EP0533392B1 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

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Publication number
EP0533392B1
EP0533392B1 EP92308211A EP92308211A EP0533392B1 EP 0533392 B1 EP0533392 B1 EP 0533392B1 EP 92308211 A EP92308211 A EP 92308211A EP 92308211 A EP92308211 A EP 92308211A EP 0533392 B1 EP0533392 B1 EP 0533392B1
Authority
EP
European Patent Office
Prior art keywords
zeolite
detergent composition
composition
detergent
sodium silicate
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.)
Expired - Lifetime
Application number
EP92308211A
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German (de)
English (en)
Other versions
EP0533392A2 (fr
EP0533392A3 (en
Inventor
Andrew Paul Unilever Research Chapple
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Publication date
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Publication of EP0533392A2 publication Critical patent/EP0533392A2/fr
Publication of EP0533392A3 publication Critical patent/EP0533392A3/en
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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
    • 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
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O

Definitions

  • the present invention relates to detergent compositions, especially particulate detergent compositions, containing a detergency builder system which is a combination of a defined alkali metal aluminosilicate and a defined lamellar crystalline sodium silicate.
  • the invention is especially but not exclusively concerned with compositions suitable for the laundering of fabrics in domestic or commercial washing machines.
  • Detergent compositions for heavy-duty fabric washing conventionally contain materials - detergency builders - to lower the concentration of calcium water hardness ions in the wash liquor and thus to give good detergency in hard water as well as in soft water.
  • Alkali metal aluminosilicate ion-exchangers are now well-known replacements for the inorganic phosphates traditionally used as detergency builders in fabric washing detergents. It is also well known that zeolites show certain deficiencies in detergency building, as compared with phosphates, and that supplementary building power is generally desirable. In many zero-phosphate premium detergent powders now on the European market, homo- or copolymers of acrylic acid are included for this purpose.
  • US 4 664 839, US 4 728 443 and US 4 820 439 disclose a lamellar crystalline sodium silicate having the composition NaMSi x O 2x+1 ⁇ yH 2 O wherein M denotes sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20.
  • This material is useful as a detergency builder and may be used in conjunction with other detergency builders, for example, zeolite A.
  • EP 405 122A discloses a builder for detergents composed of 20-80 wt% of hydrated zeolite and 20-80 wt% of lamellar crystalline sodium silicate.
  • the zeolite is preferably a synthetic material obtained as described in US 4 274 975 (Procter & Gamble).
  • Detergent compositions containing the two materials in ratios of 0.5:1, 1:1 and 2:1 are specifically disclosed.
  • WO 92 03525A (Procter & Gamble), published on 5 March 1992, discloses particulate laundry detergent compositions containing a three-component non-phosphorus builder system comprising a sodium aluminosilicate zeolite (20-60 wt%), a water-soluble monomeric or oligomeric carboxylate chelating agent such as sodium citrate (10-30 wt%), and a crystalline layered sodium silicate (10-65 wt%), the percentages being based on the builder system.
  • Preferred zeolites specifically mentioned are zeolite A, zeolite X, zeolite P and zeolite HS.
  • JP 01 153 800A discloses textile-softening granular detergent compositions containing detergent-active compounds, bentonite clay, water-soluble crystalline layered sodium silicate of the formula given above, and aluminosilicate (zeolite).
  • Detergent compositions containing zeolite A and layered silicate (Na-SKS-6) in proportions of 3:1, 1:1 and 1:3 are specifically disclosed.
  • EP 384 070A (Unilever) describes and claims a novel zeolite P (maximum aluminium zeolite P, or zeolite MAP) having an especially low silicon to aluminium ratio, not greater than 1.33, preferably not greater than 1.15 and more preferably not greater than 1.07. This material is demonstrated to be a more weight-effective detergency builder than conventional zeolite 4A.
  • the present invention is based on the discovery that the novel combination of zeolite MAP and lamellar silicate provides an especially effective detergency builder system, the detergency being better than would be predicted from knowledge of the individual builder efficacies of the two materials.
  • the present invention provides a detergent composition comprising:
  • the present invention provides a detergency builder composition comprising:
  • the invention provides a method of washing fabrics, which includes the step of bringing the fabrics into contact with an aqueous wash liquor containing a detergent composition as defined above and/or a detergency builder composition as defined above.
  • the invention provides the use of lamellar silicate as defined above as a detergency builder in a detergency builder composition or a detergent composition containing zeolite MAP.
  • the detergent composition is a mixture of the detergent composition
  • the detergent composition of the invention contains, as essential components, a detergent-active compound, and a detergency builder system.
  • the inventive step lies in the choice of the detergency builder system, while the detergent-active compound and other optional ingredients may be conventional.
  • the detergency builder system of the invention contains two essential components: zeolite MAP and a lamellar crystalline sodium silicate.
  • Zeolite MAP and its use in detergent compositions are described and claimed in EP 384 070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range of 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 especially material having a ratio not greater than 1.07.
  • Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilicate.
  • zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percentages of zeolite are expressed in terms of the anhydrous material.
  • the second essential component of the detergency builder system of the invention is a lamellar crystalline sodium silicate having the composition NaMSi x O 2x+1 ⁇ yH 2 O wherein M denotes sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
  • Na-SKS-6 Both natural and synthetic compounds of this formula are of interest, the synthetic material known as Na-SKS-6 being especially preferred.
  • This material is commercially available from Hoechst AG; its preparation is described, and it is defined in terms of its X-ray diffraction pattern, in the aforementioned US 4 664 839.
  • Detergent compositions of the invention preferably comprise from 10 to 45 wt%, more preferably from 12 to 30 wt%, of zeolite MAP; and from 2 to 30 wt%, more preferably from 3 to 25 wt%, of the lamellar silicate.
  • the ratio of zeolite MAP (a) (anhydrous basis) to lamellar crystalline silicate (b) is preferably within the range of from 0.1:1 to 10:1, more preferably from 0.2:1 to 7:1.
  • the synergistic effect is particularly marked at ratios ranging from 0.3:1 to 3:1, more especially from 0.5:1 to 2:1.
  • the detergent compositions of the invention will contain, as essential ingredients, one or more detergent-active compounds (surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
  • surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
  • detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
  • Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkyl sulphates, particularly C 12 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the aliphatic C 12 -C 15 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol; and non-ethoxylated nonionic surfactants, for example, alkylpolyglycosides, and alkyl glyceryl ethers and esters.
  • Preferred detergent-active systems suitable for compositions intended for use in automatic fabric washing machines, comprises anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap.
  • the total amount of detergent-active compounds present may suitably lie in the range of from 5 to 40 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 precursor.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
  • Preferred bleach precursors are peracetic acid precursors, especially tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors; and the novel quaternary ammonium and phosphonium bleach activators disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company), more especially cholyl p-sulphophenyl carbonate (CSPC).
  • TAED tetraacetylethylene diamine
  • CSPC cholyl p-sulphophenyl carbonate
  • the bleach system may also include a bleach stabiliser (heavy metal sequestrant).
  • a bleach stabiliser heavy metal sequestrant
  • the amount of soluble (amorphous) silicates in the compositions of the invention is preferably kept to a relatively low level: preferably below 5 wt%, and more preferably below 1 wt%.
  • compositions of the invention may advantageously contain alkali metal carbonate, to provide alkalinity rather than for detergency building.
  • alkali metal, preferably sodium, carbonate may suitably range from 2 to 20 wt%, preferably from 5 to 15 wt%. However, the presence of sodium carbonate is not essential.
  • compositions of the invention include fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, lather control agents, fabric softening agents, pigments, coloured speckles, and perfumes. This list is not intended to be exhaustive.
  • Detergent compositions of the invention may be prepared by any suitable method.
  • the particulate detergent compositions which are the preferred embodiment of the invention are suitably prepared by any tower (spray-drying) or non-tower process.
  • a base powder is first prepared by spray-drying a slurry of compatible heat-insensitive ingredients, and any ingredients unsuitable for processing via the slurry may then be sprayed on or admixed (postdosed).
  • the skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
  • 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 incorporated post-tower.
  • the lamellar silicate is preferably postdosed.
  • particulate detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as granulation.
  • Particulate detergent compositions of the invention may be prepared to any suitable bulk density.
  • Compositions having bulk densities of at least 400 g/l, more preferably at least 500 g/l, are of especial interest.
  • the detergency builder system of the invention may be exist as a composition in its own right that may be used for water softening or added to the wash liquor to enhance the performance of an unbuilt or underbuilt detergent composition in hard water.
  • Such a composition may, for example, form the building or water-softening component of a Baukasten (building block) detergent composition as described and claimed in EP 419 036A (Unilever), in which a main wash powder is supplied together with separately packaged additives (builder, bleach) that need only be used when the wash conditions demand them.
  • Baukasten building block
  • additives builder, bleach
  • a composition of this type may in principle contain no components other than the two essential components (zeolite MAP and lamellar silicate), although in practice it may be desirable to include other ingredients, for example, sodium carbonate, and binders such as nonionic surfactants or cellulose derivatives.
  • a builder composition of the type under discussion may also be used as a raw material or premix in the manufacture of more fully formulated detergent compositions.
  • the invention also includes within its scope detergent compositions prepared by admixing the two builder materials (zeolite MAP and lamellar silicate) separately and independently with other detergent ingredients.
  • the detergent compositions and detergency builder compositions of the invention are especially suitable for washing textile fabrics, and have been assessed with this end-use in mind.
  • the builder system is of potential use and interest for any other type of cleaning product requiring a built detergent system, for example, machine dishwashing compositions.
  • a detergent composition was prepared to the following formulation: wt% Linear alkylbenzene sulphonate 6.8 Nonionic surfactant (3EO) 3.1 Nonionic surfactant (7EO) 6.9 Soap 1.73 Builder (see below) 31.8 Sodium carboxymethylcellulose 0.83 Sodium carbonate 9.6 Sodium alkaline silicate 0.55 Sodium perborate monohydrate 16.25 Tetraacetylethylenediamine (granule) 6.6 Protease granule (Savinase 6.0T) 1.1 Antifoam granule 1.2 Moisture to 100.0
  • the builder systems used in the individual Examples were as follows: A, B 1, 4 2, 5 3, 6 (a) Zeolite MAP 31.8 23.8 15.9 8.0 (b) Na-SKS-6 - 8.0 15.9 23.8 Ratio (a):(b) 2.98 1.0 0.34
  • the zeolite MAP was prepared by a method similar to that described in Examples 1 to 3 of EP 384 070A (Unilever). Its silicon to aluminium ratio was 1.07.
  • the Na-SKS-6 supplied by Hoechst AG, was as described in US 4 664 839 and US 4 820 439 (Hoechst).
  • the last column represents the predicted result if zeolite MAP were totally replaced by Na-SKS-6 (see Examples C and D below).
  • compositions were as follows: C D Linear alkylbenzene sulphonate 6.0 6.0 Nonionic surfactant (3EO) 2.75 2.75 Nonionic surfactant (7EO) 4.25 4.25 Soap 1.65 1.65 Zeolite 4A 24.00 - Na-SKS-6 0.50 45.00 Acrylic/maleic copolymer 4.00 4.00 Sodium carboxymethylcellulose 0.83 0.83 Sodium carbonate 10.00 10.00 Sodium sulphate 33.39 12.89 Sodium perborate monohydrate 7.50 7.50 Tetraacetylethylenediamine (granule) 2.77 2.77 Protease granule (Savinase 6.0T) 0.40 0.40 Antifoam granule 1.00 1.00 Moisture and minor ingredients -to 100.00-
  • Detergencies (delta R 460 ) were compared in the Tergotometer using test cloth 1, at 40°C, water hardnesses of 25°FH and 40°FH (total) and a product dosage of 5 g/litre, and were as follows: 25°FH 40°FH Example C (45% SKS-6) 20.8 11.8 Example D (24% zeolite, 0.5% SKS-6) 24.2 13.3
  • the zeolite 4A used in this experiment was Wessalith P ex Degussa.
  • Example 14 of EP 384 070A (Unilever) demonstrates that zeolite MAP of silicon to aluminium ratio 1.12, as the sole builder in a detergent composition, gives significantly better detergency on test cloth 1 (referred to as AS 9), at two different product dosages, than does zeolite 4A.
  • AS 9 test cloth 1
  • zeolite MAP too must be a substantially more weight-effective builder than Na-SKS-6, and it can be predicted that the detergency scores for Na-SKS-6 alone in experiments corresponding to Examples A, 1-3, B and 4-6 would have been considerably lower than those for zeolite MAP alone.
  • the synergistic benefit observed when zeolite MAP is partially replaced by Na-SKS-6 is therefore particularly surprising.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (17)

  1. Composition détergente comprenant :
    (i) un ou plusieurs composés détergents actifs choisis parmi les composés détergents actifs anioniques, non ioniques, cationiques, amphotères et zwitterioniques et leurs combinaisons,
    (ii) un système adjuvant de détergence comprenant une zéolite et un silicate de sodium cristallin lamellaire,
    caractérisée en ce que le système adjuvant comprend :
    (a) une zéolite P ayant un rapport silicium : aluminium n'excédant pas 1,33 (ci-après zéolite PAM) et
    (b) un silicate de sodium cristallin lamellaire ayant la composition : NaMSixO2x+1.yH2O dans laquelle M représente le sodium ou l'hydrogène, x est un nombre de 1,9 à 4 et y est un nombre de 0 à 20.
  2. Composition détergente selon la revendication 1, caractérisée en ce que la zéolite PAM a un rapport silicium : aluminium qui ne dépasse pas 1,15.
  3. Composition détergente selon la revendication 1, caractérisée en ce que la zéolite PAM a un rapport silicium : aluminium qui ne dépasse pas 1,07.
  4. Composition détergente selon l'une quelconque des revendications précédentes, caractérisée en ce que le rapport pondéral de la zéolite PAM (a) (base anhydre) au silicate de sodium cristallin lamellaire (b) est dans la gamme de 0,1:1 à 10:1.
  5. Composition détergente selon la revendication 4, caractérisée en ce que le rapport pondéral de (a) à (b) est dans la gamme de 0,2:1 à 7:1.
  6. Composition détergente selon la revendication 5, caractérisée en ce que le rapport pondéral de (a) à (b) est dans la gamme de 0,3:1 à 3:1.
  7. Composition détergente selon la revendication 6, caractérisée en ce que le rapport pondéral de (a) à (b) est dans la gamme de 0,5:1 à 2:1.
  8. Composition détergente selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle contient de 10 à 45% en poids (base anhydre) de zéolite PAM.
  9. Composition détergente selon la revendication 8, caractérisée en ce qu'elle contient de 12 à 30% en poids (base anhydre) de zéolite PAM.
  10. Composition détergente selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle contient de 2 à 30% en poids de silicate de sodium cristallin lamellaire (b).
  11. Composition détergente selon la revendication 10, caractérisée en ce qu'elle contient de 3 à 25% en poids de silicate de sodium cristallin lamellaire (b).
  12. Composition détergente selon l'une quelconque des revendications précédentes, caractérisée en ce que le silicate de sodium cristallin lamellaire (b) a la composition : NaMSi2O5.yH2O dans laquelle M et y ont les significations données dans la revendication 1.
  13. Composition détergente selon la revendication 12, caractérisée en ce que le silicate de sodium cristallin lamellaire (b) est le Na-SKS-6.
  14. Composition détergente selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle est sous forme particulaire.
  15. Composition d'adjuvant de détergence comprenant une zéolite et un silicate de sodium cristallin lamellaire, caractérisée en ce qu'elle comprend :
    (a) une zéolite P ayant un rapport silicium : aluminium n'excédant pas 1,33 (ci-après zéolite PAM) et
    (b) un silicate de sodium cristallin lamellaire ayant la composition : NaMSixO2x+1.yH2O dans laquelle M représente le sodium ou l'hydrogène, x est un nombre de 1,9 à 4 et y est un nombre de 0 à 20.
  16. Procédé de lavage des textiles, caractérisé en ce qu'il comporte le stade de mettre en contact les textiles avec une liqueur de lavage aqueuse contenant une composition détergente selon l'une quelconque des revendications 1 à 14 et/ou une composition d'adjuvant de détergence selon la revendication 15.
  17. Utilisation de silicate de sodium cristallin lamellaire ayant la composition : NaMSixO2x+1.yH2O dans laquelle M représente le sodium ou l'hydrogène, x est un nombre de 1,9 à 4 et y est un nombre de 0 à 20, comme adjuvant de détergence dans une composition d'adjuvant de détergence contenant une zéolite P ayant un rapport silicium : aluminium n'excédant pas 1,33.
EP92308211A 1991-09-18 1992-09-10 Compositions détergentes Expired - Lifetime EP0533392B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919119958A GB9119958D0 (en) 1991-09-18 1991-09-18 Detergent compositions
GB9119958 1991-09-18

Publications (3)

Publication Number Publication Date
EP0533392A2 EP0533392A2 (fr) 1993-03-24
EP0533392A3 EP0533392A3 (en) 1995-04-12
EP0533392B1 true EP0533392B1 (fr) 1998-05-13

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EP92308211A Expired - Lifetime EP0533392B1 (fr) 1991-09-18 1992-09-10 Compositions détergentes

Country Status (8)

Country Link
EP (1) EP0533392B1 (fr)
JP (1) JPH05202384A (fr)
BR (1) BR9203532A (fr)
CA (1) CA2078155C (fr)
DE (1) DE69225449T2 (fr)
ES (1) ES2116320T3 (fr)
GB (1) GB9119958D0 (fr)
ZA (1) ZA927167B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4304474A1 (de) * 1993-02-15 1994-08-18 Henkel Kgaa Tensid- und builderhaltiges Waschmitteladditiv
EP0781320B2 (fr) † 1994-09-13 2013-10-16 Kao Corporation Procede de lavage
GB2303858A (en) * 1995-08-02 1997-03-05 Procter & Gamble Detergent composition
GB9519606D0 (en) * 1995-09-26 1995-11-29 Procter & Gamble Detergent composition
WO1997019156A1 (fr) * 1995-11-22 1997-05-29 Kao Corporation Detergent en poudre pour le nettoyage de vetements
GB9605534D0 (en) * 1996-03-15 1996-05-15 Unilever Plc Detergent compositions
GB9605533D0 (en) 1996-03-15 1996-05-15 Unilever Plc Modified aluminosilicate
FR2794646B1 (fr) 1999-06-09 2001-09-21 Ethypharm Lab Prod Ethiques Microgranules de sulfate de morphine, procede de preparation et composition les contenant
MY133398A (en) * 1999-07-09 2007-11-30 Colgate Palmolive Co Fabric cleaning composition containing zeolite
US6204239B1 (en) * 1999-11-24 2001-03-20 Colgate-Palmolive, Inc. Fabric cleaning composition containing zeolite

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265777A (en) * 1980-04-17 1981-05-05 The Procter & Gamble Company Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap
CA2001927C (fr) * 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates et detergents
JPH02178399A (ja) * 1988-12-29 1990-07-11 Lion Corp 粒状洗剤組成物
DE3920704A1 (de) * 1989-06-24 1991-01-03 Hoechst Ag Builder fuer textilwaschmittel

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Publication number Publication date
ZA927167B (en) 1994-03-18
EP0533392A2 (fr) 1993-03-24
DE69225449D1 (de) 1998-06-18
BR9203532A (pt) 1993-04-13
CA2078155C (fr) 1997-06-03
GB9119958D0 (en) 1991-10-30
ES2116320T3 (es) 1998-07-16
EP0533392A3 (en) 1995-04-12
DE69225449T2 (de) 1998-09-03
JPH05202384A (ja) 1993-08-10
CA2078155A1 (fr) 1993-03-19

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