EP0798370A1 - Flüssige schwach schäumende Waschmittel - Google Patents
Flüssige schwach schäumende Waschmittel Download PDFInfo
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- EP0798370A1 EP0798370A1 EP96870038A EP96870038A EP0798370A1 EP 0798370 A1 EP0798370 A1 EP 0798370A1 EP 96870038 A EP96870038 A EP 96870038A EP 96870038 A EP96870038 A EP 96870038A EP 0798370 A1 EP0798370 A1 EP 0798370A1
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- Prior art keywords
- alkyl
- surfactants
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- detergent composition
- silicone
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/40—Monoamines or polyamines; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
Definitions
- the present invention relates to detergent compositions having controlled sudsing profile More in particular, the invention relates to liquid detergent compositions comprising a suds suppressing system, said suds suppressing system comprising a silicone suds suppressor and a specific short chain length amine surfactant.
- suds suppressing systems include for example suds suppressing agents such as silicone.
- suds suppressing systems such as silicone can be difficult to maintain as a dispersion in liquid compositions and are difficult to process.
- silicone suds suppressors are expensive.
- European patent application No. 94922023.0 filed June 28, 1993 discloses low sudsing liquid detergent compositions comprising a conventional anionic surfactant in combination with a ⁇ -branched anionic surfactant.
- European patent application No. 94307794.1 filed October 24, 1994 describes concentrated detergent compositions comprising branched nonionic surfactants derived from 2-alkyl-alkanols and having controlled sudsing profile.
- a suds suppressor system comprising a specific mixture of fatty acids and silicone anti-foam agent and capable of providing a suds controlling profile for concentrated liquid detergent has been proposed in European patent application No. 94307979.8 filed Ocober 28, 1994.
- a suds suppressing system comprising silicone suds suppressors in combination with a specific short chain length C 6 - C 10 amine surfactant.
- WO 95/05440 discloses granular automatic dishwashing compositions comprising long-chain (>12C) amines oxides and silicone suds suppressors. Shorther-chain amines oxides are therein recognised to foam less but provide poorer cleaning. Short chain length are known in the art to be lower foaming than long chain surfactants ( J.Coll.Int.Sci ., 159 , pp 214-225 (1993) - Kirk-Othner's Enc. Chem. Techn., p 359). Indeed, European patent application No. 93870050.7 filed March 19, 1993 discloses that the following nonionic surfactants - short chain alkoxylated alcohols - are particularly efficient in cleaning and are low foaming and mild to the skin.
- Amineoxides are extensively described in general detergent formulations (J 04 011 698, GB 2 229 460), in dishwashing (WO 95/20026, WO 95/07971) and in personal cleansing applications (GB 2 160 541, US 5 290 471, DE 4 020 500).
- C 10 - C 18 amineoxides J 59 196 395, J 56087000
- betaines are generally described as suds enhancing agents (WO 94/05758, WO 92/06161, US 4 879 051).
- WO 95/20028 indeed states that the inclusion of relatively high levels of long chain amineoxides substantially enhances the grease and oil removal of the detergent compositions and allows the formulation or reasonably low sudsing, stable and homogeneous detergent compositions.
- the present invention relates to liquid detergents comprising a suds suppressing system, said system comprising a silicone suds suppressor and a specific short chain length amine surfactant selected from the formulas (i)-(viii): R 1 - NH 2 (i) R 1 - N(R 2 ) 2 (ii) R 1 - N(R 2 ) 2 ⁇ O R 1 - (CO) - N (CH 2 ) 3 - N (R 3 ) 2 (iv) R 1 - (CO) - N (CH 2 ) 3 - N (R 3 ) 2 ⁇ O R 1 - (CO) - N (CH 2 ) 2 - N (R 3 ) 2 ⁇ O R 1 - (CO) - N [(CH 2 ) 2 -O] x - N (R 3 ) 2 ⁇ O and mixtures thereof (viii) wherein R1 is a linear, branched, cyclic, saturated or unsaturated alkyl group with 6 to 10 carbon
- the liquid detergent of present invention comprise a suds suppressing system consisting of a silicone suds suppressor and a short chain length amine surfactant selected from the formulas (i)-(viii): R 1 - NH 2 (i) R 1 - N(R 2 ) 2 (ii) R 1 - N(R 2 ) 2 ⁇ O R 1 - (CO) - N (CH 2 ) 3 - N (R 3 ) 2 (iv) R 1 - (CO) - N (CH 2 ) 3 - N (R 3 ) 2 ⁇ O R 1 - (CO) - N (CH 2 ) 2 - N (R 3 ) 2 ⁇ O R 1 - (CO) - N [(CH 2 ) 2 -O] x - N (R 3 ) 2 ⁇ O and mixtures thereof (viii) wherein R1 is a linear, branched, cyclic, saturated or unsaturated alkyl group with 6 to 10 carbons atoms; R 2
- Preferred short chain length amine surfactants are selected from the group of amidopropylamines, dimethylamines, trimethylammonium salts, hydroxyethyldimethylammonium salts, bishydroxyethylmethylammonium salts, dimethylamineoxides, betaines, amidopropylbetaines; more preferred short length C 6 - C 10 amine surfactant are amineoxides and amido-propyldimethylamines; most preferred are ethylhexyl amine, octylamine and hexylamine.
- the level of short chain length amine surfactant will vary depending on the particular characteristics desired in the final detergent composition. It will generally be comprised between 0.2 to 10% by weight of the total detergent composition
- suds should not form to the extent that they overflow the washing machine.
- Suds suppressors when utilised, are preferably present in a "suds suppressing amount".
- 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.
- the weight ratio of the short chain length amine surfactant to the silicone ranges from 0.1 to 250, more preferably from 0.5 to 150, and most preferably from 1 to 50.
- the short chain length amine surfactants according to the present invention synergistically enhance the suds suppressing activity of the silicone suds suppressor.
- the silicone/short chain length amine surfactant 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 encompasses a variety of relatively high-molecular-weight polymers containing siloxane units and hydrocarbyl groups of various types.
- silicone suds controllers 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 m 2 /s to 0.1 m 2 /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 2, 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.
- the silicone/short chain length amine surfactant being cationic at loe pH can be added to the liquid detergent composition as a premix as such or as a mixture with other detergent ingredients.
- the liquid detergent composition comprising the surfactant system of the present invention mixed with detergent ingredients.
- a wide range of surfactants can be used in the detergent composition of the present invention.
- Suitable anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 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 C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -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 piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
- Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate (C 12 -C 18 E(1.0)M), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate (C 12 -C 18 E(2.25)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate (C 12 -C 18 E(3.0)M), and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate (C 12 -C 18 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
- Suitable anionic surfactants to be used are alkyl ester sulfonate surfactants including linear esters of C 8 -C 20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO 3 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 : R 3 - CH(SO 3 M) - C(O) - OR 4 wherein R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C 1 -C 6 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.
- R 3 is C 10 -C 16 alkyl
- R 4 is methyl, ethyl or isopropyl.
- methyl ester sulfonates wherein R 3 is C 10 -C 16 alkyl.
- alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 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 C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl
- M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted
- alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
- alkyl chains of C 12 -C 16 are preferred for lower wash temperatures (e.g. below about 50°C) and C 16-18 alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C).
- 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, C 9 -C 20 linear alkylbenzenesulfonates, C 8 -C 22 primary of secondary alkanesulfonates, C 8 -C 24 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 C 12 -C 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 6 -C 12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the
- Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are 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 3% to about 20% by weight of such anionic surfactants.
- Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
- These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
- the ethylene oxide is present in an amount equal to from about 5 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
- nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
- the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention.
- the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
- nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C 11 -C 15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C 12 -C 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C 14 -C 15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C 12 -C 13 linear alcohol with 6.5 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C 14 -C 15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation product of C 14 -C 15 linear alcohol with 4 moles of ethylene oxide) marketed by Shell Chemical Company, and KyroTM EOB (the condensation product of C 13 -C 15 alcohol with 9 moles ethylene oxide), marketed by The Procter
- nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
- a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
- Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
- the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2- 3-, 4-, and/or 6- positions on the preceding saccharide units.
- a polyalkylene-oxide chain joining the hydrophobic moiety and the polysaccharide moiety.
- the preferred alkyleneoxide is ethylene oxide.
- Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms.
- the alkyl group is a straight chain saturated alkyl group.
- the alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
- Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.
- Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
- the preferred alkylpolyglycosides have the formula R 2 O(C n H 2n O) t (glycosyl) x wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
- the glycosyl is preferably derived from glucose.
- the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position).
- the additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
- condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant of the nonionic surfactant systems of the present invention.
- the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
- the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
- Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
- nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
- the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
- This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
- this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
- Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C 8 -C 14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C 8 -C 18 alcohol ethoxylates (preferably C 10 avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
- Highly preferred nonionic surfactants are polyhydoxy fatty acid amide surfactants.
- nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula R 2 - C(O) - N(R 1 ) - Z, wherein R 1 is H, or R 1 is C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 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.
- R 1 is methyl
- R 2 is a straight C 11-15 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 nonionic surfactant systems of the present invention act to improve the greasy/oily stain removal properties of such laundry detergent compositions across a broad range of laundry conditions.
- the laundry detergent compositions of the present invention may also contain nonionic, ampholytic, zwitterionic, and semi-polar surfactants, as well as cationic surfactants other than those already described herein.
- Preferred other cationic surfactant systems include nonionic and ampholytic surfactants.
- Other cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
- Examples of such cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula : [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N+X- wherein R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, - CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl,
- Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula : R 1 R 2 R 3 R 4 N + X - (i) wherein R 1 is C 8 -C 16 alkyl, each of R 2 , R 3 and R 4 is independently C 1 -C 4 alkyl, C 1 -C 4 hydroxy alkyl, benzyl, and -(C 2 H 40 ) x H where x has a value from 2 to 5, and X is an anion. Not more than one of R 2 , R 3 or R 4 should be benzyl.
- the preferred alkyl chain length for R 1 is C 12 -C 15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
- Preferred groups for R 2 R 3 and R 4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions
- the laundry detergent compositions of the present invention typically comprise from 0% to about 25%, preferably from about 3% to about 15% by weight of such cationic surfactants.
- Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
- One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.
- the laundry detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.
- Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.
- the laundry detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such zwitterionic surfactants.
- Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
- Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula R 3 (OR 4 ) x N(O)(R 5 )2 wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
- the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
- amine oxide surfactants in particular include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
- the laundry detergent compositions of the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.
- the present invention further provides laundry detergent compositions comprising at least 1% by weight, preferably from about 3% to about 65%, more preferably from about 10% to about 25% by weight of total surfactants.
- 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.
- Aqueous liquid detergent compositions were prepared in accord with the present invention and were found to be very efficient in controlling suds while remaining stable upon prolonged periods of storage.
- I II III IV V Alkylsulphate 15.75 15.75 15.75 15.75 Alkylethoxylate 3.0 3.0 3.0 3.0 C 13-15 mixed etoxylated/propoxylated fatty alcohol 2.5 2.5 2.5 2.5 2.5 2.5 Polyhydroxy fatty acid amide 6.8 6.8 6.8 6.8 6.8 Silicone 0.1 0.1 0.1 0.1 0.1 0.1 Ethylhexylamine - 1.0 - - 0.5 Hexylamine 0.5 - 1.0 - - Octylamine 0.5 - - 1.0 0.5 Topped palm kernel fatty acid - 10.0 10.0 10.0 2.0 Rapeseed fatty acid 10.0 - - - 8.0 Citric acid 1.6 1.6 1.6 1.6 1.6 Protease 1.5 1.5 1.5 1.0 1.5 Amylase - 0.8 0.8 1.0 - Lipase 0.5 - - 0.1 0.5
- Non-aqueous liquid detergent compositions were prepared in accord with the present invention and were found to be very efficient in controlling suds while remaining stable upon prolonged periods of storage.
- I II III IV V Linear alkyl benzene sulfonate 20.0 20.0 20.0 20.0 20.0 C 13-15 mixed etoxylated/propoxylated fatty alcohol 18.0 18.0 18.0 18.0 18.0 Butoxy propoxy propanol 18.0 18.0 18.0 18.0 18.0 Silicone 0.9 0.9 0.9 0.9 Hexamethylenediamine tetra-E24 ethoxylate 0.9 0.9 0.9 0.9 0.9 Ethylhexylamine - 1.0 - - 0.5 Hexylamine 0.5 - 1.0 - - Octylamine 0.5 - - 1.0 0.5 Acrylic acid/maleic acid copolymer 3.3 3.3 3.3 3.3 3.3 3.3 Citric acid 1.4 1.4 1.4 1.4 Na 2 CO 3 3.4 3.4 3.4 3.4 3.4 3.4 3.4
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Silicon Polymers (AREA)
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES96870038T ES2230558T3 (es) | 1996-03-29 | 1996-03-29 | Composiciones detergente liquidas con baja formacion de espuma. |
AT96870038T ATE278001T1 (de) | 1996-03-29 | 1996-03-29 | Flüssige schwach schäumende waschmittel |
EP96870038A EP0798370B1 (de) | 1996-03-29 | 1996-03-29 | Flüssige schwach schäumende Waschmittel |
DE69633493T DE69633493T2 (de) | 1996-03-29 | 1996-03-29 | Flüssige schwach schäumende Waschmittel |
DK96870038T DK0798370T3 (da) | 1996-03-29 | 1996-03-29 | Lavtskummende flydende detergentsammensætninger |
CA002250486A CA2250486C (en) | 1996-03-29 | 1997-03-25 | Low sudsing liquid detergent compositions |
PCT/US1997/004795 WO1997036982A1 (en) | 1996-03-29 | 1997-03-25 | Low sudsing liquid detergent compositions |
JP53536897A JP3242668B2 (ja) | 1996-03-29 | 1997-03-25 | 低泡立ち性の液状洗剤組成物 |
CZ983106A CZ310698A3 (cs) | 1996-03-29 | 1997-03-25 | Málo pěnivé tekuté čisticí prostředky a jejich použití |
TR1998/01947T TR199801947T2 (xx) | 1996-03-29 | 1997-03-25 | Az k�p�ren s�v� deterjan terkipleri. |
BR9708464A BR9708464A (pt) | 1996-03-29 | 1997-03-25 | Composições detergentes líquidas de baixa formação de espuma |
CN97195043A CN1219959A (zh) | 1996-03-29 | 1997-03-25 | 低泡液体洗涤剂组合物 |
ARP970101228A AR006412A1 (es) | 1996-03-29 | 1997-03-26 | Composicion detergente liquida que comprende supresor de espuma de silicona, surfactante de amina de cadena corta, y su uso para pretratamiento y limpieza de telas, vajilla y superficies y metodo para el mismo |
ZA9702725A ZA972725B (en) | 1996-03-29 | 1997-03-27 | Low sudsing liquid detergent compositions. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96870038A EP0798370B1 (de) | 1996-03-29 | 1996-03-29 | Flüssige schwach schäumende Waschmittel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0798370A1 true EP0798370A1 (de) | 1997-10-01 |
EP0798370B1 EP0798370B1 (de) | 2004-09-29 |
Family
ID=8226132
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96870038A Expired - Lifetime EP0798370B1 (de) | 1996-03-29 | 1996-03-29 | Flüssige schwach schäumende Waschmittel |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0798370B1 (de) |
JP (1) | JP3242668B2 (de) |
CN (1) | CN1219959A (de) |
AR (1) | AR006412A1 (de) |
AT (1) | ATE278001T1 (de) |
BR (1) | BR9708464A (de) |
CA (1) | CA2250486C (de) |
CZ (1) | CZ310698A3 (de) |
DE (1) | DE69633493T2 (de) |
DK (1) | DK0798370T3 (de) |
ES (1) | ES2230558T3 (de) |
TR (1) | TR199801947T2 (de) |
WO (1) | WO1997036982A1 (de) |
ZA (1) | ZA972725B (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007197670A (ja) * | 2005-12-27 | 2007-08-09 | Kao Corp | 洗浄剤組成物 |
BRPI0721554B1 (pt) * | 2007-04-13 | 2017-11-28 | Ecolab Inc. | Floor cleaning composition with reduced foam properties, use solution containing same and surface cleaning method |
JP5337371B2 (ja) * | 2007-11-28 | 2013-11-06 | 花王株式会社 | 自動食器洗浄機用洗浄剤組成物 |
JP5491770B2 (ja) * | 2009-05-29 | 2014-05-14 | 花王株式会社 | 自動食器洗浄機用洗浄剤組成物 |
JP5491773B2 (ja) * | 2009-06-10 | 2014-05-14 | 花王株式会社 | 自動食器洗浄機用洗浄剤組成物 |
CN106807123A (zh) * | 2016-12-28 | 2017-06-09 | 广东中联邦精细化工有限公司 | 一种抑泡剂及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4584125A (en) * | 1984-08-10 | 1986-04-22 | Sws Silicones Corporation | Antifoam compositions |
WO1995020028A1 (en) * | 1994-01-25 | 1995-07-27 | The Procter & Gamble Company | Low to moderate sudsing detergent compositions containing long chain amine oxide |
CA2144781A1 (en) * | 1994-03-30 | 1995-10-01 | Thomas J. Wierenga | Detergent Compositions Comprising a Synergistic Antifoaming Combination |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7800451A (nl) * | 1977-02-03 | 1978-08-07 | Ciba Geigy | Mengsel van di- of trithiofosforzuurdiesters, werkwijzen ter bereiding en de toepassing ervan. |
US4324674A (en) * | 1980-08-28 | 1982-04-13 | Chevron Research Company | Amine salt stabilized phosphate ester-based functional fluid |
US4855070A (en) * | 1986-12-30 | 1989-08-08 | Union Carbide Corporation | Energy transmitting fluid |
-
1996
- 1996-03-29 DE DE69633493T patent/DE69633493T2/de not_active Expired - Lifetime
- 1996-03-29 ES ES96870038T patent/ES2230558T3/es not_active Expired - Lifetime
- 1996-03-29 DK DK96870038T patent/DK0798370T3/da active
- 1996-03-29 AT AT96870038T patent/ATE278001T1/de not_active IP Right Cessation
- 1996-03-29 EP EP96870038A patent/EP0798370B1/de not_active Expired - Lifetime
-
1997
- 1997-03-25 WO PCT/US1997/004795 patent/WO1997036982A1/en not_active Application Discontinuation
- 1997-03-25 CA CA002250486A patent/CA2250486C/en not_active Expired - Lifetime
- 1997-03-25 TR TR1998/01947T patent/TR199801947T2/xx unknown
- 1997-03-25 CZ CZ983106A patent/CZ310698A3/cs unknown
- 1997-03-25 CN CN97195043A patent/CN1219959A/zh active Pending
- 1997-03-25 BR BR9708464A patent/BR9708464A/pt not_active Application Discontinuation
- 1997-03-25 JP JP53536897A patent/JP3242668B2/ja not_active Expired - Fee Related
- 1997-03-26 AR ARP970101228A patent/AR006412A1/es unknown
- 1997-03-27 ZA ZA9702725A patent/ZA972725B/xx unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4584125A (en) * | 1984-08-10 | 1986-04-22 | Sws Silicones Corporation | Antifoam compositions |
WO1995020028A1 (en) * | 1994-01-25 | 1995-07-27 | The Procter & Gamble Company | Low to moderate sudsing detergent compositions containing long chain amine oxide |
CA2144781A1 (en) * | 1994-03-30 | 1995-10-01 | Thomas J. Wierenga | Detergent Compositions Comprising a Synergistic Antifoaming Combination |
Also Published As
Publication number | Publication date |
---|---|
CN1219959A (zh) | 1999-06-16 |
ZA972725B (en) | 1997-10-23 |
EP0798370B1 (de) | 2004-09-29 |
ATE278001T1 (de) | 2004-10-15 |
WO1997036982A1 (en) | 1997-10-09 |
CA2250486A1 (en) | 1997-10-09 |
CZ310698A3 (cs) | 1999-02-17 |
AR006412A1 (es) | 1999-08-25 |
CA2250486C (en) | 2003-12-16 |
DK0798370T3 (da) | 2005-01-03 |
DE69633493D1 (de) | 2004-11-04 |
JP3242668B2 (ja) | 2001-12-25 |
JP2000509078A (ja) | 2000-07-18 |
DE69633493T2 (de) | 2006-02-16 |
TR199801947T2 (xx) | 1998-12-21 |
ES2230558T3 (es) | 2005-05-01 |
BR9708464A (pt) | 1999-04-13 |
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