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WO1997005221A1 - Composition detergente - Google Patents

Composition detergente Download PDF

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Publication number
WO1997005221A1
WO1997005221A1 PCT/US1996/012503 US9612503W WO9705221A1 WO 1997005221 A1 WO1997005221 A1 WO 1997005221A1 US 9612503 W US9612503 W US 9612503W WO 9705221 A1 WO9705221 A1 WO 9705221A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent composition
composition according
zeolite
independently
alkyl
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.)
Ceased
Application number
PCT/US1996/012503
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English (en)
Inventor
Gerard Marcel Baillely
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of WO1997005221A1 publication Critical patent/WO1997005221A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • the present invention relates to a granular alkaline detergent composition
  • a granular alkaline detergent composition comprising a cationic ester surfactant and a zeolite component as a sequestering agent for water hardness.
  • water soluble inorganic phosphates such as sodium tripolyphosphate
  • sodium tripolyphosphate have been used as builders for laundry detergents.
  • alkali metal aluminosilicate ion-exchangers particularly crystalline water insoluble sodium aluminosilicate zeolites, have been proposed as replacements for the inorganic phosphates.
  • EP 21 491A (Procter & Gamble) discloses detergent compositions containing a builder system which includes zeolite A, X or P (B) or a mixture thereof.
  • EP 384070A (Unilever) discloses specific zeolite P materials having an especially low silicon to aluminium ratio not greater than 1.33 (hereinafter referred to as zeolite MAP) and describes their use as detergency builders.
  • Surfactant components have traditionally been employed in detergent products to facilitate the removal of greasy soils/stains.
  • surfactant systems comprising cationic esters have been found to be of utility in greasy soil/stain removal.
  • EP-B-21,491 discloses detergent compositions containing a nonionic cationic surfactant mixture and a builder mixture comprising aluminosilicate and polycarboxylate builder.
  • the cationic surfactant may be a cationic ester. Improved particulate and greasy/oily soil removal is described.
  • US-A-4,228,042 discloses biodegradable cationic surfactants, including cationic ester surfactants for use in detergent compositions to provide greasy/oily soil removal. The combination of these cationic surfactants with nonionic surfactants in compositions designed for particulate soil removal is also described. Anionic surfactants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic surfactant component.
  • US-A-4,239,660 discloses laundry detergent compositions containing cationic ester surfactant and nonionic surfactant at defined weight ratios and an alkalinity source. The alkalinity source enables a wash solution having a pH of from 8 to 10 to be formed within 3 minutes of dissolution of the composition in water at 100°F (37°C) at a solution concentration of 0.15%.
  • US-A-4, 260,529 discloses laundry detergent compositions having a pH of no greater than 11 containing cationic ester surfactant and nonionic surfactant at defined weight ratios.
  • Anionic surfactants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic surfactant component.
  • cationic ester surfactants in solid alkaline detergent products is the propensity for the surfactant to degrade on storage.
  • the cationic ester surfactant has a tendency to be hydrolysed, particularly when stored under conditions of high moisture and/or elevated temperatures.
  • zeolite MAP builder material into the composition together with the cationic ester surfactant.
  • crystalline layered silicate as a cobuilder has been found to further aid cationic ester storage stability.
  • the zeolite MAP builder and optionally any cobuilder are in close physical proximity, more preferably in intimate admixture within the composition.
  • zeolite builder comprising zeolite P having a silicon to aluminium ratio of not greater than 1.33 (zeolite MAP);
  • pH of a 1% solution of said composition measured at 20°C is greater than 9.25.
  • the cationic ester surfactant is selected from those having the formula:
  • R-j is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M".
  • X and Y independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group;
  • R2, R3, R , RQ, R7, and R ⁇ are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy- alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and
  • R5 is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20,
  • the first essential component of the present invention is a zeolite MAP builder, optionally in conjunction with one or more supplementary builders.
  • the zeolite MAP is typically present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • Zeolite P having a Si:AI ratio of 1.33 or less may be prepared by the following steps:
  • Preferred drying methods are spray-drying and flash drying. It appears that oven drying at too high a temperature may adversely affect the calcium binding capacity of the product under certain circumstances.
  • Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilcate, as measured by the standard method described in GB 1473201 (Henkel).
  • the calcium binding capacity is normally 160 mg CaO/g and may be as high 170 mg CaO/g.
  • zeolite MAP like other zeolites contains water of hydration
  • pu ⁇ oses of the present invention amounts and percentages of zeolite are expressed in terms of the notional anhydrous material.
  • the amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt.%.
  • the zeolite MAP detergent builder has a particle size, expressed as a dso value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the d5Q value indicates that 50% by weight of the particles have a diameter smaller than that figure.
  • the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing dso values are disclosed in EP 384070A.
  • the second essential element of the detergent compositions of the invention is a cationic ester surfactant. That is, a preferably water dispersible compound having surfactant properties comprising at least one hydrolysable ester (ie -COO-) linkage and at least one cationically charged group.
  • the cationic ester surfactant is present in amount from 0.1% to 90%, preferably from 0.5% to 40%, most preferably from 1% to 10% by weight of the detergent composition.
  • the weight ratio of zeolite MAP to cationic ester component is typically from 100:1 to 2:1, preferably from 50:1 to 3:1, most preferably from 30:1 to 4:1.
  • Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • Preferred water dispersible cationic ester surfactants are those having the formula:
  • is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M".
  • N + (R6R7R8)(CH2) S ; and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R ⁇ . R7.
  • R ⁇ are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy- alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1 ; and wherein M is a counter anion.
  • R2.R3 and R4 are independently selected from CH3 and -CH 2 CH 2 OH.
  • M is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or iodide.
  • Preferred water dispersible cationic ester surfactants are the choline esters having the formula:
  • R-j is a C ⁇
  • Particularly preferred choline esters of this type include the stearoyl choline
  • choline ester compounds among the above disclosed are cocoyi choline ester quaternary methylammonium halides.
  • the particularly preferred choline esters may be prepared by the direct esterification of a fatty acid or fatty acid mixture of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst.
  • the reaction product is then quaternized in a suitable solvent (e.g. water, ethanol, fatty acid) with a methyl halide, forming the desired cationic material.
  • a suitable solvent e.g. water, ethanol, fatty acid
  • They may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material.
  • the reaction product is then quaternized with trimethylamine, forming the desired cationic material.
  • Suitable cationic ester surfactants have the structural formulas below, wherein d may be from 0 to 20.
  • compositions have a pH measured as a 1 % solution in distilled water of at least 9.25, preferably from 10.0 to 12.5, most preferably from 10.5 to 12.0. Additional detergent components
  • the detergent composition according to the invention may contain other detergent components such as surfactants, cobuilders, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
  • other detergent components such as surfactants, cobuilders, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
  • the detergent composition according to the invention preferably includes an additional surfactant selected from anionics, nonionics, zwitterionics, ampholytics and non-cationic ester cationics.
  • the additional surfactant is preferably present in the detergent compositions at a level of from 1 % to 50%, preferably from 3% to 30%, most preferably from 5% to 20% by weight of the compositions.
  • Suitable additional anionic surfactants include anionic sulfates, olefin sulphonates, alkyl xylene sulphonates, dialkylsulphosuccinates, and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C-17 acyl-N-(C ⁇
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C ⁇ -Ci ⁇ alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C ⁇ -C-i ⁇ alkyl sulfate which has been ethoxylated with from 0.5 to 20, preferably from 0.5 to 5, moles of ethylene oxide per molecule.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C5-C22 primary or secondary alkane sulfonates, C5-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • alkoxylated nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of from 1 to 7 alkylene oxide groups per molecule.
  • the alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.
  • Preferred alkylene oxide adducts of fatty alcohols useful in the present invention can suitably be chosen from those of the general formula:
  • R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably from 10 to 22 carbon atoms, y is from 0.5 to 5 and n is 2 or 3.
  • Suitable nonionic surfactants include primary C11-C15 aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, preferably from 25% to less than 50% by weight.
  • a preferred aliphatic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.
  • alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-C15 alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.
  • Another class of nonionic sufactants 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 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • 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 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • the builder system may contain an organic or inorganic cobuilder.
  • Suitable organic cobuilders can be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and/or maleic acids in neutralised form.
  • Suitable inorganic cobuilders include carbonates and amorphous and crystalline layered silicates. Crystalline layered silicates are most preferred.
  • Suitable crystalline layered silicates have the composition:
  • NaMSi x ⁇ 2 ⁇ +i . y H2 ⁇ where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
  • M sodium or hydrogen, preferably sodium
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20.
  • Such materials are described in US Patents No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG).
  • the synthetic material is commercially available from Hoechst AG as ⁇ -Na2 Si2 ⁇ 5 (SKS6) and is described in US Patent No. 4664830.
  • the cobuilder may include an aluminosilicate zeolite A material, but where present such zeolite A builder is at a level of no more than 2% by weight of the detergent composition.
  • the detergent composition is free of zeolite A.
  • the total amount of detergency builder in the granular composition typically ranges from 1 to 80 wt.%, more preferably from 15 to 60 wt% and most preferably from 10 to 45 wt.%.
  • Detergent compositions according to the invention may also suitably contain a bleach system.
  • a bleach system preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.
  • the bleach system preferably comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a peroxyacid bleach precursor.
  • Suitable persalts include sodium perborate monohydrate and tetrahydrate and sodium percarbonate, with sodium percarbonate being most preferred.
  • the composition is substantially free of perborate tetrahydrate to ensure good storage stability of the composition at elevated temperatures.
  • Preferred bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors. Physical form
  • the detergent composition according to the invention is in solid form, for example powder, granular or tablet form. However, granular compositions are preferred.
  • At least part of, more preferably all of the cationic ester surfactant is in close physical proximity to the zeolite MAP component in the composition, preferably the two components are in close contact, most preferably they are in intimate admixture.
  • Particles, particularly made by agglomeration methods, in which such close physical proximity and especially such intimate admixture may be achieved are especially preferred.
  • Suitable coagglomerate materials include polycarboxylate builders, especially citrates, crystalline layered silicate, carbonate and bicarbonate salts.
  • the solid detergent compositions of the invention may be prepared by any suitable method.
  • Particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process.
  • a base powder is first prepared by spray-drying a slurry and then other components unsuitable for processing via the slurry can be sprayed on or admixed (postdosed).
  • the zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP to be inco ⁇ orated post-tower.
  • particulate detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as agglomeration using any commonly known detergent agglomeration methods.
  • Granular detergent compositions of the invention may be prepared to any suitable bulk density.
  • the compositions preferably have a bulk density of at least 400 g/l preferably at least 550 g/l, most preferably at least 700 g/l and, with particular preference at least 800 g/l.
  • powders of high bulk density for example, of 700 g/l or above.
  • Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and agglomeration; in both cases a high-speed mixer/granulator may advantageously be used.
  • Processes using high-speed mixer/granulators are disclosed, for example, in EP340013A, EP 367339A, EP 390251 A and EP 420317A (Unilever).
  • compositions according to the present invention are presented in the following Examples.
  • 246AS Sodium alkyl sulfate surfactant containing a alkyl chain length weight distribution of 15% C12 alkyl chains, 45% C-
  • TAS Sodium alkyl sulfate surfactant containing predominantly C15 - C-j ⁇ alkyl chains derived from tallow oil.
  • 24AE3S C12-C14 alkyl ethoxysulfate containing an average of three ethoxy groups per mole.
  • XYEZ A C ⁇ _ ⁇ primary alcohol condensed with an average of Z moles of ethylene oxide.
  • Carbonate Anhydrous sodium carbonate.
  • Perborate Sodium perborate tetrahydrate.
  • TAED Tetra acetyl ethylene diamine.
  • Silicate Amo ⁇ hous Sodium Silicate (SiO2:Na2O ratio normally follows).
  • Zeolite MAP Hydrated sodium aluminosilicate zeolite MAP having a silicon to aluminium ratio of 1.07.
  • MA/AA Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000.
  • Amylase Amylolytic enzyme sold under the tradename Termamyl 60T by Novo Industries A/S (approx. 0.9% enzyme activity).
  • BSA Amylolytic enzyme sold under the tradename LE17 by Novo Industries A/S (approx 1 % enzyme activity).
  • Protease Proteolytic enzyme sold by Novo Industries AS of activity 4.0 KNPU.
  • DTPMP Diethylene triamine penta (methylene phosphonic acid).
  • Silicone suds 12% silicone/siiica, 18% stearyl alcohol, 70% suppressor starch in granular form.
  • Example 1 The following granular laundry detergent compositions were prepared (parts by weight) in accordance with the invention. All amylase enzyme levels relate to levels of active enzyme, expressed on a 4 KNU/g activity basis.
  • All amylase enzyme levels relate to levels of active enzyme, expressed on a 4 KNU/g activity basis.

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

Abstract

L'invention porte sur une composition détergente comprenant: (a) un additif du type zéolite P présentant un rapport silice/aluminium ne dépassant pas 1,33 (zéolite MAP); et (b) un tensio-actif du type ester cationique, et dont le pH en solution à 1 % à 20 °C est supérieur à 9,25. L'invention porte également sur des compositions de détergents granulaires obtenues de préférence par des processus d'agglomération et sur leur procédés de fabrication.
PCT/US1996/012503 1995-08-02 1996-07-31 Composition detergente Ceased WO1997005221A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9515851.5 1995-08-02
GB9515851A GB2303858A (en) 1995-08-02 1995-08-02 Detergent composition

Publications (1)

Publication Number Publication Date
WO1997005221A1 true WO1997005221A1 (fr) 1997-02-13

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PCT/US1996/012503 Ceased WO1997005221A1 (fr) 1995-08-02 1996-07-31 Composition detergente

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AR (1) AR003172A1 (fr)
GB (1) GB2303858A (fr)
WO (1) WO1997005221A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19948671A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmittel
EP0881279B2 (fr) † 1997-05-26 2007-04-18 Cognis IP Management GmbH Granules contenant un tensioactif cationique
WO2007070328A1 (fr) * 2005-12-12 2007-06-21 Milliken & Company Composition de modification de surface d’un textile

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4260529A (en) * 1978-06-26 1981-04-07 The Procter & Gamble Company Detergent composition consisting essentially of biodegradable nonionic surfactant and cationic surfactant containing ester or amide
US4321165A (en) * 1977-06-29 1982-03-23 The Procter & Gamble Company Detergent compositions comprising cationic, anionic and nonionic surfactants
US4321157A (en) * 1979-11-03 1982-03-23 The Procter & Gamble Company Granular laundry compositions
US5238594A (en) * 1991-06-25 1993-08-24 Lever Brothers Co., Division Of Conopco, Inc. Detergent compositions
US5409627A (en) * 1993-03-18 1995-04-25 Lever Brothers Company, Division Of Conopco, Inc. Particulate bleaching detergent compositions containing zeolite map and a stable bleach catalyst

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4239660A (en) * 1978-12-13 1980-12-16 The Procter & Gamble Company Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source
GB9119958D0 (en) * 1991-09-18 1991-10-30 Unilever Plc Detergent compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4321165A (en) * 1977-06-29 1982-03-23 The Procter & Gamble Company Detergent compositions comprising cationic, anionic and nonionic surfactants
US4260529A (en) * 1978-06-26 1981-04-07 The Procter & Gamble Company Detergent composition consisting essentially of biodegradable nonionic surfactant and cationic surfactant containing ester or amide
US4321157A (en) * 1979-11-03 1982-03-23 The Procter & Gamble Company Granular laundry compositions
US5238594A (en) * 1991-06-25 1993-08-24 Lever Brothers Co., Division Of Conopco, Inc. Detergent compositions
US5409627A (en) * 1993-03-18 1995-04-25 Lever Brothers Company, Division Of Conopco, Inc. Particulate bleaching detergent compositions containing zeolite map and a stable bleach catalyst

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0881279B2 (fr) † 1997-05-26 2007-04-18 Cognis IP Management GmbH Granules contenant un tensioactif cationique
DE19948671A1 (de) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh Waschmittel
WO2007070328A1 (fr) * 2005-12-12 2007-06-21 Milliken & Company Composition de modification de surface d’un textile

Also Published As

Publication number Publication date
AR003172A1 (es) 1998-07-08
GB9515851D0 (en) 1995-10-04
GB2303858A (en) 1997-03-05

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