WO1994024251A1 - Compositions nettoyantes ou de blanchiment particulaires contenant des aluminosilicates - Google Patents

Compositions nettoyantes ou de blanchiment particulaires contenant des aluminosilicates Download PDF

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Publication number
WO1994024251A1
WO1994024251A1 PCT/EP1994/001115 EP9401115W WO9424251A1 WO 1994024251 A1 WO1994024251 A1 WO 1994024251A1 EP 9401115 W EP9401115 W EP 9401115W WO 9424251 A1 WO9424251 A1 WO 9424251A1
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WO
WIPO (PCT)
Prior art keywords
zeolite
cations
composition
moisture
sodium
Prior art date
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PCT/EP1994/001115
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English (en)
Inventor
Andrew Paul Chapple
Original Assignee
Unilever Plc
Unilever N.V.
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Filing date
Publication date
Application filed by Unilever Plc, Unilever N.V. filed Critical Unilever Plc
Priority to AU65669/94A priority Critical patent/AU684769B2/en
Priority to CA002155852A priority patent/CA2155852C/fr
Priority to EP94913571A priority patent/EP0695341B1/fr
Priority to SK1036-95A priority patent/SK281006B6/sk
Priority to DE69407405T priority patent/DE69407405T2/de
Priority to PL94311163A priority patent/PL177828B1/pl
Priority to BR9406174A priority patent/BR9406174A/pt
Publication of WO1994024251A1 publication Critical patent/WO1994024251A1/fr

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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to particulate detergent, bleaching or cleaning compositions containing crystalline aluminosilicates (zeolites), and also containing ingredients sensitive to moisture, especially bleach ingredients, for example, inorganic persalts such as sodium percarbonate, organic or inorganic peroxyacids, bleach precursors, or bleach catalysts.
  • bleach ingredients for example, inorganic persalts such as sodium percarbonate, organic or inorganic peroxyacids, bleach precursors, or bleach catalysts.
  • crystalline aluminosilicates zeolites
  • zeolites crystalline aluminosilicates
  • zeolite A used in sodium form.
  • Examples of prior art documents disclosing detergent compositions containing zeolites are EP 456 515A (Procter & Gamble) , EP 38 591A and EP 21 491A (Procter & Gamble), EP 87 035A (Union Carbide), US 4 604 224 and CA 1 072 853 (Colgate) .
  • the use of zeolites A, X, B (P) and Y is disclosed, and general formulae with a range of possible cations given, but sodium is always the highly preferred cation and all specific disclosure relates to zeolites in sodium form.
  • Sodium percarbonate is a well-known bleaching ingredient in bleaching and detergent compositions and is widely disclosed in the literature, although in recent years its use in commercial products has been abandoned in favour of sodium perborate.
  • Sodium percarbonate is less stable than sodium perborate in the presence of moisture, and its stabilisation in detergent powders has long been recognised as a problem. This problem becomes especially acute if sodium percarbonate is to be included in a detergent powder with a high mobile water content, when it tends to become deactivated in storage. This situation applies in particular to powders containing zeolites, because those materials contain a large amount of relatively mobile water.
  • EP 364 184A discloses non-aqueous cleaning compositions containing dispersed aluminosilicate particles which have been deactivated by treatment with an ammonium or substituted ammonium compound and thereafter heated to reduce the water content below 24 wt%.
  • the treatment reduces the aluminosilicate-catalysed decomposition of bleach precursors such as tetraacetylethylenediamine in the liquid product.
  • EP 364 184A is concerned with an environment (a non-aqueous liquid) in which the water content is strictly limited and controlled, and with aluminosilicates which must be partially dehydrated.
  • the present invention provides a particulate detergent, bleaching or cleaning composition comprising an ingredient sensitive to moisture and a crystalline aluminosilicate having exchangeable cations, wherein the exchangeable cations of the aluminosilicate include cations derived from a weak monoacidic base. More specifically, the invention provides a particulate bleaching detergent composition comprising an organic detergent surfactant, a bleach ingredient sensitive to moisture and a crystalline aluminosilicate, wherein the aluminosilicate is as defined in the previous paragraph.
  • the invention further provides the use of an aluminosilicate as defined above to improve the stability of an ingredient sensitive to moisture in a particulate detergent, bleaching or cleaning composition.
  • the invention further provides, as a novel material, zeolite P having a silicon to aluminium ratio not exceeding 1.33, preferably not exceeding 1.15 and more preferably not exceeding 1.07, having exchangeable cations wherein the exchangeable cations include cations derived from a weak monoacidic base.
  • composition of the invention has two essential ingredients: the aluminosilicate, and the moisture-sensitive ingredient.
  • compositions of the invention require as an essential ingredient a crystalline aluminosilicate (zeolite) in which the exchangeable cations consist at least in part of cations derived from a weak monoacidic base.
  • zeolite crystalline aluminosilicate
  • Such a zeolite may readily be prepared by ion exchange from a sodium zeolite, and for convenience will be referred to as an ion-exchanged zeolite, although in principle the invention would also encompass the use of directly synthesised wholly non-sodium zeolites not prepared by ion-exchange, to the extent that such materials can be prepared.
  • Zeolites capable of ion exchange are represented by the following general formula:
  • M is a monovalent cation.
  • the ratio of silicon to aluminium (y:x) can vary, as can the amount of water of hydration.
  • a partially exchanged zeolite may be represented as:
  • M 1 and M 2 are two different exchangeable monovalent cations.
  • x and x' can be determined by conventional analytical methods, for example, atomic absorption spectroscopy.
  • Preferred cations M 1 for the zeolites used in the present invention are ammonium, lithium and hydrogen. Zeolites in hydrogen and ammonium form are preferred, and zeolites in hydrogen form are especially preferred. Potassium ions, derived from a strong base, have been found to have the opposite effect, potassium zeolites giving worse stability of moisture-sensitive ingredients than the corresponding sodium zeolites.
  • the preferred cation M 2 is sodium.
  • the value of x' is best determined by difference between the aluminium content (x) and the second cation (M 2 ) content.
  • the zeolite may be of any crystal form suitable for detergents use. As indicated previously, zeolite A is the most popular detergent zeolite. The art also discloses the possible use of zeolites X, Y and P(B) although in practice those have not found favour because their calcium ion exchange is either inadequate or too slow.
  • Zeolite A has the advantage of being a "maximum aluminium" structure containing the maximum possible proportion of aluminium to silicon (or the minimum possible
  • Si:Al ratio of 1.0 so that its capacity for taking up calcium ions from aqueous solution is intrinsically greater than those of zeolite X, Y and P which generally contain a lower proportion of aluminium (or have a higher Si:Al ratio).
  • the partially or wholly ion-exchanged zeolite is zeolite A.
  • the partially or wholly ion-exchanged zeolite may be zeolite MAP as described and claimed in EP 384 070B (Unilever) as discussed above.
  • This is maximum aluminium zeolite P that is to say, zeolite P having a Si:Al ratio not greated than 1.33, preferably not greater than 1.15 and more preferably not greater than 1.07.
  • Zeolite MAP has various advantages over zeolite A, one of which is that, even in sodium form, it improves the stability of sodium percarbonate and various other bleach ingredients stability as discussed previously.
  • Ion-exchanged zeolites are described in the literature, for example, by D W Breck and E M Flanagan, "Molecular Sieves", Soc Chem Ind (London), 1968, pages 47-61; US 4 346 067 (Exxon Corporation) describes ammonium-exchanged zeolites, and EP 223 396A (Mobil Oil Corporation) describes hydrogen-exchanged zeolites, both useful as catalysts in hydrocarbon conversion reactions.
  • zeolite MAP in ion-exchanged form is believed to be a novel material and is claimed as part of the present invention.
  • the zeolites should desirably be in the ion-exchanged form to an extent of at least 5%, preferably at least 10% and more preferably at least 20 wt%, in order for the benefit of improved moisture-sensitive ingredient stability to be fully realised. Greater extents of ion- exchange do not appear to give further improvements, but neither does the benefit fall again.
  • the zeolites used in accordance with the present invention should preferably be in ion-exchanged form to an extent of at least 5%, more preferably at least 10% and most preferably at least 20%.
  • Zeolite A has been found to give good results when in 10- 50% ion-exchanged form, more especially 20-50% ion-exchanged form, while zeolite MAP has been found to give good results when in 10-90% ion-exchanged form, more especially 20-90% ion- exchanged form.
  • the ion-exchanged zeolite may conveniently be prepared by immersing the corresponding sodium zeolite in an aqueous solution of a salt of the desired cation, for example, an ammonium or lithium salt.
  • a salt of the desired cation for example, an ammonium or lithium salt.
  • Hydrogen-exchanged zeolites may be prepared similarly, by immersion in a aqueous solution of a strong acid, for example, hydrochloric acid.
  • the percentage extent of exchange can be controlled by varying the concentration of the salt or acid, and the amount of zeolite added, as described in more detail by D W Breck et al in JACS 18. 5963 et seq (1956).
  • compositions of the invention are provided.
  • the detergent, bleaching or cleaning compositions of the invention containing a builder system based on crystalline aluminosilicate (zeolite), and also contain at least one moisture-sensitive ingredient. While the invention is believed to be applicable to any moisture-sensitive ingredient, initial work has been concentrated on moisture- sensitive bleach ingredients.
  • zeolite crystalline aluminosilicate
  • moisture-sensitive bleach ingredients include peroxy bleach compounds, for example, inorganic or organic persalts and peroxyacids, bleach activators (bleach precursors), and bleach catalysts.
  • Inorganic persalts include the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates.
  • Inorganic persalts susceptible to moisture, to which the present invention is especially applicable, include sodium perborate monohydrate, and, more especially, sodium percarbonate.
  • Inorganic persalts may advantageously be used in conjunction with a bleach precursor or bleach activator.
  • Bleach precursors may themselves be susceptible to moisture and their stability therefore improved by means of the present invention.
  • a bleach stabiliser may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark) , EDTMP.
  • EDTA ethylenediamine tetraacetate
  • Dequest Trade Mark
  • EDTMP Dequest precursors
  • Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
  • peroxyacid bleach precursors suitable for use in the present invention include:
  • SPCC 2- (N,N,N-trimethylammonium) ethyl sodium-4- sulphophenyl carbonate chloride
  • CSPC cholyl-p-sulphophenyl carbonate
  • SNOBS sodium nonanoyloxybenzene sulphonate
  • Peroxyacids to which the invention is applicable may be organic or inorganic.
  • Organic peroxyacids normally have the general formula
  • R is an alkylene or substituted alkylene group containing from 1 to 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a carboxylic acid or percarboxylic acid group, or a quaternary ammonium group.
  • Typical monoperoxy acids useful in the compositions of the invention include, for example:
  • aliphatic, substituted aliphatic and arylalkyi monoperoxyacids eg peroxylauric acid, peroxystearic acid and N,N'-phthaloylaminoperoxy caproic acid (PAP);
  • Typical diperoxyacids useful in the compositions of the invention include, for example:
  • EP 458 397A and EP 458 398A Unilever
  • the bleach catalyst is defined as comprising a source of Mn and/or Fe ions and a ligand which is a macrocyclic organic compound of formula I:
  • TACN 1,4,7-triazacyclononane
  • 1,4,7-trimethyl-l,4,7- triazacyclononane (1,4,7-Me -,TACN) .
  • the aforementioned ligands may be synthesised by the methods described in K. Wieghardt et al., Inorganic Chemistry 1982, 21, page 3086.
  • the source of iron and/or manganese ions and ligand may be added separately or in the form of a mono-, di- or tetranuclear manganese or iron complex.
  • the ligand may be in the form of an acid salt such as 1,4,7-Me 3 TACN hydrochloride.
  • the source of iron and manganese ions may be a water soluble salt such as iron or manganese nitrate, chloride, sulphate or acetate or a coordination complex such as manganese acetylacetonate.
  • the source or iron and/or manganese ions should be such that the ions are not too tightly bound, ie all those sources from which the ligand of formula (I), as hereinbefore defined, may extract the Fe and Mn in a wash liquor.
  • Preferred mononuclear complexes have the formula
  • At least two R radicals may also be connected to one another so as to form a bridging unit between two oxygens that coordinate with the manganese;
  • L is a ligand of formula (I) as hereinbefore defined
  • Y is an oxidatively-stable counterion
  • Mn can be either in the II, III or IV oxidation state
  • each X independently represents a coordinating species with the exception of RO-, such as CI “ , Br ⁇ , I “ , F “ , NCS “ N 3 ⁇ , l 3 -, NH 3 , RCOO “ , RS0 3 “ , RS0 4 " in which R is alkyl or aryl, both optionally substituted, OH “ , O, 2” , HOO “ , H 2 0, SH, CN “ , OCN “ , S 4 2” and mixtures thereof;
  • RO- such as CI “ , Br ⁇ , I “ , F “ , NCS “ N 3 ⁇ , l 3 -, NH 3 , RCOO “ , RS0 3 “ , RS0 4 " in which R is alkyl or aryl, both optionally substituted, OH “ , O, 2" , HOO “ , H 2 0, SH, CN “ , OCN “ , S 4 2” and mixtures thereof;
  • p is an integer from 1-3;
  • z denotes the charge of the complex and is an integer which can be positive, zero or negative;
  • Y is a counterion the type of which is dependent upon the charge z of the complex
  • L is a ligand as hereinbefore defined.
  • Preferred dinuclear complexes have the formula
  • Mn is manganese which can independently be in the III or IV oxidation state
  • X is independently a coordinating or bridging species selected from the group consisting of H 2 0, 0 2 , OH “ , HO 2 ' SH-, S 2" , >SO, CI “ , SCN “ , N 3 " , RS0 3 “ , RCOO “ , NH 2 " and NR 3 , with R being H, alkyl, aryl, both optionally substituted, and R ⁇ OO, where R 1 is an alkyl or aryl radical, both optionally substituted;
  • L is a ligand of formula (I) as hereinbefore defined
  • z denotes the charge of the complex and is an integer which can be positive or negative, or is zero;
  • Y is a monovalent or multivalent counterion, leading to charge neutrality, which is dependent upon the charge z ofthe complex
  • the bleach catalyst is advantageously in the form of granules as described and claimed in our British Patent Application No. 93 18296.2 filed on 3 September 1993. These granules comprise:
  • a soluble core material preferably selected from sodium bicarbonate, magnesium and potassium nitrates, and magnesium sulphate,
  • binding agent selected from silicone oils, fatty acids, fatty esters, tri-, di- and monoglycerides, waxes and solid hydrocarbons.
  • a binding agent selected from silicone oils, fatty acids, fatty esters, tri-, di- and monoglycerides, waxes and solid hydrocarbons.
  • An especially preferred binding agent is cetostearyl stearate.
  • these granules will also comprise an inert solid.
  • Preferred inert materials include silicas such as Gasil, Aerosil and Sorbosil (Trade Marks); clays such as kaolin; alumina; and titanium dioxide.
  • the bleach catalyst may be in the form of granules as described and claimed in our copending application EP 544 440A filed on 18 November 1992 and published on 2 June 1993. These granules comprise:
  • a binding agent selected from water-soluble non-oxidisable polymers, alkali metal silicates, saturated fatty acid soap mixtures, and combinations of these.
  • a preferred binding agent is sodium silicate, and a preferred inert salt is sodium carbonate.
  • Preferred granules include catalyst/sodium stearate/lauric acid granules, and catalyst/sodium carbonate/sodium silicate/zeolite granules.
  • the manganese catalyst within the granules is of an average particle size as small as possible, preferably below 250 micrometres for proper distribution and to ensure fast delivery to the wash, although particles which are too small may cause handling problems during the granulation process.
  • a preferred and optimum manganese catalyst particle size is within a range of from 50 to 150 micrometres.
  • composition of the invention may, for example, be a detergent additive wholly or predominantly constituted by aluminosilicate builder and one or more moisture-sensitive bleach ingredients.
  • An additive of this type may be used in conjunction with a conventional product under conditions where high water- hardness and/or a heavily soiled load require extra building and/or extra bleaching capacity.
  • Such an additive may also form part of a Baukasten (building block) system, for example, as described in
  • EP 419 036A Unilever
  • EP 419 036A Unilever
  • composition of the invention may alternatively be a particulate detergent composition, which may suitably contain the following ingredients:
  • a builder system comprising a crystalline aluminosilicate as defined above, (c) one or more ingredients sensitive to moisture,
  • Detergent compositions of the invention containing moisture-sensitive bleach ingredients may suitably contain the following ingredients:
  • Preferred detergent compositions according to the invention may contain the following ingredients in the following proportions:
  • the bleach ingredient sensitive to moisture may be, as previously indicated, a persalt, a bleach precursor, a peroxyacid or a bleach catalyst; more particularly, sodium percarbonate, a peroxyacid, or a bleach catalyst as defined above.
  • 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.
  • suitable 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 C 8 -C 20 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 9 -C 15 primary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • non-ethoxylated nonionic surfactants for example, alkylpolyglycosides; O-alkanoyl glucosides as described in EP 423 968A (Unilever) ; and polyhydroxyamides.
  • detergent-active compound surfactant
  • amount present will depend on the intended use of the detergent composition: different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
  • the total amount of surfactant present will also depend on the intended end use, but may generally range from 2 to 60 wt%, preferably from 5 to 40 wt%.
  • Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap.
  • the detergent compositions of the invention also contains one or more detergency builders.
  • the total amount of detergency builder in the compositions will suitably range from 10 to 80 wt%.
  • the detergency builder system of the compositions of the invention is based on zeolite, optionally in conjunction with one or more supplementary builders.
  • the amount of zeolite present may suitably range from 5 to 60 wt%, more preferably from 15 to 40 wt%, calculated on an anhydrous basis (equivalent to from 6 to 75 wt%, preferably from 19 to 50 wt%, calculated on a hydrated basis) .
  • the zeolite may, if desired, be used in conjunction with other inorganic or organic builders.
  • Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever) .
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenyl alonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
  • polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates,
  • Preferred supplementary builders for use in conjunction with zeolite include citric acid salts, more especially sodium citrate, suitably used in amounts of from 3 to 20 wt%, more preferably from 5 to 15 wt%.
  • citric acid salts more especially sodium citrate
  • the combination of zeolite MAP with citrate as a detergency builder system is described and claimed in EP 448 297A (Unilever) .
  • polycarboxylate polymers more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, especially from 1 to 10 wt%, of the detergent composition; the combination of zeolite MAP with polymeric builders is described and claimed in EP 502 675A (Unilever) .
  • the bleach system is described and claimed in EP 502 675A (Unilever) .
  • the detergent compositions of the invention may contain a bleach system which includes at least one moisture-sensitive ingredient.
  • the bleach system may generally comprise a peroxy bleach compound, for example, an inorganic or organic persalt, optionally in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures; or an inorganic or organic peroxyacid.
  • a bleach stabiliser (heavy metal sequestrant) may also be present.
  • a bleach catalyst as previously defined may also be present.
  • Preferred inorganic persalts are sodium perborate monohydrate and sodium percarbonate. As indicated above, sodium percarbonate is especially sensitive to moisture and benefits particularly from the present invention.
  • sodium percarbonate or other persalts may suitably be present in an amount of from 5 to 30 wt%, preferably from 10 to 25 wt%, based on the whole composition.
  • Bleach precursors are suitably used in amounts of from 1 to 8 wt%, preferably from 2 to 5 wt%.
  • Organic or inorganic peroxyacids are normally used in an amount within the range of from 2 to 10 wt%, preferably from 4 to 8 wt%.
  • the amount of the bleach catalyst described above present in the detergent compositions of the invention is suitably from 0.02 to 0.08 wt%.
  • Other ingredients are suitably from 0.02 to 0.08 wt%.
  • detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; fluorescers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; pigments; and perfumes. This list is not intended to be exhaustive.
  • the particulate detergent compositions of the invention may be prepared by any suitable method.
  • One suitable method comprises spray-drying a slurry of compatible heat-insensitive ingredients, including the zeolite, any other builders, and at least part of the detergent-active compounds, and then spraying on or postdosing those ingredients unsuitable for processing via the slurry, including sodium percarbonate and any other bleach ingredients.
  • compatible heat-insensitive ingredients including the zeolite, any other builders, and at least part of the detergent-active compounds
  • spraying on or postdosing those ingredients unsuitable for processing via the slurry including sodium percarbonate and any other bleach ingredients.
  • the skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
  • compositions of the invention may also be prepared by wholly non-tower procedures, for example, dry-mixing and granulation, or by so-called "part-part" processes involving a combination of tower and non-tower processing steps.
  • 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 EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever) .
  • Sodium zeolite 4A powder (Wessalith (Trade Mark) P ex Degussa) was converted to a partially ammonium-exchanged form as follows.
  • the calculated ammonium (NH,) content for full exchange of zeolite A is 10.0 wt% NH 4 .
  • the material prepared as described above had an ammonium (NH 4 ) content of 5.04 wt%, corresponding to 50.4% exchange.
  • Ammonium-exchanged zeolite MAP was prepared, by the method described in Example 1, from sodium zeolite MAP prepared by a method similar to that described in Examples 1 to 3 of EP 384 070A (Unilever) .
  • the starting zeolite MAP had a silicon to aluminium ratio of 1.0.
  • the calculated ammonium content for full exchange of zeolite MAP is 10.4 wt%.
  • the exchanged material had an ammonium (NH 4 ) content of 7.95 wt%, corresponding to 76.4% exchange.
  • Sodium zeolite 4A was converted to (partially) lithium- exchanged form by a method similar to that used in Example 1, using 0.2 molar lithium chloride solution instead of ammonium sulphate solution.
  • Lithium zeolite MAP was prepared from the sodium zeolite MAP used in Example 2, by the method described in Example 3.
  • Example 5 Lithium zeolite MAP was prepared from the sodium zeolite MAP used in Example 2, by the method described in Example 3.
  • the dried zeolite was ground in a pestle and mortar and stored under ambient conditions for several days to rehydrate fully.
  • Partially hydrogen-exchanged zeolite MAP was prepared from the sodium zeolite MAP used in Example 2 by the method described in Example 5.
  • Partially potassium-exchanged zeolite A was prepared from the sodium zeolite A used in Example 1 by the method described in Example 3, except that the lithium chloride solution was replaced by 0.2 molar potassium chloride solution. Comparative Example B
  • Partially potassium-exchanged zeolite MAP was prepared from the sodium zeolite MAP used in Example 2 by the method described in Example 4, except that the lithium chloride solution was replaced by 0.2 molar potassium chloride solution.
  • Test samples were prepared by mixing 3.75 g of each of the following zeolites with 1.25 g of sodium percarbonate (the 500-710 micrometre sieve fraction of Oxyper (Trade Mark) ex Interox) , to give mixtures consisting of 75 wt% zeolite and 25 wt% percarbonate.
  • sodium percarbonate the 500-710 micrometre sieve fraction of Oxyper (Trade Mark) ex Interox
  • ammonium-exchanged, lithium- exchanged and hydrogen-exchanged zeolites all greatly improved the storage stability of the sodium percarbonate, the ammonium-exchanged material giving the largest benefit; while the potassium-exchanged material gave rather worse results than the all-sodium zeolite.
  • Test samples were prepared as described in Examples 15 to 17, each containing 3.75 g (75 wt%) of zeolite and 1.25 g (25 wt%) of sodium percarbonate:
  • ammonium zeolite MAP (Example 18) resulted in virtually no percarbonate loss even after 14 days' open storage in very unfavourable conditions.
  • Detergent granules were prepared by granulating zeolite with nonionic surfactant in a laboratory-scale granulator, using in each case just sufficient nonionic surfactant to achieve granulation.
  • the nonionic surfactant used was Synperonic (Trade Mark) A7 ex ICI, a C 12 -C 15 primary alcohol ethoxylated with an average of 7 moles of ethylene oxide per mole of alcohol.
  • the zeolites used were the ammonium-exchanged zeolites of Examples 1 and 2, and the corresponding sodium zeolites (the starting materials used in Examples 1 and 2).
  • the compositions of the granules were as follows:
  • test samples were sieved, and the 250-700 micrometre fraction was used in the test described below to determine percarbonate storage stability.
  • Each test sample was prepared by mixing detergent granules (8.75 g) with sodium percarbonate (1.25 g) .
  • the percentage compositions of the test samples were therefore as follows:
  • Detergent base powders were prepared by mixing zeolite A, in sodium or ion-exchanged form, with a liquid surfactant blend - coconut alcohol sulphate (cocoPAS) , coconut alcohol 3E0 nonionic surfactant, coconut alcohol 7E0 nonionic surfactant and water - in a laboratory-scale granulator.
  • zeolite A in sodium or ion-exchanged form
  • a liquid surfactant blend - coconut alcohol sulphate (cocoPAS) coconut alcohol 3E0 nonionic surfactant
  • coconut alcohol 7E0 nonionic surfactant coconut alcohol 7E0 nonionic surfactant
  • the zeolites were as used in previous Examples: the ammonium zeolite A was that of Example 1, and the sodium zeolite the raw material of Example 1. The differences in formulation reflect the different carrying capacities of the two zeolites.
  • the base powders were mixed with manganese catalyst granules to give powders having the following formulations:
  • the catalyst granules had the following formulation:
  • Example 31 showed slight discoloration, while the powder of Comparative Example L was quite badly discoloured.
  • panellists allocated the following discoloration scores:
  • Detergent base powders were prepared by mixing zeolite MAP, in sodium or ion-exchanged form, with the liquid surfactant blend used in Examples 31 and L, in a laboratory- scale granulator.
  • the ammonium-exchanged zeolite MAP was that of Example 2, and the sodium zeolite MAP the raw material of Example 2. Again, the differences between the formulations reflect the different carrying capacities of the two zeolites.
  • the base powders were mixed with manganese catalyst granules to give powders having the following formulations:
  • the powder of Comparative Example M (containing sodium zeolite MAP) was significantly less discoloured that the powder of Comparative Example L (containing sodium zeolite A), the discoloration score being 2.
  • Example 33 contained 95 wt% of the base powder of Example 31 (ammonium-exchanged zeolite A)
  • Comparative Example N contained 95 wt% of the base powder of Comparative Example A (sodium zeolite A) .
  • Each powder also contained 5 wt% of the catalyst granules. Storage tests were carried out as in earlier Examples, and the panel assessment results were as follows:
  • Example 34 ammonium-exchanged zeolite MAP
  • Example P sodium zeolite MAP
  • Example 34 contained 95 wt% of the base powder of Example 32 (ammonium-exchanged zeolite MAP)
  • Comparative Example P contained 95 wt% of the base powder of Comparative Example M (sodium zeolite MAP)
  • Each powder also contained 5 wt% of the catalyst granules. Storage tests were carried out as in earlier Examples, and the panel assessment results were as follows:
  • Panellists showing a preference for Powder 34 7 Panellists showing a preference for Powder P 1
  • the discoloration scores were as follows:
  • This Example describes an accelerated storage test to show the effect of zeolite type on the decomposition of the manganese catalyst Mn l,4,7-Me 3 TACN.
  • the catalyst not in granular form, was in direct contact with zeolitic base powder.
  • Crystalline catalyst (0.26 g) was granulated with 7EO nonionic surfactant (3 g) and zeolite (10 g) to give the following compositions:
  • the granules were stored at 37°C and 70% relative humidity and their colour assessed visually at regular time intervals.
  • Comparative Example Q showed significant levels of brown discoloration after 24 hours' storage.
  • the granules of Example 35 showed no discoloration even after 7 days' storage.

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Abstract

Des compositions nettoyantes, détersives ou de blanchiment particulaires contenant des ingrédients sensibles à l'humidité, par exemple des ingrédients de blanchiment, ainsi que de l'aluminosilicate cristallin (du zéolite), peuvent présenter un accroissement notable de la stabilité desdits ingrédients sensibles à l'humidité, en particulier du percarbonate de sodium ou de certains catalyseurs de blanchiment, dans la mesure où les cations échangeables de l'aluminosilicate cristallin comprennent des cations d'une base monoacide faible tels que des ions d'ammonium, de lithium ou d'hydrogène.
PCT/EP1994/001115 1993-04-19 1994-04-07 Compositions nettoyantes ou de blanchiment particulaires contenant des aluminosilicates WO1994024251A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU65669/94A AU684769B2 (en) 1993-04-19 1994-04-07 Particulate bleaching or cleaning compositions containing aluminosilicates
CA002155852A CA2155852C (fr) 1993-04-19 1994-04-07 Compositions detergentes, javellisantes ou nettoyantes en poudre contenant des aluminosilicates
EP94913571A EP0695341B1 (fr) 1993-04-19 1994-04-07 Compositions nettoyantes ou de blanchiment particulaires contenant des aluminosilicates
SK1036-95A SK281006B6 (sk) 1993-04-19 1994-04-07 Časticová detergentná, bieliaca alebo čistiaca zmes
DE69407405T DE69407405T2 (de) 1993-04-19 1994-04-07 Teilchenförmige, alumosilikathalige bleich- oder reinigungsmittelzusammensetzungen
PL94311163A PL177828B1 (pl) 1993-04-19 1994-04-07 Ziarnista kompozycja detergentowa, bieląca lub czyszcząca
BR9406174A BR9406174A (pt) 1993-04-19 1994-04-07 Composição detergente particulada alvejante ou de limpeza zeolito e uso de um aluminossilicato cristalino

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB939308047A GB9308047D0 (en) 1993-04-19 1993-04-19 Particulate detergent,bleaching or cleaning compositions containing aluminosilicates
GB9308047.1 1993-04-19

Publications (1)

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EP (1) EP0695341B1 (fr)
JP (1) JP2677710B2 (fr)
AU (1) AU684769B2 (fr)
BR (1) BR9406174A (fr)
CA (1) CA2155852C (fr)
CZ (1) CZ290131B6 (fr)
DE (1) DE69407405T2 (fr)
ES (1) ES2110232T3 (fr)
GB (1) GB9308047D0 (fr)
HU (1) HU217991B (fr)
IN (1) IN181903B (fr)
MY (1) MY116334A (fr)
PL (1) PL177828B1 (fr)
SK (1) SK281006B6 (fr)
TW (1) TW333556B (fr)
WO (1) WO1994024251A1 (fr)
ZA (1) ZA942679B (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2299097A (en) * 1995-03-24 1996-09-25 Procter & Gamble Detergent composition
WO2001004246A1 (fr) * 1999-07-09 2001-01-18 Colgate-Palmolive Company Composition de nettoyage d'etoffes, contenant une zeolithe
US6235704B1 (en) 1997-07-30 2001-05-22 Basf Aktiengesellschaft Solid textile detergent formulation based on glycin-N and N-Diacetic acid derivatives
US6492321B2 (en) 1999-12-08 2002-12-10 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent bar comprising amorphous silica and salt of carboxylic and/or sulphonic acid
WO2003093405A2 (fr) * 2002-05-02 2003-11-13 The Procter & Gamble Company Compositions detergentes et composants de ces compositions
WO2010070088A1 (fr) 2008-12-18 2010-06-24 Basf Se Mélange de tensioactifs contenant des composants ramifiés à chaîne courte et des composants ramifiés à chaîne longue
WO2011003904A1 (fr) 2009-07-10 2011-01-13 Basf Se Mélange de tensioactifs contenant des constituants à chaîne courte et à chaîne longue
WO2011117350A1 (fr) 2010-03-25 2011-09-29 Basf Se Procédé électrochimique de nettoyage de textiles
US9435073B2 (en) 2010-03-25 2016-09-06 Basf Se Electrochemical textile-washing process
EP3089820A4 (fr) * 2013-12-31 2017-11-22 EcoWater Systems, LLC Régénération de zéolite
US11441105B2 (en) 2017-12-15 2022-09-13 Rhodia Operations Composition containing lanthanide metal complex

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2013259A (en) * 1978-01-25 1979-08-08 Kao Corp Bleaching detergent composition
JPS5626715A (en) * 1979-08-07 1981-03-14 Mizusawa Ind Chem Ltd Manufacture of zeolite builder having superior dispersibility
US4389325A (en) * 1982-01-25 1983-06-21 Monsanto Company Chloroisocyanurate compositions

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JPS54100406A (en) * 1978-01-25 1979-08-08 Kao Corp Bleaching detergent composition comprising aluminosilicate
ZA805231B (en) * 1980-05-19 1981-08-26 Mobil Oil Corp Low acidity alkali metal containing zeolites
JPS6291240A (ja) * 1985-06-05 1987-04-25 Toyo Soda Mfg Co Ltd モルデナイトのリチウムイオン交換方法
GB8823705D0 (en) * 1988-10-10 1988-11-16 Unilever Plc Liquid detergent products
ES2100924T3 (es) * 1990-05-21 1997-07-01 Unilever Nv Activacion de blanqueador.
JPH04219135A (ja) * 1990-12-19 1992-08-10 Kobe Steel Ltd 分子篩性吸着材
GB9104547D0 (en) * 1991-03-05 1991-04-17 Unilever Plc Detergent compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2013259A (en) * 1978-01-25 1979-08-08 Kao Corp Bleaching detergent composition
JPS5626715A (en) * 1979-08-07 1981-03-14 Mizusawa Ind Chem Ltd Manufacture of zeolite builder having superior dispersibility
US4389325A (en) * 1982-01-25 1983-06-21 Monsanto Company Chloroisocyanurate compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Derwent World Patents Index; Class E33, AN 81-31774D *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2299097A (en) * 1995-03-24 1996-09-25 Procter & Gamble Detergent composition
US6235704B1 (en) 1997-07-30 2001-05-22 Basf Aktiengesellschaft Solid textile detergent formulation based on glycin-N and N-Diacetic acid derivatives
WO2001004246A1 (fr) * 1999-07-09 2001-01-18 Colgate-Palmolive Company Composition de nettoyage d'etoffes, contenant une zeolithe
US6492321B2 (en) 1999-12-08 2002-12-10 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent bar comprising amorphous silica and salt of carboxylic and/or sulphonic acid
US6878680B2 (en) 2002-05-02 2005-04-12 Procter & Gamble Detergent compositions and components thereof
WO2003093405A3 (fr) * 2002-05-02 2004-04-08 Procter & Gamble Compositions detergentes et composants de ces compositions
WO2003093405A2 (fr) * 2002-05-02 2003-11-13 The Procter & Gamble Company Compositions detergentes et composants de ces compositions
CN1326983C (zh) * 2002-05-02 2007-07-18 宝洁公司 洗涤剂组合物及其组分
WO2010070088A1 (fr) 2008-12-18 2010-06-24 Basf Se Mélange de tensioactifs contenant des composants ramifiés à chaîne courte et des composants ramifiés à chaîne longue
WO2011003904A1 (fr) 2009-07-10 2011-01-13 Basf Se Mélange de tensioactifs contenant des constituants à chaîne courte et à chaîne longue
WO2011117350A1 (fr) 2010-03-25 2011-09-29 Basf Se Procédé électrochimique de nettoyage de textiles
US9435073B2 (en) 2010-03-25 2016-09-06 Basf Se Electrochemical textile-washing process
EP3089820A4 (fr) * 2013-12-31 2017-11-22 EcoWater Systems, LLC Régénération de zéolite
US11441105B2 (en) 2017-12-15 2022-09-13 Rhodia Operations Composition containing lanthanide metal complex

Also Published As

Publication number Publication date
PL177828B1 (pl) 2000-01-31
CZ243095A3 (en) 1996-01-17
TW333556B (en) 1998-06-11
ES2110232T3 (es) 1998-02-01
SK281006B6 (sk) 2000-10-09
SK103695A3 (en) 1995-12-06
ZA942679B (en) 1995-10-19
AU684769B2 (en) 1998-01-08
HU9501986D0 (en) 1995-09-28
JP2677710B2 (ja) 1997-11-17
GB9308047D0 (en) 1993-06-02
DE69407405D1 (de) 1998-01-29
HUT73065A (en) 1996-06-28
CA2155852A1 (fr) 1994-10-27
PL311163A1 (en) 1996-02-05
CA2155852C (fr) 1999-05-11
EP0695341B1 (fr) 1997-12-17
MY116334A (en) 2004-01-31
AU6566994A (en) 1994-11-08
EP0695341A1 (fr) 1996-02-07
JPH08504876A (ja) 1996-05-28
HU217991B (hu) 2000-05-28
CZ290131B6 (cs) 2002-06-12
DE69407405T2 (de) 1998-04-09
IN181903B (fr) 1998-10-31
BR9406174A (pt) 1996-01-09

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