EP0863973A1 - Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite - Google Patents

Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite

Info

Publication number
EP0863973A1
EP0863973A1 EP96933155A EP96933155A EP0863973A1 EP 0863973 A1 EP0863973 A1 EP 0863973A1 EP 96933155 A EP96933155 A EP 96933155A EP 96933155 A EP96933155 A EP 96933155A EP 0863973 A1 EP0863973 A1 EP 0863973A1
Authority
EP
European Patent Office
Prior art keywords
builder
zeolite
detergent composition
bicarbonate
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.)
Withdrawn
Application number
EP96933155A
Other languages
German (de)
English (en)
Other versions
EP0863973A4 (fr
Inventor
Jonathan Richard Clare
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 EP0863973A1 publication Critical patent/EP0863973A1/fr
Publication of EP0863973A4 publication Critical patent/EP0863973A4/fr
Withdrawn legal-status Critical Current

Links

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only

Definitions

  • the present invention relates to a detergent composition
  • a detergent composition comprising both zeolite as a sequestering agent for water hardness and bicarbonate builder.
  • Detergent compositions for fabric washing conventionally contain detergency builders which lower the concentration of calcium and magnesium water hardness ions in the wash liquor and thereby provide good detergency effect in both hard and soft water.
  • inorganic phosphates such as sodium tripolyphosphate
  • inorganic phosphates have been used as builders for laundry detergents.
  • alkali metal aluminosilicate ion exchangers particularly crystalline sodium aluminosilicate zeolite A, have been proposed as replacements for the inorganic phosphates.
  • EP 21 491 A (Procter & Gamble) discloses detergent compositions containing a building system which includes zeolite A, X or P (B) or a mixture thereof.
  • EP 384070 A (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 its use as a detergency builder.
  • Zeolite builders are typically used in detergent compositions with cobuilders to provide optimum building capacity for the detergent composition as a whole.
  • Carbonate is a particularly commonly used cobuilder, which is favoured in part, for its ability to provide both building capacity and alkalinity to a wash solution.
  • a problem may occur when a water insoluble zeolite having a small particle size, is used as a detergency builder in a fabric laundering detergent composition also containing relatively high levels of carbonate cobuilder.
  • the problem has been found to be particularly pronounced when the zeolite builder is zeolite MAP.
  • a small particle size for a zeolite MAP component that is to say particles having a particle size, measured as a d5Q value, of up to 1.0 micrometres has previously been taught to be preferred in the art, as represented, for example, by EP 384070 A.
  • the problem relates to the aforementioned detergent compositions having a marked incompatibility with printed cotton fabrics.
  • the use of detergent compositions containing small particle size zeolite tends to lead to the removal of printed pigment from a printed cotton fabric surface.
  • the presence of relatively high levels of carbonate cobuilder has been found to exarcebate this effect.
  • the Applicant has surprisingly found that this problem can be ameliorated by the partial or complete replacement of the carbonate component of the detergent composition by a bicarbonate builder component.
  • the present invention is thus based on the unexpected finding that the printed cotton fabric care profile of a detergent composition comprising zeolite of small particle size, bicarbonate builder and relatively low levels of carbonate builder is superior to that of comparably alkaline and built compositions containing principally carbonate cobuilder.
  • the present invention provides a detergent composition containing
  • weight ratio any carbonate builder to the bicarbonate builder is less than 4:1.
  • the zeolite builder comprises zeolite P having a silcon to aluminium ratio of not greater than 1.33 (zeolite MAP).
  • the detergent composition according to the invention is formulated to be especially useful in the laundering of coloured fabrics and preferably is free of bleach.
  • the composition is substantially free of an optical brightener.
  • the first essential component of the present invention is an aluminosilicate zeolite builder.
  • the zeolite builder is typically present at a level of from 1% to 80%, more preferably from 15% to 40% by weight ofthe compositions.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO2) z (SiO2)y] XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof.
  • Zeolite A has the formula
  • Zeolite X has the formula Nagg [(Al ⁇ 2)86(Si ⁇ 2)lfj6]* 276 H 2 O.
  • Zeolite MAP is described in EP 384070 A (Unilever). It is defmed 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:Al ratio of 1.33 or less may be prepared by the following steps:
  • Na2 ⁇ :Al2 ⁇ 3 within the range of from 1.4 to 2.0 and a sodium silicate having a mole ratio Si ⁇ 2:Na2 ⁇ within the range of from 0.8 to
  • 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 ofthe notional anhydrous material.
  • the amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt.%.
  • the zeolite builder used in the present invention has a particle size d5Q of less than 1.0 micrometres, preferably from 0.05 to 0.9 micrometres, most preferably from 0.2 to 0.7 micrometres.
  • the dso value indicates that 50% by weight of the particles have a diameter smaller than that figure.
  • the particle size may be determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope or by means of a laser granulometer.
  • Zeolite builder having the required particle size according to the present invention can, for example, be prepared by the conventional techniques as described above while adopting one or more ofthe following steps :-
  • the detergent compositions contain bicarbonate builder.
  • bicarbonate builder it is meant herein any compound capable of releasing bicarbonate ions to a wash solution.
  • Preferrred bicarbonate builders include the alkali and alkaline earth bicarbonate salts, particularly sodium bicarbonate.
  • the bicarbonate builder is typically present at a level of from 0.5% to 60%, * preferably from 2% to 40%, most preferably from 3% to 20% by weight of the detergent composition.
  • the bicarbonate builder is preferably present at a weight ratio of zeolite builder to bicarbonate builder of from 20:1 to 1 :5, more preferably from 10:1 to 2:1, most preferably from 5 : 1 to 1 : 1.
  • the detergent compositions may contain other organic or inorganic builders.
  • any carbonate builder that is of inorganic compound capable of releasing carbonate ions into a wash solution
  • any carbonate builder is present only at a level wherein the weight ratio of the carbonate builder to the bicarbonate builder is less than 4:1, preferably less than 2:1, more preferably less than 1: 1.
  • the detergent composition is free from carbonate builder.
  • 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 amo ⁇ hous and crystalline layered silicates.
  • Suitable crystalline layered silicates have the composition:
  • 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 is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
  • the synthetic material is commercially available from Hoechst AG as ⁇ -Na2 Si2 ⁇ 5 (SKS6) and is described in US Patent No. 4664830.
  • the total amount of detergency builder in the granular composition typically ranges from 10 to 80 wt.%, more preferably from 15 to 60 wt% and most preferably from 10 to 45 wt.%.
  • the detergent composition according to the invention may contain other detergent components such as surfactants, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
  • other detergent components such as surfactants, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
  • the detergent composition according to the invention preferably includes a surfactant selected from anionics, nonionics, zwitterionics, ampholytics and cationics.
  • the 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 ofthe compositions.
  • suitable detergent-active compounds are available and fully described in the literature (for example "Surface Active Agents and Detergents” Volumes I and II by Schwartz, Perry and Berch).
  • 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-C17 acyl-N-(C ⁇ -C4 alkyl) and -N-(C j -C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C ⁇ -Ci g 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 Cg-Ci g 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, C6-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • the nonionic surfactant is preferably a hydrophobic nonionic surfactant, particularly an alkoxylated nonionic surfactant, having a hydrophilic lipophilic balance (hlb) value of ⁇ 9.5, more preferably ⁇ 10.5.
  • suitable hydrophobic alkoxylated nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of less than 5 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 ofthe 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 3.5 and n is 2 or 3.
  • Preferred nonionic surfactants include primary C1 1-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 particularly 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.
  • Detergent compositions according to the invention may also contain a bleach system. Where present, this 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.
  • 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.
  • Preferred bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • the detergent compositions are free of bleach and of particular utility in the washing of loads containing brightly coloured fabrics.
  • Preferred detergent compositions according to the invention are characterised by having a pH measured as a 1% solution of the detergent composition in distilled water at 25°C of ⁇ 10.5, preferably ⁇ 10.4, most preferably ⁇ 10.3.
  • compositions having a low level of reserve alkalinity are advantageous in that they have a further reduced tendency to cause the removal of printed pigment from printed cotton fabrics.
  • Reserve alkalinity is expressed as g of NaOH per 100 g of composition as determined by acid titration of a sample, as 1% solution in distilled water to a pH of 9.5.
  • Preferred values of reserve alkalinity are ⁇ 8.0 g preferably ⁇ 5.0 g, most preferably ⁇ 3.0 g NaOH per lOOg of composition.
  • the detergent composition according to the invention may be of any physical type, for example powders, liquids and gels. However, granular and liquid compositions are preferred.
  • the detergent compositions of the invention may be prepared by any suitable method.
  • the 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 builder is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite builder to be incorporated post-tower.
  • the crystalline layered silicate, where this is employed, is also incorporated via a non-tower process and is preferably postdosed.
  • particulate detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as granulation.
  • the 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 ⁇ preferably at least 550 g/1, most preferably at least 700 g/1 and, with particular preference at least 800 g/1.
  • the benefits ofthe present invention are particularly evident in powders of high bulk density, for example, of 700 g/1 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 granulation; in both cases a high-speed mixer/granulator may advantageously be used.
  • Processes using high-speed mixer/granulators are disclosed, for example, in EP340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
  • the detergent composition of the invention may be formulated as a liquid detergent composition which may be aqueous or anhydrous.
  • the term "liquid” used herein includes pasty viscous formulations such as gels.
  • the liquid detergent composition generally has a pH of from 6.5 to 10.5.
  • the total amount of detergency builder in the liquid composition is preferably from 5 to 70% ofthe total liquid composition.
  • compositions according to the present invention are presented in the following Examples.
  • the abbreviated component identifications have the following meanings:
  • SKS6 Crystalline layered silicate available from Hoechst AG as SKS6 (tradename)
  • Zeolite A Hydrated sodium aluminosilicate zeolite A having a particle size, expressed as a (I 0 value, of 0.6 micrometres
  • MA AA Copolymer of 1:4 maleic acrylic acid average molecular weight about 80,000.
  • Alcalase Proteolytic enzyme sold under the tradename Alcalase by Novo Industries A S (approx 1% enzyme activity by weight)
  • the detergent compositions according to the invention which comprise zeolite builder of larger particle size and bicarbonate builder optionally with relatively low levels of carbonate builder, show good results in stain removal and lower printed cotton fabric damage as compared with a comparably alkaline and built bicarbonate- free composition comprising small particle size zeolite and principally carbonate builder.

Landscapes

  • 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

Cette invention concerne une composition détergente comprenant un adjuvant à base de zéolite possédant une taille des particule d50 inférieure à 1,0 micron, ainsi qu'un adjuvant à base de bicarbonate. Un adjuvant à base de carbonate peut éventuellement être présent en faibles quantités, le rapport de poids entre tout adjuvant à base de carbonate et l'adjuvant à base de bicarbonate restant inférieur à 4:1.
EP96933155A 1995-09-26 1996-09-26 Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite Withdrawn EP0863973A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9519607 1995-09-26
GBGB9519607.7A GB9519607D0 (en) 1995-09-26 1995-09-26 Detergent composition
PCT/US1996/015452 WO1997012025A1 (fr) 1995-09-26 1996-09-26 Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite

Publications (2)

Publication Number Publication Date
EP0863973A1 true EP0863973A1 (fr) 1998-09-16
EP0863973A4 EP0863973A4 (fr) 1999-02-10

Family

ID=10781288

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96933155A Withdrawn EP0863973A4 (fr) 1995-09-26 1996-09-26 Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite

Country Status (5)

Country Link
EP (1) EP0863973A4 (fr)
BR (1) BR9610735A (fr)
CA (1) CA2232956A1 (fr)
GB (1) GB9519607D0 (fr)
WO (1) WO1997012025A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6638902B2 (en) * 2001-02-01 2003-10-28 Ecolab Inc. Stable solid enzyme compositions and methods employing them

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4666740A (en) * 1976-12-02 1987-05-19 The Colgate-Palmolive Co. Phosphate-free concentrated particulate heavy duty laundry detergent
WO1995002036A1 (fr) * 1993-07-05 1995-01-19 Unilever Plc Composition detergente ou composant contenant un tensioactif anionique et son procede de preparation
EP0653481A1 (fr) * 1993-11-11 1995-05-17 The Procter & Gamble Company Composition de détergent granulaire
WO1995016016A1 (fr) * 1993-12-07 1995-06-15 The Procter & Gamble Company Composition detergente contenant un tensioactif a l'oxyde d'amine sous forme d'agglomerats

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9305599D0 (en) * 1993-03-18 1993-05-05 Unilever Plc Detergent compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4666740A (en) * 1976-12-02 1987-05-19 The Colgate-Palmolive Co. Phosphate-free concentrated particulate heavy duty laundry detergent
WO1995002036A1 (fr) * 1993-07-05 1995-01-19 Unilever Plc Composition detergente ou composant contenant un tensioactif anionique et son procede de preparation
EP0653481A1 (fr) * 1993-11-11 1995-05-17 The Procter & Gamble Company Composition de détergent granulaire
WO1995016016A1 (fr) * 1993-12-07 1995-06-15 The Procter & Gamble Company Composition detergente contenant un tensioactif a l'oxyde d'amine sous forme d'agglomerats

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9712025A1 *

Also Published As

Publication number Publication date
EP0863973A4 (fr) 1999-02-10
GB9519607D0 (en) 1995-11-29
BR9610735A (pt) 1999-07-13
WO1997012025A1 (fr) 1997-04-03
CA2232956A1 (fr) 1997-04-03

Similar Documents

Publication Publication Date Title
CA2087308C (fr) Compositions de detergents
US5958871A (en) Detergent composition based on zeolite-bicarbonate builder mixture
WO1997012025A1 (fr) Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite
WO1996024656A1 (fr) Composition detergente contenant de la zeolithe map et mineral d'argile
GB2303858A (en) Detergent composition
GB2288187A (en) Detergent composition
EP0964907A1 (fr) Composition detergente contenant un adjuvant de zeolite particulaire et un agent lubrifiant
EP0802970B1 (fr) Composition detergente comprenant la zeolite map et des enzymes amylases
US6440922B1 (en) Detergent composition comprising zeolite and amylase enzyme
GB2287948A (en) Laundry detergent composition
EP0880578A1 (fr) Composition detergente comportant de la zeolite et une enzyme proteolytique
EP0859824A1 (fr) Composition detergente
CA2210293C (fr) Composition detergente comprenant de la zeolite et une enzyme amylase
EP0787174A1 (fr) Composition detergente
MXPA98002410A (es) Composicion detergente a base de una mezcla mejoradora de detergencia de zeolita y bicarbonato
WO1996021705A1 (fr) Composition detergente
MXPA98002501A (en) Detergent composition containing a zeolite detergent improvement and a lubricant for elmi
MXPA98002408A (en) Deterge composition
MXPA98002409A (en) Detergent composition comprising zeolite and enzyme proteolit
EP0733699A2 (fr) Composition détergente
GB2287950A (en) Detergent composition
MXPA97002939A (en) Deterge composition
MXPA97005327A (en) Detergent composition comprising zeolite and enzyme amil
CA2203134A1 (fr) Composition detergente
MXPA97005330A (en) Deterge composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19980311

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

A4 Supplementary search report drawn up and despatched

Effective date: 19981228

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20010403