EP0704523A1 - Betain enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung - Google Patents

Betain enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung Download PDF

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Publication number
EP0704523A1
EP0704523A1 EP94202828A EP94202828A EP0704523A1 EP 0704523 A1 EP0704523 A1 EP 0704523A1 EP 94202828 A EP94202828 A EP 94202828A EP 94202828 A EP94202828 A EP 94202828A EP 0704523 A1 EP0704523 A1 EP 0704523A1
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EP
European Patent Office
Prior art keywords
dye transfer
alkyl
transfer inhibiting
oxide
composition according
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.)
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Application number
EP94202828A
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English (en)
French (fr)
Inventor
Abdennaceur Fredj (Nmn)
Gregory Bruce Huntington
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP94202828A priority Critical patent/EP0704523A1/de
Priority to PCT/US1995/011178 priority patent/WO1996010621A1/en
Priority to JP8511774A priority patent/JPH10506664A/ja
Priority to MX9702354A priority patent/MX9702354A/es
Publication of EP0704523A1 publication Critical patent/EP0704523A1/de
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/90Betaines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/28Heterocyclic compounds containing nitrogen in the ring
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3792Amine oxide containing polymers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • C11D3/42Brightening agents ; Blueing agents

Definitions

  • the present invention relates to a composition and a process for inhibiting dye transfer between fabrics during washing. More in particular, the present invention relates to dye transfer inhibiting compositions comprising dye transfer inhibiting agents and betaine surfactants.
  • Dye transfer inhibiting agents have been used within detergent compositions to inhibit dye transfer. Examples of said polymers are described in prior art documents such as DE 2 814 287-A which relates to detergent compositions comprising 0.1 to 10 wt% water-soluble or water-dispersible N-vinyl imidazole homo- or copolymer in combination with anionic and/or nonionic surfactants and other detergent ingredients.
  • EP 372 291 relates to a process for washing discolouration-sensitive textiles.
  • the wash liquor contains anionic/nonionic surfactants and watersoluble polymers e.g. (co)polymers N-vinylimidazole, N-vinyloxazolidone or N-vinylpyrrolidone.
  • EP 327 927 describes a granular detergent additive comprising water-soluble polymeric compounds based on N-vinylpyrrolidone and/or N-vinylimidazole and/or N-vinyloxazolidone and cationic compounds.
  • DE 4027832-A discloses electrolyte-free liquid detergent compositions comprising zeolite A, nonionic surfactants and dye transfer inhibiting polymers.
  • the dye transfer inhibiting polymers are homo-and copolymers selected from N-vinylpyrrolidone and/or N-vinylimidazole and/or N-vinyloxazolidone.
  • Copending European Patent Application No. 92202168.8 describes polyamine N-oxide containing polymers which are very efficient in eliminating transfer of solubilized or suspended dyes.
  • dye transfer inhibiting agents are very compatible with surfactant systems containing betaines.
  • dye transfer inhibiting performance of the dye transfer inhibiting agents has been increased in the presence of said betaines.
  • liquid dye transfer inhibiting compositions of the present invention are very useful when the liquid detergent compositions are in direct contact with the fabrics such as during pretreatment. These compositions also provide excellent skin mildness for hand-wash operations.
  • a process is also provided for laundering operations involving colored fabrics.
  • the present invention relates to dye transfer inhibiting compositions containing one or more of a betaine surfactant and a dye transfer inhibiting agent.
  • the weight ratio of the betaine surfactant to the dye transfer inhibiting agent is from 5000:1 to 2:1, more preferably from 1000:1 to 3:1 and most preferably from 500:1 to 4:1.
  • the detergent compositions according to the present invention comprise a betaine surfactant, present in an amount of from 0.25% to 40%, more preferably from 0.5% to 30% and most preferably from 1% to 15% by weight of the compositions.
  • the betaine surfactant has the general formula : wherein R1 is C8-C18 alkyl R2 and R3 are C1-C5 alkyl, C1-C5 alcohol or H. R4 is C1-C5 alkyl or C1-C5 alcohol. Y is n&m are 0 or 1 X- is CH2COO- or SO3-.
  • R1 has an average carbon chain length of from 12 to 14 carbon atoms and may be derived from synthetic sources, in which case the chain length may incorporate some branching, or from natural fats and oils, in which case the chains are linear and may include minor amounts of C8-C10 and C14-C18 moieties.
  • Synthetic sources for the R1 group may be the same as those mentioned previously for the alkyl group in the alkyl sulphate component.
  • compositions incorporating the C12-C14 amido betaine and C12-C14 sulpho betaine display the benefits of the invention, the most preferred compositions utilise a C12-C14 alkyl betaine as the zwitterionic surfactant component, the C12-C14 alkyl group being derived from a coconut or palm kernel oil feedstock.
  • the dye transfer inhibiting compositions according to the present invention comprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of a dye transfer inhibiting agent.
  • Said dye transfer inhibiting agents are normally incorporated into detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith.
  • Especially suitable dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones, polyvinylimidazoles, brighteners, metallo catalysts or mixtures thereof.
  • the polyamine N-oxide polymers suitable for use contain units having the following structure formula : R - A x - P (I) wherein P is a polymerisable unit, whereto the R-N-O group can be attached to or wherein the R-N-O group forms part of the polymerisable unit or a combination of both.
  • A is NC(O), C(O)O, C(O), -O-,-S-, -N ⁇ ;
  • x is O or 1;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures : wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
  • polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups.
  • polyamine oxides wherein R groups can be aromatic such as phenyl.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
  • the amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000.
  • the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation.
  • the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000.
  • the polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
  • the amine oxide unit of the polyamine N-oxides has a PKa ⁇ 10, preferably PKa ⁇ 7, more preferred PKa ⁇ 6.
  • the polyamine oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
  • the N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1,000,000, preferably from 20,000-200,000.
  • Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.
  • the average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113, "Modern Methods of Polymer Characterization".
  • N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 10,000 to 20,000.
  • N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith.
  • the N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
  • the detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP" having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • PVP K-15 is also available from ISP Corporation.
  • polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • the detergent compositions of the present invention may also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent.
  • Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • the detergent compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles have an average about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • the detergent compositions herein may also contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino , morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • R1 is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R1 is anilino
  • R2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R1 is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradesman Tinopal AMS-GX by Ciba Geigy Corporation.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • Metallo-catalysts can be used in the compositions according to the present invention.
  • Metallo-catalysts are disclosed for use as dye transfer inhibiting agents in copending European Patent Application 93870149.7 and 94870078.6.
  • Preferred metallo-catalysts herein include the manganese-based metallo-catalysts.
  • 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.
  • 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 C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component,
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (C12-C18E(1.0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (C12-C18E(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (C12-C18E(3.0)M), and C12-C18 alkyl polyethoxylate (4.0) sulfate (C12-C18E(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 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(SO3M) - C(O) - OR4 wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R3 is C10-C16 alkyl
  • R4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R3 is C10-C16 alkyl.
  • alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.
  • alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
  • alkyl chains of C12-C16 are preferred for lower wash temperatures (e.g. below about 50°C) and C16 ⁇ 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, C9-C20 linear alkylbenzenesulfonates, C8-C22 primary of secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of
  • 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 Igepal TM CO-630, marketed by the GAF Corporation; and Triton TM 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 Tergitol TM 15-S-9 (the condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide), Tergitol TM 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol TM 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol TM 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol TM 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol TM 45-4 (the condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide) marketed by Shell Chemical Company, and Kyro TM EOB (the condensation product of C13-C15 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 R2O(C n H 2n O) t (glycosyl) x wherein R2 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 Pluronic TM 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 Tetronic TM 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 C8-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C8-C18 alcohol ethoxylates (preferably C10 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 R2 - C(O) - N(R1) - Z, wherein R1 is H, or R1 is C1 ⁇ 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5 ⁇ 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R1 is methyl
  • R2 is a straight C11 ⁇ 15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • the 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 cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as nonionic surfactants other than those already described herein.
  • Preferred cationic surfactant systems include nonionic and ampholytic surfactants.
  • 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 ][R4(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(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzy
  • Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula : R1R2R3R4N+X ⁇ (i) wherein R1 is C8-C16 alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and - (C2H40) x H where x has a value from 2 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 R1 is C12-C15 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.
  • 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; C12 ⁇ 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 R1 is -CH2-O-C(O)-C12 ⁇ 14 alkyl and R2R3R4 are methyl).
  • 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 R3(OR4) x N(O)(R5)2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R4 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 R5 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 R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C10-C18 alkyl dimethyl amine oxides and C8-C12 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 builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2O5).
  • Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane -hexacarboxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivatives disclosed in British Patent No. 1,425,343.
  • Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (sks/6), and a water-soluble carboxylate chelating agent such as citric acid.
  • a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (sks/6)
  • a water-soluble carboxylate chelating agent such as citric acid.
  • a suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
  • suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well 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.
  • Preferred builder systems for use in granular compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
  • builder materials that can form part of the builder system for use in granular compositions the purposes of the invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amiono polyalkylene phosphonates and amino polycarboxylates.
  • inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amiono polyalkylene phosphonates and amino polycarboxylates.
  • organic materials such as the organic phosphonates, amiono polyalkylene phosphonates and amino polycarboxylates.
  • suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of this type are disclosed in GB-A-1,596,756.
  • Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • 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 ingredients that can be included in the detergent compositions of the present invention include bleaching agents.
  • bleaching agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one or more bleach activators.
  • bleaching compounds will typically be present at levels of from about 1% to about 10%, of the detergent composition.
  • bleaching compounds are optional components in non-liquid formulations, e.g. granular detergents. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition.
  • the bleaching agent component for use herein can be any of the bleaching agents useful for detergent compositions including oxygen bleaches as well as others known in the art.
  • this invention further provides a method for cleaning fabrics, fibers, textiles, at temperatures below about 50°C, especially below about 40°C, with a detergent composition containing polyamine N-oxide containing polymers, optional auxiliary detersive surfactants, optional detersive adjunct ingredients, and a bleaching agent.
  • the bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.
  • oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551.
  • bleaching agents that can be used encompasses the halogen bleaching agents.
  • hypohalite bleaching agents include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1-5% by weight.
  • the bleaches suitable for the present invention include peroxygen bleaches.
  • suitable water-soluble solid peroxygen bleaches include hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and peroxyhydrates.
  • Preferred bleaches are percarbonates and perborates.
  • the hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.
  • bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as the
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
  • peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
  • Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718.
  • detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.
  • detergent ingredients that can be included are detersive enzymes which can be included in the detergent formulations for a wide variety of purposes including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of active enzyme per gram of the composition.
  • proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms.
  • proteases suitable for removing protein-based stains that are commercially available include those sold under the tradenames Alcalase , Savinase and Esperase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands) and FN-base by Genencor, Optimase and opticlean by MKC.
  • Protease A is described in European Patent Application 130,756.
  • Protease B is described in European Patent Application Serial No. 87303761.8.
  • Protease C is a variant of an alkaline serine protease from Bacillus , particularly Bacillus lentus , in which arginine replaced lysine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274.
  • Protease C is described in EP 90915958:4; U.S.
  • protease which are described in copending application U.S. Serial No. 08/136,797, entitled Protease-containing Cleaning Compositions and copending Application U.S. Serial No. 08/136,626, entitled Bleaching Compositions Comprising Protease Enzymes, which are incorporated herein by reference.
  • Genetically modified variants, particularly of Protease C, are also included herein.
  • Amylases include, for example, -amylases obtained from a special strain of B.licheniforms, described in more detail in British Patent Specification No. 1,296,839 (Novo).
  • Amylolytic proteins include, for example, Rapidase, Maxamyl (International Bio-Synthetics, Inc.) and Termamyl, (Novo Industries).
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028 ; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).
  • Other suitable cellulases are cellulases originated from Humicola Insulens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids. Such cellulase are described in Copending European patent application No. 93200811.3, filed March 19, 1993.
  • Especially suitable cellulase are the cellulase having color care benefits.
  • Examples of such cellulases are cellulase described in European patent application No. 91202879.2, filed November 6, 1991 Carezyme (Novo).
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunoligical cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • Lipase such as M1 Lipase (Ibis) and Lipolase (Novo).
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes of pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT Internation Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.
  • an enzyme stabilization system is preferably utilized.
  • Enzyme stabilization techniques for aqueous detergent compositions are well known in the art.
  • one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate and calcium propionate.
  • Calcium ions can be used in combination with short chain carboxylic acid salts, preferably formates. See, for example, U.S. patent 4,318,818. It has also been proposed to use polyols like glycerol and sorbitol.
  • Alkoxy-alcohols dialkylglycoethers, mixtures of polyvalent alcohols with polyfunctional aliphatic amines (e.g., such as diethanolamine, triethanolamine, di-isopropanolamime, etc.), and boric acid or alkali metal borate.
  • Enzyme stabilization techniques are additionally disclosed and exemplified in U.S. patent 4,261,868, U.S. Patent 3,600,319, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5.
  • Non-boric acid and borate stabilizers are preferred.
  • Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319 and 3,519,570.
  • enzyme oxidation scavengers which are described in Copending European Patent aplication N 92870018.6 filed on January 31, 1992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a suds suppressor exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672.
  • Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published April 28, 1977.
  • An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer.
  • Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl-alcanols are 2-butyl-octanol which are commercially available under the trade name Isofol 12 R.
  • compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as Aerosil R .
  • the suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
  • detergent compositions may be employed, such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents and/or encapsulated or more encapsulated perfumes.
  • Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts.
  • Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4,41-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:21 disulphonate, disodium 4, - 41-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:21 - disulphonate, disodium 4,41 - bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:21 - disulphonate, monosodium 41,411 -bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,41 -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,21 - disulphonate, disodium 4,41
  • molecular weight 1000-10000 more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight.
  • These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033.
  • a particular preferred polymer in accordance with EP-A-0 272 033 has the formula (CH3(PEG)43) 0.75 (POH) 0.25 [T-PO) 2.8 (T-PEG) 0.4 ]T(PO- H) 0.25 ((PEG)43CH3) 0.75 where PEG is -(OC2H4)O-,PO is (OC3H6O) and T is (pcOC6H4CO).
  • modified polyesters as random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol.
  • the target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups.
  • some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist “secondarily” of such species.
  • the selected polyesters herein contain about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000.
  • the polyesters and their method of preparation are described in detail in EPA 311 342.
  • the detergent compositions according to the invention can be in liquid, paste, gels, bars or granular forms.
  • Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. greater than about 600 g/l; in such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.
  • 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 amound 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 present invention also relates to a process for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
  • the process comprises contacting fabrics with a laundering solution as hereinbefore described.
  • the process of the invention is conveniently carried out in the course of the washing process.
  • the washing process is preferably carried out at 5 °C to 75 °C, especially 20 to 60, but the polymers are effective at up to 95°C and higher temperatures.
  • the pH of the treatment solution is preferably from 6 to 11, especially from 7.0 to 10.5.
  • compositions of the 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 substrates, such as fabrics, fibers, skin etc., for example laundry detergent compositions, automatic and non automatic dishwashing compositions.
  • a liquid detergent composition according to the present invention is prepared, having the following compositions :
  • the extent of dye transfer from different colored fabrics is studied using a launder-o-meter test that simulates a 30 min wash cycle.
  • the launder-o-meter beaker contains 200 ml of a detergent solution, a 10cmx10cm piece of the colored fabric and a multifiber swatch which is used as a pick-up tracer for the bleeding dye.
  • the multifiber swatch consists of 6 pieces (1.5cmx5cm each) of different material (polyacetate, cotton, polyamide, polyester, wool and orlon) which are sewn together.
  • the extent of dye transfer is assessed by a Hunter Colour measurement.
  • the Hunter Colour system evaluates the colour of a fabric sample in terms of the DE value which represents the change in the Hunter L, a, b , values which are determined by reflecting spectrometrie.
  • %DTI percent dye transfer inhibition
  • %DTI DE o (no DTI agent) - DE 1 (+DTI agent) DE o (no DTI agent) x 100
  • Example 1 demonstrates the enhanced dye transfer inhibiting performance of the polyamine N-oxide polymers in the presence of coco dimethyl betaine surfactant in comparison with alkyl sulfate.
  • a liquid detergent composition according to the present invention is prepared, having the following compositions : % by weight of the total detergent composition A B C Betaine 4 6 9 Linear alkylbenzene sulfonate 10 - - Alkyl alkoxylated sulfate - 9 - Polyhydroxy fatty acid - - 9 Trimethyl ammonium chloride C12-C14 - - 4 Alkyl sulphate 4 4 4 Fatty alcohol (C12-C15) ethoxylate 12 12 12 Fatty acid 10 10 10 10 Oleic acid 4 4 4 Citric acid 1 1 1 1 Diethylenetriaminepentamethylene Phosphonic acid 1.5 1.5 1.5 NaOH 3.4 3.4 3.4 Propanediol 1.5 1.5 1.5 Ethanol 10 10 10 Ethoxylated tetraethylene pentamine 0.7 0.7 0.7 Poly(4-vinylpyridine)-N-oxide 0-1 0-1 0-1 Thermamyl R 300 KNU/g 0.13 0.13 0.13 Carezyme
  • a compact granular detergent composition according to the present invention is prepared, having the following formulation: % by weight of the total detergent composition A B C Betaine 2 4 8 Linear alkyl benzene sulphonate 11.40 - - Alkyl alkoxylated sulfate - 10 - Polyhydroxy fatty acid - - 9 Trimethyl ammonium chloride C12-C14 - - 4 Tallow alkyl sulphate 1.80 1.80 1.80 C45 alkyl sulphate 3.00 3.00 3.00 C45 alcohol 7 times ethoxylated 4.00 4.00 4.00 Tallow alcohol 11 times ethoxylated 1.80 1.80 1.80 Dispersant 0.07 0.07 0.07 Silicone fluid 0.80 0.80 0.80 Trisodium citrate 14.00 14.00 14.00 Citric acid 3.00 3.00 3.00 3.00 Zeolite 32.50 32.50 32.50 Maleic acid actylic acid copolymer 5.00 5.00 Cellulase (active protein) 0.03 0.03 0.03 Protease 0.60
  • compositions are very good at displaying excellent detergent performance with outstanding color-care performance on colored fabrics and mixed loads of colored and white fabrics.
  • This Example illustrates laundry bars in accordance with the invention.
  • the laundry bars exemplified herein are prepared by standard extrusion processes so as to be suitable for handwashing soiled fabrics.
  • Table III sets forth the various ingredients in the laundry bars.
  • TABLE III Component (% Weight) A B C12 ⁇ 18 alkyl ethoxy (0.6) sulfate 10.1 8.9 Neodol 23-91 0.5 0.4 Neodol 23-32 0.5 0.4 C12 ⁇ 14 N-methyl glucamide 0.9 0.8 Betaine 5.7 5.0

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP94202828A 1994-09-30 1994-09-30 Betain enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung Withdrawn EP0704523A1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP94202828A EP0704523A1 (de) 1994-09-30 1994-09-30 Betain enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung
PCT/US1995/011178 WO1996010621A1 (en) 1994-09-30 1995-09-01 Dye transfer inhibiting compositions containing betaines
JP8511774A JPH10506664A (ja) 1994-09-30 1995-09-01 ベタインを含有する染料移動抑制組成物
MX9702354A MX9702354A (es) 1994-09-30 1995-09-01 Composiciones que inhiben la transferencia de colorante que contienen betainas.

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EP94202828A EP0704523A1 (de) 1994-09-30 1994-09-30 Betain enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung

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Cited By (11)

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WO1999033943A1 (en) * 1997-12-29 1999-07-08 Colgate-Palmolive Company Detergent composition having improved cleaning power
EP1023430A1 (de) * 1997-09-19 2000-08-02 Isp Investments Inc. Wasserlösliche farbstoff komplexierende polymere als farbstoffübertragungsinhibitoren in wäschewasch- und weichspülerzusammensetzungen
US6180593B1 (en) 1998-09-30 2001-01-30 Goldschmidt Rewo Gmbh & Co. Kg Fabric softeners with improved color-retaining action
WO2006042716A1 (de) 2004-10-20 2006-04-27 Clariant Produkte (Deutschland) Gmbh Flüssigwaschmittel enthaltend anionische tenside und farbfixiermittel
WO2006042717A1 (de) * 2004-10-20 2006-04-27 Clariant Produkte (Deutschland) Gmbh Flüssigwaschmittel anthaltend sekundäres alkansulfonat und farbfixiermittel
US7541326B2 (en) 2004-09-10 2009-06-02 Clariant Produkte (Deutschland) Gmbh Liquid washing agent containing a color fixing agent
US7541327B2 (en) 2004-10-23 2009-06-02 Clariant Produkte (Deutschland) Gmbh Liquid detergents containing colour fixing agents
US7585831B2 (en) 2004-10-23 2009-09-08 Clariant Produkte (Deutschland) Gmbh Liquid detergent comprising a dye fixing agent
WO2017129310A1 (de) * 2016-01-28 2017-08-03 Henkel Ag & Co. Kgaa C8-10-alkylamidoalkylbetain als antiknitterwirkstoff
WO2022162221A1 (en) * 2021-02-01 2022-08-04 Unilever Ip Holdings B.V. Detergent composition
WO2022162062A1 (en) * 2021-02-01 2022-08-04 Unilever Ip Holdings B.V. Detergent composition

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US6150324A (en) * 1997-01-13 2000-11-21 Ecolab, Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal

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EP0068232A2 (de) * 1981-06-19 1983-01-05 Henkel Kommanditgesellschaft auf Aktien Flüssiges Waschmittel mit Zusätzen zur Verhinderung der Farbstoffübertragung
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EP0538228A1 (de) * 1991-10-14 1993-04-21 The Procter & Gamble Company Waschmittelzusammensetzungen zur Vermeidung der Farbstoffübertragung
WO1994002580A1 (en) * 1992-07-15 1994-02-03 The Procter & Gamble Company Surfactant-containing dye transfer inhibiting compositions

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FR2144721A1 (de) * 1971-07-02 1973-02-16 Procter Gamble Europ
US4005029A (en) * 1973-08-01 1977-01-25 The Procter & Gamble Company Laundering adjunct
EP0068232A2 (de) * 1981-06-19 1983-01-05 Henkel Kommanditgesellschaft auf Aktien Flüssiges Waschmittel mit Zusätzen zur Verhinderung der Farbstoffübertragung
EP0090310A1 (de) * 1982-03-29 1983-10-05 Henkel Kommanditgesellschaft auf Aktien Mittel zum Waschen und färbungsschonenden Bleichen von Textilien
EP0538228A1 (de) * 1991-10-14 1993-04-21 The Procter & Gamble Company Waschmittelzusammensetzungen zur Vermeidung der Farbstoffübertragung
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1023430A1 (de) * 1997-09-19 2000-08-02 Isp Investments Inc. Wasserlösliche farbstoff komplexierende polymere als farbstoffübertragungsinhibitoren in wäschewasch- und weichspülerzusammensetzungen
EP1023430A4 (de) * 1997-09-19 2000-11-15 Isp Investments Inc Wasserlösliche farbstoff komplexierende polymere als farbstoffübertragungsinhibitoren in wäschewasch- und weichspülerzusammensetzungen
WO1999033943A1 (en) * 1997-12-29 1999-07-08 Colgate-Palmolive Company Detergent composition having improved cleaning power
US6180593B1 (en) 1998-09-30 2001-01-30 Goldschmidt Rewo Gmbh & Co. Kg Fabric softeners with improved color-retaining action
US7541326B2 (en) 2004-09-10 2009-06-02 Clariant Produkte (Deutschland) Gmbh Liquid washing agent containing a color fixing agent
WO2006042717A1 (de) * 2004-10-20 2006-04-27 Clariant Produkte (Deutschland) Gmbh Flüssigwaschmittel anthaltend sekundäres alkansulfonat und farbfixiermittel
WO2006042716A1 (de) 2004-10-20 2006-04-27 Clariant Produkte (Deutschland) Gmbh Flüssigwaschmittel enthaltend anionische tenside und farbfixiermittel
US7544652B2 (en) 2004-10-20 2009-06-09 Clariant Produkts (Deutschland) Gmbh Liquid detergent comprising anionic surfactants and colour fixing agent
US7541327B2 (en) 2004-10-23 2009-06-02 Clariant Produkte (Deutschland) Gmbh Liquid detergents containing colour fixing agents
US7585831B2 (en) 2004-10-23 2009-09-08 Clariant Produkte (Deutschland) Gmbh Liquid detergent comprising a dye fixing agent
WO2017129310A1 (de) * 2016-01-28 2017-08-03 Henkel Ag & Co. Kgaa C8-10-alkylamidoalkylbetain als antiknitterwirkstoff
WO2022162221A1 (en) * 2021-02-01 2022-08-04 Unilever Ip Holdings B.V. Detergent composition
WO2022162062A1 (en) * 2021-02-01 2022-08-04 Unilever Ip Holdings B.V. Detergent composition

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WO1996010621A1 (en) 1996-04-11
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