EP0785978A1 - Detergent compositions containing amines and anionic surfactants - Google Patents
Detergent compositions containing amines and anionic surfactantsInfo
- Publication number
- EP0785978A1 EP0785978A1 EP95904050A EP95904050A EP0785978A1 EP 0785978 A1 EP0785978 A1 EP 0785978A1 EP 95904050 A EP95904050 A EP 95904050A EP 95904050 A EP95904050 A EP 95904050A EP 0785978 A1 EP0785978 A1 EP 0785978A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- detergent composition
- amines
- liquid detergent
- amine
- 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- Withdrawn
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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
- C11D1/65—Mixtures of anionic with cationic compounds
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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
- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
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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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
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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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
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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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
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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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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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
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
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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
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with 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
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic 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
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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
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
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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
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
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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
Definitions
- the present invention relates to detergent compositions containing surfactants selected from amines. More particularly, the invention is directed to detergent compositions containing anionic surfactants selected from the group consisting of alkyl al oxylated sulfates and alkyl sulfates, said composition further containing specific primary and/or tertiary amines.
- Detergent compositions useful for cleaning purposes, such as laundering of fabrics, have commonly utilized a variety of surfactants.
- a surfactant system comprising anionic surfactants selected from the group consisting of alkyl alkoxylated sulfates and alkyl sulfates, said surfactant system further comprising a cosurfactant selected from the group of primary or tertiary amines.
- Liquid detergent compositions formulated with said surfactant system are extremely useful when the liquid detergent compositions are in direct contact with the fabrics such as during pretreatment.
- EP 160 762, EP 137 615 and EP 137 616 disclose liquid detergents which comprise cyclohexylamine.
- EP 177 165 discloses detergent compositions which comprise anionics, cellulase and a variety of primary, secondary, tertiary and quaternary amines.
- EP 11 340 discloses soften through the wash detergent compositions which comprise tertiary amines and clay.
- DE 32 07 487, GB 2 094 826, GB 2 095 275 and EP 137 397 disclose compositions which comprise anionics and quaternary amines.
- EP 120 528 discloses compositions comprising anionics, as well as tertiary amines.
- EP 26 528 and EP 26 529 disclose compositions comprising anionics and quaternary amines.
- Detergent compositions containing 1) primary or tertiary amines of the type useful herein in combination with 2) oleoyl sarcosinate are disclosed in U.S. Patent Application Serial No. 08/252,127, filed June 1, 1994.
- Compositions of this invention may or may not contain oleoyl sarcosinate surfactants.
- the detergent compositions according to the present invention comprise anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates, characterized in that said detergent composition further comprises specific primary and/or a tertiary amines.
- the detergent compositions preferably comprise at least 5%, more preferably from 10% to 65% and most preferably from 15% to 40% by weight of the surfactant system as described hereinabove.
- the weight ratio of the amine cosurfactant to the alkyl alkoxylated sulfates and alkyl sulfates is from 1:1 to 1:250, more preferably from 1:5 to 1:100 and most preferably from 1:10 to 1:40.
- the detergent compositions according to the present invention comprise anionic surfactants selected from the group of alkylalkoxy sulfates and alkyl sulfates. Alkyl alkoxylated sulfates and/or alkyl sulfates
- the alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m S03M wherein R is an unsubstituted CIQ ⁇ C 24 alkyl or hydroxyalkyl group having a c 10" c 24 alkyl component, preferably a 12- 18 alkyl or hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, 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 CIQ ⁇ C 24 alkyl or hydroxyalkyl group having a c 10" c 24 alkyl component, preferably a 12- 18 alky
- Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
- Specific examples of substituted ammonium cations include ethanol-, triethanol-, methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkyla ines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
- Exemplary surfactants are Ci2 ⁇ C15 alkyl polyethoxylate (1.0) sulfate (C12-C15E(1.0)M) , Ci2 _ C 15 alkyl polyethoxylate (2.25) sulfate (C 12 -C!5E(2.25)M) , c 12 _c 15 alkyl polyethoxylate (3.0) sulfate (C12-C15E(3.0)M) , and i2 ⁇ c 15 alkyl polyethoxylate (4.0) sulfate ( ⁇ 2 ⁇ Ci5E(4.0)M), wherein M is conveniently selected from sodium and potassium.
- the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C ⁇ Q- C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a c 10" c 18 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 C ⁇ Q- C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a c 10" c 18 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 or substitute
- methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) .
- alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
- ami-nes refer to primary or tertiary amines which is believed to form a mixed micelle with the anionic surfactant and where the carbon chain length of the alkyl group is equal or greater than Cg.
- Suitable primary amines for use herein include amines according to the formula R ⁇ R2 R 3 N wherein R ⁇ and R2 are both H, R3 is a C4-C18, preferably Cg-C] ⁇ alkyl chain, R3 alkyl chains may be straight or branched and may be interrupted with up to 12 ethylene oxide moieties, most preferably interrupted with up to 5 ethylene oxide moieties.
- Preferred amines according to the formula herein above are n-alkyl amines.
- Suitable amines for use herein may be selected from 1-hexylamine, 1- octylamine, laurylamine, palmitylamine, stearylamine, oleylamine, coconutalkylamine, tallowalkylamine.
- R1R2R3N amines according to the formula R1R2R3N wherein Ri and R2 are both H ;
- R3 is R4X(CH 2 )n' x is -0-,-C(0)NH- or -NH- /
- R4 is a C4-C1.8, preferably Cg-Ci2 alkyl chain and R4 may be branched or straight, n is between 1 to 5.
- Preferred amines according to the formula herein above 3-isopropoxypropylamine, 3-(2- methoxyethoxy)-propylamine and 2-(2-aminoethoxy)-ethanol, Cg- octyl oxy propylamine, 2-ethylhexyloxypropylamine, lauryl amido propylamine and coco amido propylamine.
- Suitable tertiary amines for use herein include amines tertiary amines having the formula R1R2R3N wherein neither R ⁇ nor R2 is H, RI and R2 are C ⁇ Cg alkylchains or
- n is between 2 to 4 and x is between 1 to 6;
- R3 is either a C4-C ⁇ s, preferably Cg-C] ⁇ alkyl chain, or R3 is
- R X(CH 2) n' whereby X is -0-, -C(0)NH- or -NH- R 4 is a C4-C 18 , n is between 1 to 5, and R5 is H or C1-C2 alkyl.
- R3, R4 are preferably Cg-Ci2 alkyl chains and may be straight or branched ; R3 alkyl chains may be interrupted with up to 12 ethylene oxide moieties, most preferably interrupted with up to 5 ethylene oxide moieties.
- Suitable tertiary amines for use herein include coconutalkyldimethylamine, dimethyloleylamine, hexadecyltris (ethyleneoxy)dimethylamine,tallowalkylbis(2- hydroxyethy1)amine, stearoylbis (2-hydroxyethyl)amine and oleoylbis (2-hydroxyethyl) amine.
- the preferred materials are the trialkyl amines marketed under the tradename ADOGEN, the long chain alkyldimethyl amines marketed under the tradename ARMEEN and the ethoxylated amines marketed under the tradename ETHOMEEN.
- the most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1- decylamine, 1-dodecylamine.
- n-dodecyldimethylamine ARMEEN DM12D
- ETHOMEEN C/12, BEROL 307 bishydroxyethylcoconutalkylamine
- oleylamine 7 times ethoxylated BEROL 28
- lauryl amido propylamine and coco amido propylamine.
- amine cosurfactant and anionic surfactant herein form complexes which enhance packing of the surfactants at the oil/water interface, thereby lowering interfacial tension and improving detergency.
- the amine surfactants would be at least partially protonated in the product and during the wash thus can form positively charged species capable of complexing with the anionic surfactant.
- Another aspect of the invention relates to the surprising finding that low amounts of certain primary and/or tertiary amines of the present invention provide suds control to the detergent compositions formulated therewith.
- the amounts in which the amines are used for controlling the suds are from 0.1 to 10%, preferably from 0.1 to 5%, most preferably from 0.5 to 4% by weight of the detergent composition.
- Detergent ingredients preferably from 0.1 to 10%, preferably from 0.1 to 5%, most preferably from 0.5 to 4% by weight of the detergent composition.
- a 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.
- the detergent compositions according to the present invention will preferably comprise a surfactant system which is substantially free of linear alkylbenzene sulfonate surfactant.
- alkyl ester sulfonate surfactants including linear esters of c 8 ⁇ c 20 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.
- alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula :
- R 3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
- R 4 is a C ⁇ -Cg hydrocarbyl, preferably an alkyl, or combination thereof
- 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 Cio-Cig alkyl
- R 4 is methyl, ethyl or isopropyl.
- methyl ester sulfonates wherein R 3 is C ⁇ o -c 16 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, c 8 ⁇ c 22 primary of secondary alkanesulfonates, C ⁇ ⁇ 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 oleoyl 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 Ci2 ⁇ c 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Ci2 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolysaccharides such as the s
- 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 C ⁇ .2" C 5 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
- 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
- R 2 - C(O) - NtR 1 ) - Z wherein R 1 is H, or R 1 is C ⁇ _4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 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.
- R 1 is methyl
- R 2 is a straight C ⁇ _i5 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.
- compositions of the present invention may comprise amine oxide in accordance with the general formula I:
- R' is preferably selected from hydrogen, methyl and -CH2OH.
- R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R is a primary alkyl moiety.
- R is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
- R may be somewhat longer, having a chainlength in the range c 12 ⁇ c 24-
- amine oxides are illustrated by C12-14 alkyldimethyl amine oxide,hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and
- the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
- amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
- Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C.
- Amine oxides suitable for use herein are - made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
- Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
- Preferred embodiments include hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, and tetradecyldimethylamine oxide dihydrate.
- R 1 H
- R' CH OH
- hexadecylbis(2- hydroxyethyl)amine oxide tallowbis(2- hydroxyethyl)amine oxide
- stearylbis(2-hydroxyethyl)amine oxide oleylbis(2- hydroxyethyl)amine oxide.
- the laundry detergent compositions of the present invention typically comprise nonionic surfactants in the weight ratio of anionic surfactant to nonionic surfactant from 6:1 to 1:3, preferably from 5:1 to 2:1.
- Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
- cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula :
- 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 -CH2CH2-, -CH2CH(CH3>-, -CH2CH(CH2 ⁇ H)-, -CH2CH2CH2-, and mixtures thereof
- each R 4 is selected from the group consisting of C 1 -C alkyl, C1-C hydroxyalkyl-, benzyl ring structures formed by joining the two R 4 groups, -CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH wherein R 6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0
- R 5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R 5 is not more than about 18
- each y is from 0 to about 10 and the sum of the
- Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
- R ⁇ is Cg-Cig alkyl
- each of R2, R3 and R4 is independently C1-C alkyl, C1-C hydroxy alkyl, benzyl, and - (C2H4 ⁇ ) x H where x has a value from 1 to 5, and X is an anion.
- R2, R3 or R4 should be benzyl.
- the preferred alkyl chain length for R ⁇ is Ci2 ⁇ i5 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 R2 R 3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
- quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide;
- O-C(O)-C12--14 alkyl and R2R3R4 are methyl).
- the laundry detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of such cationic 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 succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate.
- Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
- polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
- suitable fatty acid builders for use herein are saturated or unsaturated C10- 18 fatty acids, as well as the corresponding soaps.
- Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
- the preferred unsaturated fatty acid is oleic acid.
- Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
- Detergency builder salts are normally included in amounts of from 3% to 50% by weight of the composition preferably from 5% to 30% and most usually from 5% to 25% by weight.
- detergent compositions may be employed, such as enzymes and stabilizers therefore, soil- suspending agents, soil-release polymers, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes.
- enzymes and stabilizers therefore, soil- suspending agents, soil-release polymers, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes.
- the liquid compositions according to the present invention are in "concentrated form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
- the level of water is less than 50%, preferably less than 30%, more preferably less than 20% of water by weight of the detergent compositons.
- Said concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs.
- the liquid compositions are especially effective when applied directly to soils and stains in a pretreatment step.
- 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, skin etc., for example hard surface cleaning compositions(with or without abrasives) , laundry detergent compositions, automatic and non- automatic dishwashing compositions.
- liquid detergent compositions are made % by weight of the detergent compositions
- a B C D c 12 ⁇ c 15 Alkyl ethoxylated sulfate 21 11.0 17 16.
- Octylamine 0.. 1 0. 0.
- Monoethanolamine 8 8 0.5 9 Sodiumhydroxide 1 1 2.5 1 Propanediol 12.7 14.5 13.1 10.
- Amylase (300KNU/g) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Lipolase (lOOKNU/g) 0.15 0.15 0.15 0.15 0.15 Protease (34g/l) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Endo-A (5000 CEVU/g) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
- compositions (A-D) are found to be very efficient in the removal of greasy/oily soils under various usage conditions while having a controlled suds profile.
- octylamine was replaced in Compositions (A-D) by Bis (2-hydroxyethyl) coco amine, Oleyl amine 7EO, lauryl amido propylamine and coco amido propylamine.
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Abstract
A liquid detergent composition comprising anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates, characterized in that said detergent composition further comprises an amine selected from i) primary amines having the formula: R1R2R3N, wherein R1 and R2 are both H; and wherein R3 is C4-C18, or R4X(CH2)n, whereby X is -O-, -C(O)NH- or -NH-, R4 is a C6-C18, n is between 1 to 5; ii) tertiary amines having the formula R1R2R3N, wherein neither R1 nor R2 is H, R?1 and R2¿ are C¿1?-C8 alkylchains or (II), whereby n is between 1 to 5 and x is between 1 to 5, R3 is either C4-C18 or R4X(CH2)n, whereby X is -O-, -C(O)NH- or -NH-, R4 is a C6-C18, n is between 1 to 5 and R5 is H or C1-C2 alkyl; and iii) mixtures of said primary and tertiary amines.
Description
DETERGENT COMPOSITIONS CONTAINING AMINES AND ANIONIC SURFACTANTS
Field of the invention
The present invention relates to detergent compositions containing surfactants selected from amines. More particularly, the invention is directed to detergent compositions containing anionic surfactants selected from the group consisting of alkyl al oxylated sulfates and alkyl sulfates, said composition further containing specific primary and/or tertiary amines.
Background of the invention
Detergent compositions useful for cleaning purposes, such as laundering of fabrics, have commonly utilized a variety of surfactants.
The ability of surfactants to clean a large variety of soils and stains from fabrics present in the typical load of laundry is of high importance in the evaluation of detergent performance. Unfortunately, the relative ability of each surfactant to meet various performance criteria is among others depending on the presence of cosurfactants.
The recent trend towards partial or total replacement of Linear alkyl- benzene sulfonate surfactants (LAS) has urged the detergent formulators to rebalance their formulations with different surfactants. For example, quaternary ammonium salts are less efficient in boosting the greasy cleaning performance in Nil-LAS formulations.
There is thus a standing desire for performance and flexibility reasons to make available a surfactant system capable of providing optimum detergency performance which is equivalent to that of LAS-containing detergents.
The above objective has been met by a surfactant system comprising anionic surfactants selected from the group consisting of alkyl alkoxylated sulfates and alkyl sulfates, said surfactant system further comprising a cosurfactant selected from the group of primary or tertiary amines.
It has been surprisingly found that detergent compositions containing said surfactant system exhibit detergency performance equivalent to that of LAS-containing detergents .
In addition, it has been found that a small amount of certain primary and tertiary amines according to the present invention constitutes an efficient and compatible sud suppressing system. This additional benefit allows to use the amines in a dual function, e.g. surfactant and suds suppressor, thereby facilitating the formulation of concentrated liquid detergents.
Liquid detergent compositions formulated with said surfactant system are extremely useful when the liquid detergent compositions are in direct contact with the fabrics such as during pretreatment.
Amines have been described in the art in liquid detergent compositions. EP 160 762, EP 137 615 and EP 137 616 disclose liquid detergents which comprise cyclohexylamine. EP 177 165 discloses detergent compositions which comprise anionics, cellulase and a variety of primary, secondary, tertiary and quaternary amines. EP 11 340 discloses soften through the wash detergent compositions which comprise tertiary amines and clay. DE 32 07 487, GB 2 094 826, GB
2 095 275 and EP 137 397 disclose compositions which comprise anionics and quaternary amines. EP 120 528 discloses compositions comprising anionics, as well as tertiary amines. EP 26 528 and EP 26 529 disclose compositions comprising anionics and quaternary amines. Detergent compositions containing 1) primary or tertiary amines of the type useful herein in combination with 2) oleoyl sarcosinate are disclosed in U.S. Patent Application Serial No. 08/252,127, filed June 1, 1994. Compositions of this invention may or may not contain oleoyl sarcosinate surfactants.
Summary of the invention
The detergent compositions according to the present invention comprise anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates, characterized in that said detergent composition further comprises specific primary and/or a tertiary amines.
The detergent compositions preferably comprise at least 5%, more preferably from 10% to 65% and most preferably from 15% to 40% by weight of the surfactant system as described hereinabove.
Preferably, the weight ratio of the amine cosurfactant to the alkyl alkoxylated sulfates and alkyl sulfates is from 1:1 to 1:250, more preferably from 1:5 to 1:100 and most preferably from 1:10 to 1:40.
Detailed description of the Invention
The detergent compositions according to the present invention comprise anionic surfactants selected from the group of alkylalkoxy sulfates and alkyl sulfates.
Alkyl alkoxylated sulfates and/or alkyl sulfates
The alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mS03M wherein R is an unsubstituted CIQ~C24 alkyl or hydroxyalkyl group having a c10"c24 alkyl component, preferably a 12- 18 alkyl or hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, 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 ethanol-, triethanol-, methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkyla ines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are Ci2~ C15 alkyl polyethoxylate (1.0) sulfate (C12-C15E(1.0)M) , Ci2_ C15 alkyl polyethoxylate (2.25) sulfate (C12-C!5E(2.25)M) , c12_c15 alkyl polyethoxylate (3.0) sulfate (C12-C15E(3.0)M) , and i2~c15 alkyl polyethoxylate (4.0) sulfate ( χ2~ Ci5E(4.0)M), wherein M is conveniently selected from sodium and potassium.
The alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C^Q- 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 piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) .
The amine
The ami-nes as used herein refer to primary or tertiary amines which is believed to form a mixed micelle with the anionic surfactant and where the carbon chain length of the alkyl group is equal or greater than Cg.
Suitable primary amines for use herein include amines according to the formula R^R2R3N wherein R^ and R2 are both H, R3 is a C4-C18, preferably Cg-C]^ alkyl chain, R3 alkyl chains may be straight or branched and may be interrupted with up to 12 ethylene oxide moieties, most preferably interrupted with up to 5 ethylene oxide moieties. Preferred amines according to the formula herein above are n-alkyl amines. Suitable amines for use herein may be selected from 1-hexylamine, 1- octylamine, laurylamine, palmitylamine, stearylamine, oleylamine, coconutalkylamine, tallowalkylamine.
Other suitable primary amines include amines according to the formula R1R2R3N wherein Ri and R2 are both H ; R3 is R4X(CH2)n' x is -0-,-C(0)NH- or -NH-/ R4 is a C4-C1.8, preferably Cg-Ci2 alkyl chain and R4 may be branched or straight, n is between 1 to 5. Preferred amines according to the formula herein above 3-isopropoxypropylamine, 3-(2- methoxyethoxy)-propylamine and 2-(2-aminoethoxy)-ethanol, Cg- octyl oxy propylamine, 2-ethylhexyloxypropylamine, lauryl amido propylamine and coco amido propylamine.
Suitable tertiary amines for use herein include amines tertiary amines having the formula R1R2R3N wherein neither R^ nor R2 is H, RI and R2 are Cι~Cg alkylchains or
whereby n is between 2 to 4 and x is between 1 to 6;
R3 is either a C4-Cιs, preferably Cg-C]^ alkyl chain, or R3 is
R X(CH2)n' whereby X is -0-, -C(0)NH- or -NH- R4 is a C4-C18, n is between 1 to 5, and R5 is H or C1-C2 alkyl.
R3, R4 are preferably Cg-Ci2 alkyl chains and may be straight or branched ; R3 alkyl chains may be interrupted with up to 12 ethylene oxide moieties, most preferably interrupted with up to 5 ethylene oxide moieties.
Suitable tertiary amines for use herein include coconutalkyldimethylamine, dimethyloleylamine, hexadecyltris (ethyleneoxy)dimethylamine,tallowalkylbis(2- hydroxyethy1)amine, stearoylbis (2-hydroxyethyl)amine and oleoylbis (2-hydroxyethyl) amine.
Of all of the foregoing amines the preferred materials are the trialkyl amines marketed under the tradename ADOGEN, the long chain alkyldimethyl amines marketed under the tradename ARMEEN and the ethoxylated amines marketed under the tradename ETHOMEEN. The most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1- decylamine, 1-dodecylamine. Especially desirable for odor characteristics are n-dodecyldimethylamine (ARMEEN DM12D) and bishydroxyethylcoconutalkylamine (ETHOMEEN C/12, BEROL 307)and oleylamine 7 times ethoxylated(BEROL 28), lauryl amido propylamine and coco amido propylamine.
While not intending to be limited by theory, it is believed that the amine cosurfactant and anionic surfactant herein form complexes which enhance packing of the surfactants at the oil/water interface, thereby lowering interfacial tension and improving detergency. The amine surfactants would be at least partially protonated in the product and during the wash thus can form positively charged species capable of complexing with the anionic surfactant.
Another aspect of the invention relates to the surprising finding that low amounts of certain primary and/or tertiary amines of the present invention provide suds control to the detergent compositions formulated therewith.
The amounts in which the amines are used for controlling the suds are from 0.1 to 10%, preferably from 0.1 to 5%, most preferably from 0.5 to 4% by weight of the detergent composition.
Detergent ingredients
In another embodiment of the present invention, a liquid detergent composition is provided 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. The detergent compositions according to the present invention will preferably comprise a surfactant system which is substantially free of linear alkylbenzene sulfonate surfactant.
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.
Other suitable anionic surfactants that can 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 :
R3 - CH(S03M) - C(O) - OR4
wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a Cχ-Cg 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 Cio-Cig alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is Cιo-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, c8~c22 primary of secondary alkanesulfonates, Cθ~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 oleoyl 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 Ci2~c18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Ci2 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(CH2CH2θ) jζ-CH2C00- M+ wherein R is a Cg-C22 alkyl, k is an integer from 0 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 Cτ.2" C 5 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 (CnH2n0)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.
Very suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula
R2 - C(O) - NtR1) - Z, wherein R1 is H, or R1 is Cι_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 C ι_i5 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.
Highly preferred nonionics are amine oxide surfactants. The compositions of the present invention may comprise amine oxide in accordance with the general formula I:
1 R (EO) (PO) (BO) N(0) (CH R') .qH 0 (I) x y z 2 2 2 In general, it can be seen that the structure (I) provides one long-chain moiety R (EO) (PO) (BO) and two
X V z short chain moieties, CH R' . R' is preferably selected from hydrogen, methyl and -CH2OH. In general R1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R is a primary alkyl moiety. When x+y+z = 0, R is a hydrocarbyl moiety having chainlength of from about 8 to about 18. When x+y+z is different from 0, R may be somewhat longer, having a chainlength in the range c12~c24- The general formula also encompasses amine oxides wherein x+y+z = 0, Ri = Cg-Ciβ, R' = H and q = 0-2, preferably 2. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide,hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and
5,071,594, incorporated herein by reference.
The invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points
in the range 30°C to 90°C. Amine oxides suitable for use herein are - made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers. Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
Preferred embodiments include hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, and tetradecyldimethylamine oxide dihydrate.
Whereas in certain of the preferred embodiments R1 = H, there is some latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments wherein R' = CH OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2- hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
When included therein, the laundry detergent compositions of the present invention typically comprise nonionic surfactants in the weight ratio of anionic surfactant to nonionic surfactant from 6:1 to 1:3, preferably from 5:1 to 2:1.
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 :
[R2 (OR3)y] [R (OR3)y]2R5N+X~
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3>-, -CH2CH(CH2θH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is
selected from the group consisting of C1-C alkyl, C1-C hydroxyalkyl-, benzyl ring structures formed by joining the two R4 groups, -CH2CHOH-CHOHCOR6CHOHCH2OH wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
RlR2R3R4N+x" (i)
wherein R^ is Cg-Cig alkyl, each of R2, R3 and R4 is independently C1-C alkyl, C1-C hydroxy alkyl, benzyl, and - (C2H4θ)xH where x has a value from 1 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl.
The preferred alkyl chain length for R^ is Ci2~ i5 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 R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide;
Ci2-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein Rx is -CH2-
O-C(O)-C12--14 alkyl and R2R3R4 are methyl).
Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
When included therein, the laundry detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of such cationic surfactants.
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 succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
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. The preferred unsaturated fatty acid is oleic acid.
Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
Detergency builder salts are normally included in amounts of from 3% to 50% by weight of the composition preferably from 5% to 30% and most usually from 5% to 25% by weight.
Other components used in detergent compositions may be employed, such as enzymes and stabilizers therefore, soil- suspending agents, soil-release polymers, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes.
Preferably, the liquid compositions according to the present invention are in "concentrated form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. The level of water is less than 50%, preferably less than 30%, more preferably less than 20% of water by weight of the detergent compositons.
Said concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs.
The liquid compositions are especially effective when applied directly to soils and stains in a pretreatment step. 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, skin etc., for example hard surface cleaning compositions(with or without abrasives) , laundry detergent compositions, automatic and non- automatic dishwashing compositions.
The following examples are meant to exemplify compositions of the present inventions, but are not necessarily meant to limit the scope of the invention.
EXAMPLE I
The following liquid detergent compositions are made % by weight of the detergent compositions
A B C D c12~c15 Alkyl ethoxylated sulfate 21 11.0 17 16. Octylamine 0.. 1 0. 0. c12~c14 alkyldimethyl amine oxide 3 2 12"c15 Alkyl sulfate 5 17.0 10 c12~c14 N-methyl glucamide 5 5.0 4.0 5 c12~c14 fatty alcohol ethoxylate 1 1 1 1 c12~c16 Fatty acid 7 7 4 6 Citric acid anhydrous 4.5 4.5 3 4 Diethylene triamine penta methy¬ lene phosphonic acid 1.0 1.0 2.0 2. Monoethanolamine 8 8 0.5 9 Sodiumhydroxide 1 1 2.5 1 Propanediol 12.7 14.5 13.1 10. Ethanol 1.8 1.8 4.7 5.
Amylase (300KNU/g) 0.1 0.1 0.1 0.1 Lipolase (lOOKNU/g) 0.15 0.15 0.15 0.15 Protease (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 0.3 Boric acid 2.4 2.4 2 2.8
Sodium xylene sulfonate 3 DC 3225C 03 0.04 0, 03 0.04 2-butyl-octanol 03 0.04 0, 04 0.03 Branched silicone ,3 0.3 0, 3 0.3 Water & Minors -up to 100%-
The above liquid detergent compositions (A-D) are found to be very efficient in the removal of greasy/oily soils under various usage conditions while having a controlled suds profile. The same results were obtained when octylamine was replaced in Compositions (A-D) by Bis (2-hydroxyethyl) coco amine, Oleyl amine 7EO, lauryl amido propylamine and coco amido propylamine.
Claims
1. A liquid detergent compositions comprising anionic surfactants selected from the group of alkyl alkoxy sulfates and alkyl sulfates, characterized in that said detergent composition further comprises an amine selected from i) primary amines having the formula R1R2R3N wherein R^ and R2 are both H ; and wherein R3 is C4-C18 or R4X(CH2)n whereby X is -0-, -C(0)NH- or -NH-/ R4 is a C4-C18, n is between 1 to 5; ii) tertiary amines having the formula R1R2R3N wherein neither Rl nor R2 is H, RI and R2 are Ci-Cg alkylchains or
whereby n is between 1 to 5 and x is between 1 to 5, R3 is either C4-C18 °~ 4X(CH2)n whereby X is -0-, -C(0)NH- or -NH-^4 is a C -Cig, n is between 1 to 5, and R5 is H or Cχ-C.2 alkyl; and; iii) mixtures of said primary and tertiary amines.
2. A liquid detergent composition acording to claim 2 wherein said primary amine is selected from n-alkylamines, 8-C14 alkyl amidopropyl amines, χo~c12 alkyl propylene diamines, and C8-C12 alkyl oxypropyl amines..
3. A liquid detergent composition according to claim 2 wherein said n-alkylamine is 1-octylamine.
4. A liquid detergent composition according to claim 1 wherein the amine is selected from the tertiary amine wherein R]_, R2
are both whereby n is between 1 to 5 and x is between 1 to 5 and wherein R3 is C -C18 alkyl chain and wherein R5 is H or CH3.
5. A liquid detergent composition according to Claim 1 wherein the amine is a tertiary amine selected from C -C12 alkyl dimethyl amines and amines of the formula wherein R4 is Cg-Cj2 aMcyl and n is 2 or 3.
6. A liquid detergent composition according to claims 1-5 wherein the weight ratio of the primary or/and tertiary amine to the alkyl alkoxylated sulfates and alkyl sulfates is from 1:1 to 1:250, more preferably from 1:5 to 1:100 and most preferably from 1:10 to 1:40.
7. A liquid detergent composition according to Claim 6 wherein the anionic surfactants are selected from the alkyl ethoxylated sulfate and Ci2~ci5 alkyl sulfate.
8. A liquid detergent composition according to Claims 1-7 further comprising a nonionic surfactant selected from the polyhydroxy fatty acid amides and/or amine oxides.
9. A liquid detergent composition according to claim 8 wherein said amine oxide is Ci2~c14 alkyl dimethyl amine oxide.
10. A liquid detergent composition according to Claims 1-9 further comprising other surfactants, builders, enzymes and other conventional detergent ingredients.
11. A liquid detergent composition according to Claims 1-10 which is free of linear alkylbenzene sulfonate surfactant.
12. Use of the primary amines and/or tertiary amines as defined in claims 1-5 in detergent compositions for the controlling of suds
13. Use of a liquid detergent composition according to Claims 1-11 for pretreatment of fabrics.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1994/011779 WO1996012000A1 (en) | 1994-10-13 | 1994-10-13 | Detergent compositions containing amines and anionic surfactants |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0785978A1 true EP0785978A1 (en) | 1997-07-30 |
Family
ID=22243129
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95904050A Withdrawn EP0785978A1 (en) | 1994-10-13 | 1994-10-13 | Detergent compositions containing amines and anionic surfactants |
EP95924620A Withdrawn EP0833884A1 (en) | 1994-10-13 | 1995-06-20 | Detergent compositions containing amines and anionic surfactants |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95924620A Withdrawn EP0833884A1 (en) | 1994-10-13 | 1995-06-20 | Detergent compositions containing amines and anionic surfactants |
Country Status (9)
Country | Link |
---|---|
EP (2) | EP0785978A1 (en) |
JP (2) | JP4063866B2 (en) |
AU (2) | AU1288195A (en) |
BR (2) | BR9408622A (en) |
CA (2) | CA2202506C (en) |
CZ (2) | CZ111097A3 (en) |
HU (1) | HUT78084A (en) |
TR (2) | TR199501261A2 (en) |
WO (1) | WO1996012000A1 (en) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE185592T1 (en) * | 1995-03-01 | 1999-10-15 | Weigert Chem Fab | CLEANING PRODUCTS FOR SURGICAL INSTRUMENTS |
AR003725A1 (en) * | 1995-09-29 | 1998-09-09 | Procter & Gamble | LIQUID DETERGENT COMPOSITIONS CONTAINING AN AMINE, ALKYL SULPHATE AND ADDITIONAL ANIONIC SURFACTANT. |
DE19646587A1 (en) * | 1996-11-12 | 1998-05-14 | Clariant Gmbh | New fatty alcohol sulfates and alkyl ether sulfates with trialkylammonium counterions and their preparation and use |
WO1998029527A1 (en) * | 1996-12-31 | 1998-07-09 | The Procter & Gamble Company | Thickened, highly aqueous liquid detergent compositions |
US5916575A (en) * | 1997-01-27 | 1999-06-29 | The Procter & Gamble Company | Cleaning products |
US6740627B1 (en) | 1999-02-08 | 2004-05-25 | The Procter & Gamble Company | Diols and polymeric glycols in dishwashing detergent compositions |
AR017744A1 (en) * | 1999-02-08 | 2001-09-12 | Procter & Gamble | POLYMERIC GLYCOLS AND DIOLES FOR IMPROVED DETERGENT COMPOSITIONS FOR THE WASHING OF VAJILLA |
AR017746A1 (en) * | 1999-09-16 | 2001-09-12 | Procter & Gamble | DETERGENT COMPOSITIONS FOR WASHING DISHES CONTAINING COLOR STABILIZING PHOSPHONATES |
DE10045289A1 (en) * | 2000-09-13 | 2002-03-28 | Henkel Kgaa | Fast-drying detergent and cleaning agent, especially hand dishwashing liquid |
EP1354872A1 (en) | 2002-04-17 | 2003-10-22 | Kao Corporation | Sulfuric acid ester amine salts, sulfonic acid amine salts, production thereof and softener composition |
JP5396707B2 (en) * | 2007-11-07 | 2014-01-22 | ライオンハイジーン株式会社 | Cleaning composition |
WO2010057973A1 (en) * | 2008-11-21 | 2010-05-27 | Thermphos Trading Gmbh | Solid surface treatment composition containing amine neutralized phosphonate |
WO2010057976A1 (en) * | 2008-11-21 | 2010-05-27 | Thermphos Trading Gmbh | Liquid surface treatment composition with phosphonic acid derivatives neutralized with a binary amine system |
US7723281B1 (en) * | 2009-01-20 | 2010-05-25 | Ecolab Inc. | Stable aqueous antimicrobial enzyme compositions comprising a tertiary amine antimicrobial |
JP6097639B2 (en) * | 2013-06-10 | 2017-03-15 | 株式会社Adeka | Cleaning composition and method of using the same |
JP6118663B2 (en) * | 2013-06-28 | 2017-04-19 | ライオン株式会社 | Dishwasher cleaner |
JP6118664B2 (en) * | 2013-06-28 | 2017-04-19 | ライオン株式会社 | Liquid detergent for dishwashers |
JP6118660B2 (en) * | 2013-06-28 | 2017-04-19 | ライオン株式会社 | Dishwasher cleaner |
JP6118662B2 (en) * | 2013-06-28 | 2017-04-19 | ライオン株式会社 | Liquid detergent for dishwashers |
KR101859464B1 (en) * | 2013-06-28 | 2018-05-21 | 라이온 가부시키가이샤 | Detergent for dishwasher |
JP6238451B2 (en) * | 2014-04-16 | 2017-11-29 | ライオン株式会社 | Liquid detergent for textile products |
US11591546B2 (en) | 2017-01-20 | 2023-02-28 | Ecolab Usa Inc. | Cleaning compositions employing extended chain anionic surfactants |
CN110573602B (en) | 2017-06-26 | 2021-11-12 | 花王株式会社 | Liquid detergent composition for hard surface |
DE102017223459A1 (en) * | 2017-12-20 | 2019-06-27 | Henkel Ag & Co. Kgaa | Detergent containing amine oxide and sugar surfactants |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU5503373A (en) * | 1972-06-06 | 1974-11-07 | Colgate Palmolive Co | Low-foaming detergent composition |
GB1375639A (en) * | 1973-07-24 | 1974-11-27 | ||
DE2648304A1 (en) * | 1975-10-31 | 1977-05-05 | Procter & Gamble Europ | LIQUID DETERGENT |
EP0203660B1 (en) * | 1985-05-28 | 1989-01-04 | Unilever N.V. | Liquid cleaning and softening compositions |
-
1994
- 1994-10-13 WO PCT/US1994/011779 patent/WO1996012000A1/en not_active Application Discontinuation
- 1994-10-13 CA CA002202506A patent/CA2202506C/en not_active Expired - Fee Related
- 1994-10-13 BR BR9408622A patent/BR9408622A/en not_active IP Right Cessation
- 1994-10-13 JP JP51317696A patent/JP4063866B2/en not_active Expired - Lifetime
- 1994-10-13 CZ CZ971110A patent/CZ111097A3/en unknown
- 1994-10-13 AU AU12881/95A patent/AU1288195A/en not_active Abandoned
- 1994-10-13 EP EP95904050A patent/EP0785978A1/en not_active Withdrawn
-
1995
- 1995-06-20 EP EP95924620A patent/EP0833884A1/en not_active Withdrawn
- 1995-09-29 CA CA002202505A patent/CA2202505C/en not_active Expired - Fee Related
- 1995-09-29 AU AU36869/95A patent/AU3686995A/en not_active Abandoned
- 1995-09-29 JP JP8513248A patent/JPH10509468A/en active Pending
- 1995-09-29 HU HU9901140A patent/HUT78084A/en unknown
- 1995-09-29 CZ CZ971109A patent/CZ110997A3/en unknown
- 1995-09-29 BR BR9509349A patent/BR9509349A/en not_active IP Right Cessation
- 1995-10-13 TR TR95/01261A patent/TR199501261A2/en unknown
- 1995-10-13 TR TR95/01262A patent/TR199501262A2/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9612000A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU3686995A (en) | 1996-05-06 |
AU1288195A (en) | 1996-05-06 |
WO1996012000A1 (en) | 1996-04-25 |
CA2202505C (en) | 2001-02-06 |
HUT78084A (en) | 1999-08-30 |
JPH10509468A (en) | 1998-09-14 |
CZ111097A3 (en) | 1997-09-17 |
TR199501262A2 (en) | 1996-06-21 |
EP0833884A1 (en) | 1998-04-08 |
TR199501261A2 (en) | 1996-06-21 |
CA2202506C (en) | 2001-02-13 |
CA2202505A1 (en) | 1996-04-25 |
JP4063866B2 (en) | 2008-03-19 |
BR9509349A (en) | 1997-11-25 |
JPH10507469A (en) | 1998-07-21 |
CZ110997A3 (en) | 1997-09-17 |
BR9408622A (en) | 1997-09-16 |
CA2202506A1 (en) | 1996-04-25 |
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