, particularly upon prolonged storage.
  • The above objectives have been met by a suds suppressing system comprising silicone-antifoam agent in combination with a specific mixture of fatty acids.
  • It has been surprisingly found that the addition of specific mixture of fatty acids provide a synergistic enhancement in the suds-suppression effectiveness of the silicone antifoam agent. This finding allows us to reduce the level of silicone antifoam agent while maintaining the suds controlling profile of silicone-containing detergents.
  • Summary of the invention
  • The present invention relates to concentrated Nil-Las containing liquid detergents comprising a silicone oil and a fatty acid mixture characterized in that said fatty acid comprises
    • i) at least 20% of unsaturated fatty acid;
    • ii) at least 30% of fatty acid having 16 or more carbon atoms.
    All percentages, ratios herein are by weight, unless otherwise specified. Detailed description of the invention
  • The present invention relates to concentrated liquid detergents, in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. Th elevel of water in the concentrated liquid detergents of the present invention is less than 50%, preferably less than 40%, more preferably less than 30% of water by weight of the total detergent compositions.
  • The concentrated liquid detergents of the present invention comprise a silicone oil and a fatty acid mixture characterized in that said fatty acid mixture comprises
    • i) at least 20% of unsaturated fatty acid;
    • ii) at least 30% of fatty acid having 16 or more carbon atoms.
    Preferred fatty acid mixtures comprise comprise at least 40% of unsaturated fatty acid and at least 50% of fatty acid having 16 or more carbon atoms.
  • Examples of fatty acids suitable for use in the fatty acid mixture of the present invention include palmitoleic, safflower, sunflower, soyabean, oleic, linoleic, linolenic, ricinoleic, rapeseed oil or mixtures thereof. Mixtures of saturated and unsaturated fatty acids can also be used herein. Preferred mixtures include mixtures of palmkernel fatty acid and rapeseed fatty acid in a ratio of from 9:1 to 1:9, preferably from 3:1 to 1:9. Suitable sources of fatty acids are well known. For example see Bailey's Industrial Oil and fat Products, Third edition, Swern, published by Interscience Publisher, 1964.
    It will be recognized that the fatty acid will be present in the detergent compositions primarily in the form of a soap. Suitable cations include sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, tetraalkylammonium e.g. tetramethylammonium up to tetradecylammonium etc. cations.
  • The amount of fatty acid will vary depending on the particular characteristics desired in the final detergent composition.
  • For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount". By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • Preferably, the weight ratio of the fatty acid mixture to the silicone from 1:1 to 400:1, more preferably from 10:1 to 200:1.
  • It has been found that the specific selected fatty acids according to the present invention synergistically enhance the suds suppressing activity of the silicone suds suppressor. The silicone/fatty acid combination according to the present invention gives a statistically significant better suds suppressing activity which is better than the sum of the individual suds suppressing activity of both ingredients.
  • In industrial practice, the term "silicone suds suppressor" has become a generic term which emcompasses a variety of relatively high-molecular-weight polymers containing siloxane units and hydrocarbyl groups of various types. Generally, the silicone sudscontrollers can be described as siloxanes having the general structure :
    Figure imgb0001

    wherein n is from 20 to 2.000, and where each R independently can be an alkyl or an aryl radical. Examples of such substituents are methyl, ethyl, propyl, isobutyl, and phenyl. Preferred polydiorganosiloxanes are polydimethylsiloxanes having trimethylsilyl endblocking units and having a viscosity at 25°C of from 5 x 10⁻⁵ m²/s to 0.1 m²/s i.e. a value of n in the range 40 to 1500. These are preferred because of their ready availability and their relatively low cost.
  • Other suitable silicone oils that can be used for the present invention are functional silicone oils. Preferred functional silicone oils are anionic or cationic type of silicone oils.
  • Other silicone include combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well-known in the art and are, for example, disclosed in U.S. Patent 4,265,779, and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M.S.
  • Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839, which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
  • Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672 and in U.S. Patent 4,652,392.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of :
    • (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500cs. at 25°C;
    • (ii) from about 5 to about 50 parts per 100 parts by weight of (I) of siloxane resin composed of (CH₃)₃SiO1/2 units of SiO₂ units in a ratio of from (CH₃)₃sIo1/2 units and to SiO₂ units of from about 0.6:1 to about 1.2:1, and
    • (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.
  • In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The preferred primary silicone suds suppressor is branched/crosslinked.
  • To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5 weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant, and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight % and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471 and 4,983,316, U.S. Patent 5,288,431 and U.S. Patents 4,639,489 and 4,749,740.
  • The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
  • The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol copolymer of polyethylene-polypropylene glycol.
  • The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PURONIC L101.
  • Silicone suds suppressors are typically utilized in amounts up to about 2.0% by weight of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs mimimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.05% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
    In terms of processing, the silicone/fatty acid mixture can be added to the liquid detergent composition as a premix as such or as a mixture with other detergent ingredients.
  • Adjunct detergent ingredients
  • The detergent compositions according to the present invention comprise a surfactant system which is free of linear alkylbenzene sulfonate surfactant (Nil-Las). Preferably, the surfactant is preferably selected from anionic surfactants selected from the group of alkylalkoxy sulfates and alkyl sulfates.
  • A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in US Patent 3,664,961 issued to Norris on May 23, 1972.
  • Preferred anionic surfactants include the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO₃M wherein R preferably is a C₁₀-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀-C₁₈ alkyl component, more preferably a C₁₂-C₁₅ alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubstituted C₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀-C₂₄ alkyl component, preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, more preferably C₁₂-C₁₅ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C₁₂-C₁₅ alkyl polyethoxylate (1.0) sulfate (C₁₂-C₁₅E(1.0)M), C₁₂-C₁₅ alkyl polyethoxylate (2.25) sulfate (C₁₂-C₁₅E(2.25)M), C₁₂-C₁₅ alkyl polyethoxylate (3.0) sulfate (C₁₂-C₁₅E(3.0)M), and C₁₂-C₁₅ alkyl polyethoxylate (4.0) sulfate (C₁₂-C₁₅E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • Other suitable anionic surfactants to be used are alkyl ester sulfonate surfactants including linear esters of C₈-C₂₀ carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO₃ according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula :
    Figure imgb0002

    wherein R³ is a C₈-C₂₀ hydrocarbyl, preferably an alkyl, or combination thereof, R⁴ is a C₁-C₆ hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R³ is C₁₀-C₁₆ alkyl, and R⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R³ is C₁₀-C₁₆ alkyl.
  • Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C₉-C₂₀ linear alkylbenzenesulfonates, C₈-C₂₂ primary of secondary alkanesulfonates, C₈-C₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, C₈-C₂₄ alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C₁₂-C₁₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C₆-C₁₂ diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO(CH₂CH₂O)k-CH₂COO-M+ wherein R is a C₈-C₂₂ alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • When included therein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants.
  • One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Especially preferred nonionic surfactants of this type are the C₉-C₁₅ primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C₁₂-C₁₅ primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula

            RO (CnH2nO)tZx

    wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula
    Figure imgb0003

    wherein R¹ is H, or R¹ is C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R² is C₅₋₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • The detergent compositions herein may also contain additional suds suppressors. These include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g. stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g. K, Na and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin", as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Other suds suppressors useful herein comprise the secondary alcohols (e.g. 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150 872. The secondary alcohols include the C₆-C₁₆ alkyl alcohols having a C₁-C₁₆ chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 20:1.
  • When utilized mainly as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 15% by weight of the detergent composition. Preferably from about 5% to about 15% of fatty monocarboxylate suds suppressor is utilized. In addition, the compositions herein will generally comprise from 0% to about 5% of suds suppressor.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Though less preferred for obvious environmental reasons, phosphate builders can also be used herein.
    Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
    Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
    Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. Another preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
  • Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
  • Other components used in detergent compositions may be employed, such as enzymes and stabilizers or activators therefore, soil-suspending agents, abrasives, bactericides, tarnish inhibitors, coloring agents, corrosion inhibitors and perfumes. Especially preferred are combinations with enzyme technologies which also provide a type of color care benefit. Examples are cellulase for color maintenance/rejuvenation. Other examples are the polymers disclosed in EP 92870017.8 filed January 31, 1992 and enzyme oxidation scavengers disclosed in EP 92870018.6 filed January 31, 1992.
  • Also particulary suitable are amine base catlyst stabilizers disclosed in EP 92870019.4 filed January 31, 1992.
  • The detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • The detergent compositions according to the present invention include compositions which are to be used for cleaning of substrates, such as fabrics, fibers, hard surfaces, etc., for example laundry detergent compositions and automatic and non-automatic dishwashing compositions, hard surface cleaners.
  • The following examples are meant to exemplify compositions of the present inventions, but are not necessarily meant to limit the scope of the invention.
  • The following liquid detergent compositions were made :
    I II III IV
    C₁₂-C₁₅ Alkyl sulfate 7 15 7 15
    C₁₂-C₁₅ Alkyl ethoxylated sulfate 19 3 19 3
    C₁₂-C₁₄ N-methyl glucamide 6 6 6 6
    C₁₂-C₁₄ fatty alcohol ethoxylate 5 5 5 5
    Citric acid anhydrous 3.5 3.5 3.5 3.5
    Diethylene triamine penta methylene phosphonic acid 2 2 2.0 2.0
    Monoethanolamine 12.8 11.0 12.8 11.0
    Propanediol 13.1 10.0 13.1 10.0
    Ethanol 4.7 5.4 4.7 5.4
    Amylase (300KNU/g) 0.1 0.1 0.1 0.1
    Lipolase(100KNU/g) 0.15 0.15 0.15 0.15
    FNA-Base(34g/l) 0.5 0.5 0.5 0.5
    Endo-A (5000 CEVU/g) 0.05 0.05 0.05 0.05
    Carezyme (5000 CEVU/g) 0.09 0.09 0.09 0.09
    Terephthalate-based polymer 0.5 0.5 0.5 0.5
    Brightener 0.15 0.15 0.15 0.15
    Boric acid
    Aerosil 200 0.01 0.01 0.01 0.01
    Branched silicone 0.15 0.15 0.15 0.15
    Rapeseed fatty acid 3 4 5 3
    Topped Palm Kernel Fatty acid 7 6 5 7
    Water & Minors ------up to 100%------
  • The above liquid detergent compositions (I-IV) were found to be very efficient in controlling suds while remaining stable upon prolonged periods of storage.

Claims (10)

  1. A concentrated Nil-Las containing liquid detergent comprising a silicone oil and a fatty acid mixture characterized in that said fatty acid mixture comprises
    i) at least 20% of unsaturated fatty acid;
    ii) at least 30% of fatty acid having 16 or more carbon atoms
  2. A liquid detergent composition according to claim 1 wherein the weight ratio of the fatty acid mixture to the silicone is from 1:1 to 400:1, more preferably from 10:1 to 200:1.
  3. A liquid detergent composition according to claim 1 wherein the fatty acid mixture comprises at least 40% of unsaturated fatty acid and at least 50% of fatty acid having 16 or more carbon atoms.
  4. A detergent composition according to Claims 1-3 further comprising surfactants, builders, enzymes and other conventional detergent ingredients.
  5. A detergent composition according to Claims 1-4 further comprising an anionic surfactant selected from an alkyl ethoxylated sulfate and/or alkyl sulfate surfactant.
  6. A detergent composition according to Claim 5 further comprising a nonionic surfactant selected from the polyhydroxy fatty acid amides.
  7. A detergent composition according to Claim 6 wherein the nonionic surfactant is C12-C14 N-methyl glucamide.
  8. A detergent composition according to claims 1-7 which is in the form of an additive.
  9. Use of a detergent composition according to claims 1-8 for the cleaning of fabrics, dishes and hard surfaces.
  10. Use of a detergent composition according to Claims 1-7 for pretreatment of fabrics, dishes and hard surfaces.
EP94307979A 1994-10-28 1994-10-28 Stable liquid detergent compositions Withdrawn EP0709451A1 (en)

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CN 95196870 CN1170428A (en) 1994-10-28 1995-10-13 Stable liquid detergent compositions comprising fatty acid and silicone oil
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BR9509534A BR9509534A (en) 1994-10-28 1995-10-13 Stable liquid detergent compositions consisting of fatty acid and silicone oil
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WO2008125143A1 (en) * 2007-04-13 2008-10-23 Ecolab Inc. Floor cleaning composition with reduced foaming properties
JP5396707B2 (en) * 2007-11-07 2014-01-22 ライオンハイジーン株式会社 Cleaning composition
JP7376543B2 (en) * 2021-09-16 2023-11-08 花王株式会社 Cleaning composition for dishwashers

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EP0816480A1 (en) * 1996-06-26 1998-01-07 The Procter & Gamble Company Low sudsing liquid detergent compositions
EP1019471A1 (en) * 1996-07-03 2000-07-19 The Procter & Gamble Company Cleansing compositions
EP1019471A4 (en) * 1996-07-03 2002-08-14 Procter & Gamble Cleansing compositions
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US6358898B1 (en) 1997-12-22 2002-03-19 Dow Corning Australia Pty. Ltd. Personal care products having stable emulsions
US6784144B2 (en) 1997-12-22 2004-08-31 Dow Corning Australia Pty. Ltd. Stable emulsions
EP0976435A1 (en) * 1998-07-29 2000-02-02 Dow Corning Corporation Foam control agents
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WO2007017619A1 (en) * 2005-08-10 2007-02-15 Appaya Raghunath Naik Detergent formulations based on soap and fatty acid n-methyl glucamide
EP2264138A1 (en) * 2009-06-19 2010-12-22 The Procter & Gamble Company Liquid hand dishwashing detergent composition
WO2010147933A1 (en) * 2009-06-19 2010-12-23 The Procter & Gamble Company Liquid hand dishwashing detergent composition
US8901058B2 (en) 2009-06-19 2014-12-02 The Procter & Gamble Company Liquid hand dishwashing detergent composition
US8901059B2 (en) 2009-06-19 2014-12-02 The Procter & Gamble Company Liquid hand dishwashing detergent composition
RU2608735C1 (en) * 2009-06-19 2017-01-23 Дзе Проктер Энд Гэмбл Компани Liquid detergent composition for hand dish washing
EP2264138B2 (en) 2009-06-19 2023-03-08 The Procter & Gamble Company Liquid hand dishwashing detergent composition
WO2013053390A1 (en) 2011-10-12 2013-04-18 Dequest Ag Cleaning composition with improved stain removal
CN110914399A (en) * 2017-09-12 2020-03-24 花王株式会社 Liquid detergent composition for hard surface

Also Published As

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WO1996013566A1 (en) 1996-05-09
JPH10508060A (en) 1998-08-04
CN1170428A (en) 1998-01-14
MX9703106A (en) 1997-07-31
BR9509534A (en) 1997-09-30

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