SK281006B6 - Particulate bleaching or cleaning compositions - Google Patents

Abstract

Particulate detergent, bleaching or cleaning compositions containing moisture-sensitive ingredients, for example bleach ingredients, and also containing crystalline aluminosilicate (zeolite), whilst at least 5 wt.% of the exchangeable cations of the crystalline aluminosilicate include cations of a weak monoacidic base, for example, ammonium, lithium or hydrogen ions.

Description

The invention relates to particulate detergent, bleaching or cleaning compositions which contain crystalline aluminosilicates (zeolites) and also contain moisture-sensitive components, in particular bleaching components, for example inorganic peroxy salts, such as sodium percarbonate, organic and inorganic peracids, bleach precursors or bleach catalysts .

BACKGROUND OF THE INVENTION

The ability of crystalline aluminosilicates (zeolites) to sequester calcium ion from aqueous solutions by an ion exchange mechanism has made them a well-known substitute for phosphates as a detergent component. Many particulate detergent compositions currently marketed in Europe, Japan and the USA contain zeolites.

Although many crystalline forms of zeolites are known, zeolites A in sodium form have always been preferred zeolites for use as detergents.

Examples of prior art documents describing detergent compositions containing zeolites are EP456 515A (Procter & Gambia), EP38 591A and EP 21 491A (Procter & Gambia), EP 87 O35A (Union Carbide), US 4,604,224 and CA 1,072,853 ( Colgate). The use of zeolites A, X, B (P) and Y is known and given the general composition of formulations with a range of possible cations, but the sodium cation is always a highly preferred cation and all specific descriptions refer to zeolites in sodium form.

Sodium percarbonate is a well known bleach component in bleach and detergent compositions and is widely described in the literature, although its use in commercial products has been replaced in recent years in favor of sodium perborate. Sodium percarbonate is less stable in the presence of moisture than sodium perborate and its stabilization in detergent powders has long been considered a problem. This problem becomes particularly acute if sodium percarbonate is to be incorporated in detergent powders with a high mobile water content, where it tends to deactivate upon storage. This situation is particularly true for zeolite-containing powders, since these materials contain a large amount of relatively mobile water.

This problem is solved in GB 2 013 259A (Kao), which proposes as one solution the use of zeolite in which the sodium cations have been partially replaced by calcium or magnesium ions. This measure improves the stability of sodium percarbonate, but at the expense of reduced detergency (ion exchange of calcium and magnesium). An alternative approach to the stability problem of sodium percarbonate in zeolite-containing particulate detergent compositions is described in EP 522 726A (Unilever) according to which conventional zeolite A is replaced by maximum aluminum zeolite P (zeolite MAP), a material described and claimed in EP 384 070A (Unilever). The use of this zeolite provides a significant improvement in the storage stability of sodium percarbonate.

A similar improvement in storage stability has been observed for sodium perborate monohydrate as described in EP 552 053 (Unilever); bleach precursors as described in EP 552 054A (Unilever); peracids as described in U.S. Pat. EP / 93/03369 filed November 29, 1993 and published as WO 94/13773 A (Unilever).

The present invention is based on the discovery that a further significant improvement in the storage stability of sodium percarbonate and other moisture sensitive ingredients in zeolite-containing particulate detergent and cleaning compositions can be achieved by using zeolites in which the sodium ions have been fully or partially exchanged for other cations. This is surprising because the ion-exchanged forms generally have no lower moisture content than their sodium counterparts, and in this invention fully hydrated forms have been used in environments where there is no limitation on the mobile water content. An improvement is observed for both zeolite A and MAP zeolite.

EP 364 184A (Unilever) discloses non-aqueous cleaning compositions containing dispersed aluminosilicate particles which have been deactivated by treatment with an ammonium or substituted ammonium compound and then heated to reduce the water content below 24% by weight. This treatment reduces the aluminosilicate catalyzed decomposition of bleach precursors such as tetraacetylenediamine in the liquid product. In contrast to the present invention, EP 364 184A deals with an environment (non-aqueous liquid) in which the water content is strictly limited and controlled, and with aluminosilicates which must be partially dehydrated.

SUMMARY OF THE INVENTION

The invention provides a particulate detergent, bleaching or cleaning composition comprising a moisture-sensitive bleaching component and a crystalline silico-silicate having exchangeable cations, wherein the exchangeable aluminosilicate cations include ammonium, lithium or hydrogen ions or combinations thereof.

More specifically, the invention provides a particulate bleaching detergent composition comprising an organic detergent surfactant, a moisture-sensitive bleaching component, and a crystalline silicate silicate wherein the aluminosilicate is as defined in the preceding paragraph.

The invention further provides the use of an aluminosilicate as defined above to improve the stability of the moisture-sensitive bleaching component in the particulate detergent, bleaching or cleaning composition.

The invention further provides as a novel material a zeolite P having a silicon to aluminum ratio not exceeding 1.33, preferably not exceeding 1.15 and more preferably not exceeding 1.07, which has exchangeable cations, wherein the exchangeable cations include ammonium, lithium or hydrogen ions or combinations thereof.

The composition of the invention has two essential components: an aluminosilicate and a moisture sensitive bleaching component.

Ion exchanged zeolite

The compositions of the invention require crystalline aluminosilicate (zeolite) as an essential component in which the exchangeable cations consist at least in part of cations including ammonium, lithium or hydrogen ions or combinations thereof.

Such zeolite can be readily prepared by ion exchange sodium zeolite, and for convenience will be referred to as ion-exchanged zeolite, although in principle the invention should also include the use of directly synthesized non-fully sodium exchanged non-ionic zeolites to the extent such materials can be prepared.

Ion exchange capable zeolites are represented by the following general formula:

M _x (SiO ₂ ) _y (AlO ₂ ) _x .zH ₂ O,

Wherein M is a monovalent cation. The ratio of silicon to aluminum (y: x) can vary, as can the amount of hydration water.

Zeolites with partially exchanged cations can be represented as:

M'xMV _{t ') (SiO2) y} (A10 _{2) x} .zH ₂ 0, wherein M ¹ and M ² are two different exchangeable monovalent cations.

Thus, the percentage (mole) of exchange shown below can be defined for the cation M ¹ as - x 100.

X

The values of x and x 'may be determined by conventional analytical methods, for example by atomic absorption spectroscopy.

Preferred M ¹ cations for the zeolites used in this invention are ammonium, lithium and hydrogen cations. Zeolites in hydrogen and ammonium form are preferred and zeolites in hydrogen form are particularly preferred. Potassium ions derived from a strong base have been found to have the opposite effect, potassium zeolites giving less stability to the moisture-sensitive components than the corresponding sodium zeolites.

A preferred cation of M ² is sodium.

If M ¹ is a hydrogen ion, the value x 'is best defined by the difference between the content of aluminum (x) and the content of the second cation (M ² ).

The zeolite may be in any crystalline form suitable for use in detergents. As previously indicated, zeolite A is the most popular detergent zeolite. The possible use of zeolites X, Y and P (B) is also described in this field, although in practice they have not found favor because their cation exchange with calcium is either inadequate or too slow.

Zeolite A has the advantage that it has a maximum aluminum structure which contains the maximum possible ratio of aluminum to silicon (or a minimum possible Si: Al ratio of 1.0) and thus its capacity to capture calcium ions from the aqueous solution is internally greater than capacity of zeolites X, Y and P, which generally contain a smaller proportion of aluminum (or have a higher Si: Al ratio).

Accordingly, in one preferred embodiment of the invention, the partially or totally ion-exchanged zeolite is zeolite A.

Alternatively and most preferably, the partially or totally ion-exchanged zeolite may be a zeolite MAP as described and claimed in EP 384 070B (Unilever). This is the maximum aluminum zeolite P, that is, a zeolite P with a Si: Al ratio not greater 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 the stability of various other bleaching ingredients, as discussed above.

Ion exchange zeolites are described in the literature, for example D.W. Breck and E.M. Flanagan, Molecular Sieves, Soc. Chem. Ind. (London), 1968, pages 47 to 61; US 4,346,067 (Exxon Corporation) discloses ammonium exchanged zeolites and EP 223 396A (Mobil Oil Corporation) discloses hydrogen exchanged zeolites, both useful as catalysts in hydrocarbon conversion reactions.

However, zeolite MAP in ion-exchanged form is believed to be a novel material and is claimed as part of this invention.

Scope of exchange

It seems that the zeolites should suitably be in the ion-exchange form in the range of at least 5%, preferably at least 10% and more preferably at least 20% in order to fully realize the improved stability of the moisture-sensitive component. Larger ion exchange ranges do not provide further improvement, but this benefit does not decrease again.

Accordingly, the zeolites used in the present invention should preferably be in an ion-exchanged form in the range of at least 5%, more preferably at least 10% and most preferably at least 20%.

It has been found that zeolite A gives good results in a form with an exchange range of 10 to 50%, more preferably in a form with an exchange range of 20 to 50%, while zeolite MAP has been found to give good results when in a form with an exchange range of 10 to 50%. up to 90%, more preferably in a form with an exchange range of 20 to 90%.

The lower bounds herein are specifically applicable to ammonium exchanged zeolites. The corresponding boundary for other cations need not necessarily be identical, but could be readily ascertained by one skilled in the art using the methods described in the examples herein.

Preparation of zeolite with exchanged ions

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.

Hydrogen-exchanged zeolites may be similarly prepared by immersion in an aqueous solution of a strong acid such as hydrochloric acid.

The percentage of the exchange range can be controlled by varying the salt or acid concentration and the amount of zeolite added, as described in more detail by D.W. Breck et al. in JACS 78, 5963 etseq (1956). Compositions of the Invention

The detergent, bleach or cleaning compositions of the present invention comprise a crystalline aluminosilicate (zeolite) based detergent system, and also contain at least one moisture sensitive component. While the invention is considered applicable to any moisture sensitive component, the initial work has concentrated on the moisture sensitive bleaching components.

Moisture sensitive bleaching components

Examples of moisture sensitive bleaching ingredients include peroxy bleaches, for example, inorganic or organic peroxy salts and peracids, bleach activators (bleach precursors), and bleach catalysts.

Inorganic peroxo salts

Inorganic persalts include alkali metal perborates, percarbonates, perphosphates, persilicates and persulfates. Inorganic moisture sensitive hypersalts to which this invention is particularly applicable include sodium perborate monohydrate and especially sodium percarbonate.

The inorganic peroxy salts can advantageously be used in conjunction with a bleach precursor or bleach activator. The bleach precursors may themselves be moisture sensitive and their stability can thus be improved by the present invention.

A bleach stabilizer (heavy metal sequestrant) may also be present. Suitable bleach stabilizers include ethylenediaminetetraacetate (EDTA) and polyphosphonates such as Dequest (trade mark), EDTMP.

SK 281006-6

Bleach precursors

Preferred bleach precursors are peroxocarbonyl acid precursors, more particularly peroxoacetic acid precursors and peroxobenzoic acid precursors; and percarbonate precursors.

Examples of peroxyacid bleach precursors suitable for use in the present invention include:

N, N, Ν ', N ¹ - tetraacetylethylenediamine (TAED) 2- (N, N, N-trimethylammonium) ethyl-4-syphophenyl carbonate sodium chloride (SPCC), also known as cholyl-p-sulfophenyl carbonate (CSPC);

sodium nanoyloxybenzenesulfonate (SNOBS);

Sodium 4-benzoyloxybenzenesulfonate (SBOBS);

Sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (STHOBS);

and glucose pentaacetate (GPA).

peroxyacids

The peroxyacids to which this invention is applicable may be organic or inorganic.

Organic peroxyacids normally have the general formula:

ABOUT

II

HOOC-C-R Y, wherein R is an alkylene or substituted alkylene group containing from 1 to 20 carbon atoms, optionally with an internal amide bond; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imidoaromatic or non-aromatic group, a carboxylic acid or peroxocarboxylic acid group, or a quaternary ammonium group.

Typical monoperoxyacids useful in the compositions of the invention include, for example:

(i) a peroxybenzoic acid and a peroxybenzoic acid substituted on the ring, for example, peroxyalphanaftoic acid;

(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxo acids, such as peroxolauric acid, peroxostearic acid and N, N'-phthaloylaminoperoxocaproic acid (PAP);

(iii) 6-octylamino-6-oxyperoxohexanoic acid.

Typical diperoxy acids useful in the compositions of the invention include, for example:

(iv) 1,12-diperoxododecanedioic acid (DPDA);

(v) 1,9-diperoxoazelaic acid;

(vi) diperoxisilic acid, diperoxosebic acid and diperoxoisophthalic acid;

(vii) 2-decyldiperoxobutane-1,4-dioic acid; and (viii) 4,4'-sulfonylbisperoxobenzoic acid.

(ix) N, N'-terephthaloyl-di (6-aminoperoxocaproic acid), also known as N, N'-di (5-percarboxypentyl) terephthalamide (TPCAP).

Bleaching mixtures

For example, the compositions of the present invention may be a detergent additive consisting wholly or predominantly of aluminosilicate and one or more moisture sensitive bleaching components.

An additive of this type can be used in conjunction with conventional products under conditions where high water hardness and / or heavy soiling require increased detergency and / or increased bleaching capacity.

Such an addition may also form part of a modular system, for example as described in EP 419 036A (Unilever), where it may be used together with a poorly detergent and / or non-bleaching main laundry detergent.

Detergent mixtures

The compositions of the present invention may alternatively be particulate detergent compositions which may suitably comprise the following ingredients:

(a) one or more organic surfactants,

(b) a detergent system comprising crystalline aluminosilicate as defined;

(c) one or more moisture-sensitive components,

(d) optionally other detergent ingredients.

The detergent compositions of the present invention containing moisture sensitive bleaching ingredients may suitably comprise the following ingredients:

(a) one or more organic surfactants,

(b) a detergent system comprising crystalline aluminosilicate as defined;

(c) a bleaching system comprising one or more moisture-sensitive components;

(d) optionally other detergent ingredients.

Preferred detergent compositions of the invention may contain the following ingredients in the following amounts:

(a) from 2 to 60% by weight of one or more organic surfactants;

(b) from 10 to 80% by weight of detergent builders, including zeolite in partially or totally ion-exchanged form;

c) from 5 to 40% by weight of a bleaching system comprising a whitening component sensitive to moisture, and (d) optionally other detergent ingredients up to 100% by weight.

The moisture-sensitive bleaching component may be, as previously indicated, a peroxy salt, a bleach precursor, a peracid or a bleach catalyst; more particularly a percarbonate, peracid or bleach catalyst as defined.

Surfactants

The detergent compositions of the present invention will also contain as essential ingredients one or more detergent active (s), which may be selected from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active ingredients and mixtures thereof.

Many detergent active substances 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.

Preferred detergent active agents that can be used are soaps and synthetic non-soap anionic and nonionic agents.

Anionic surfactants are well known to those skilled in the art. Examples include alkylbenzenesulfonates, especially sodium linear alkylbenzenesulfonates having an alkyl chain length of C ₈ -C ₁₅ ; primary and secondary alkyl sulfates, especially sodium sulfates of primary C 12 -C ₁₅ alcohols; alkyl ether; olefin sulphonates; alkyl xylene sulphonates; dialkyl; and fatty acid sulfonate esters. Sodium salts are generally preferred.

Nonionic surfactants which may be used include ethoxylates of primary and secondary alcohols, especially C ₈ -C ₂ primary and secondary aliphatic alcohol

Plain ethoxylated with an average of 1 to 20 moles of ethylene oxide per mole of alcohol, more preferably primary and secondary C ₉ -C ₁₅ alcohols ethoxylated with an average of 1 to 10 moles of ethylene oxide per mole of alcohol.

Also of interest are nonethoxylated nonionic surfactants, for example alkyl polyglycosides; O-alkanoyl glucosides as described in EP 423 968A (Unilever); and polyhydroxyamides.

The choice of detergent (surfactant) and amount used will depend on the intended use of the detergent composition: various surfactant systems may be selected as well known to the skilled detergent builder for handwashing products and for various types of washing machines .

The total amount of surfactant present will also depend on the intended end use, but will generally range from 2 to 60% by weight, preferably from 5 to 40% by weight.

Detergent compositions suitable for use in most automatic fabric washing machines generally comprise anionic non-soap surfactants or nonionic surfactants, or combinations of the two in some proportion, optionally together with soap.

Detergent system

The detergent compositions of the invention also contain one or more detergent ingredients. The total amount of detergent component in the compositions will suitably range from 10 to 80% by weight.

The detergent system of the compositions of the invention is based on zeolite, optionally in conjunction with one or more additional detergent ingredients.

The amount of zeolite present may suitably range from 5 to 60% by weight, more preferably from 15 to 40% by weight, calculated on the anhydrous basis (equivalent to 6 to 75% by weight, preferably from 19 to 50% by weight, calculated on the hydrated basis).

The zeolite can, if desired, be used in conjunction with other inorganic or organic detergent ingredients.

Inorganic detergent builders that may be present include sodium carbonate, if desired with calcium carbonate seed crystals, as described in GB 1 437 950 (Unilever). Organic detergent builders that may further be present include polycarboxylate polymers such as polyacrylates and acrylate / maleate copolymers, and acrylic phosphates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxy succinates, carboxymethyloxy malonates, dipicolinates, hydroxyethyliminodiacetates, alkyl and alkenyl malonates and succinates, and sulfonated fatty acid salts. This list is not exhaustive.

Preferred additional detergent ingredients for use in conjunction with zeolite include salts of citric acid, more preferably sodium citrate, suitably used in an amount of from 3 to 20% by weight, more preferably from 5 to 15% by weight. This combination of zeolite MAP with citrate as a detergent builder system is described and claimed in EP 448 297A (Unilever).

Also preferred are polycarboxylate polymers, more preferably acrylic / maleic copolymers, suitably used in an amount of from 0.5 to 15% by weight, especially from 1 to 10% by weight of the detergent composition; this combination of zeolite MAP with polymeric detergent builders is described and claimed in EP 502 675A (Unilever).

Bleaching system

As previously indicated, the detergent compositions of the invention may comprise a bleaching system comprising at least one moisture-sensitive component. The bleaching system may generally comprise peroxy bleaching agents, for example inorganic or organic peroxy salts, optionally in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures; or inorganic or organic peracids. A bleach stabilizer (heavy metal sequestrant) may also be present. According to a preferred embodiment of the invention, a bleach catalyst as defined above may also be present.

Preferred inorganic persalts are sodium perborate monohydrate and sodium percarbonate. As indicated, sodium percarbonate is particularly sensitive to moisture and the present invention is particularly preferred.

In the detergent compositions of the present invention, sodium percarbonate or other peroxy salts may suitably be present in an amount of from 5 to 30% by weight, preferably from 10 to 25% by weight, based on the total composition.

The bleach precursors are suitably used in amounts of from 1 to 8% by weight, preferably from 2 to 5% by weight.

Organic or inorganic peracids are normally used in an amount ranging from 2 to 10% by weight, preferably from 4 to 8% by weight.

The amount of bleach catalyst described herein is present in the detergent compositions of the present invention suitably from 0.02 to 0.08% by weight.

Other ingredients

Other materials that may be present in the detergent compositions of the invention include sodium silicate; anti-redeposition agents such as cellulosic polymers; fluorescent substances; inorganic salts such as sodium sulfate; where appropriate, suds suppressors or foam enhancers; pigments; and perfumes. This list is not exhaustive.

Preparation of detergent compositions

The particulate detergent compositions of the present invention can be prepared by any suitable method.

One suitable method comprises spray-drying a slurry of compatible thermally insensitive ingredients including zeolite, any other detergent ingredients, and at least a portion of the detergent active agents; and then spraying or post-dosing those ingredients that are unsuitable for slurry processing, including sodium percarbonate and any other bleaching ingredients. A detergent expert will have no difficulty in deciding which ingredients to slurry and which should not.

The compositions of the invention may also be prepared by completely non-tower processes, for example by dry mixing and granulating, or by a so-called partpart process comprising a combination of tower and non-tower processing steps.

Advantages of the invention are observed with powders of high bulk density, for example 700 g / l or more. Such powders can be prepared either by post-densification of the spray-dried powders or by completely non-tower methods such as dry blending and granulation; in both cases, a high speed mixer / granulator may be advantageously used.

Processes using high speed mixers / granulators are described, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).

DETAILED DESCRIPTION OF THE INVENTION

The invention is further illustrated by the following examples in which parts and percentages are by weight unless otherwise indicated. The examples denoted by numbers are according to the invention, while the examples denoted by letters are comparative.

Examples 1 to 14, Comparative Examples A and B

Preparation of ion-exchanged zeolites

Example 1

Preparation of ammonium exchanged zeolite

Sodium zeolite powder 4A (Wessalith P (Trade Mark) ex Degussa)) was converted to a partially ammonium-exchanged form as described below.

150 g of hydrated sodium zeolite 4A was slurried with 1 liter of a 0.2 mol / L ammonium sulfate solution (pH adjusted to 9 with ammonium hydroxide) for 1 hour at 60 ° C. Then the slurry was filtered and the filter cake was slurried again with another 1 liter of fresh ammonium sulfate solution. This procedure was repeated to carry out 3 replacement steps. The zeolite was finally filtered and washed with demineralized water and then oven dried at 100 ° C. The dried zeolite was crushed in a pestle and stored for several days at room temperature to completely rehydrate.

The calculated ammonium (NH ₄ ⁺ ) content for the fully exchanged zeolite is 10.0% by weight of NH ₄ . The material prepared as described had an ammonium (NH ₄ ⁺ ) content of 5.04% by weight, which corresponds to a 50.4% exchange.

Example 2

Preparation of ammonium exchanged zeolite MAP

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 1-3 of EP 384 070A (Unilever). The starting zeolite MAP had a silicon to aluminum ratio of 1.0.

The calculated ammonium content for the fully exchanged zeolite MAP is 10.4% by weight. The exchanged material had an ammonium (NH ₄ ⁺ ) content of 7.95% by weight, corresponding to 76.4% exchange.

Example 3

Preparation of lithium exchanged zeolite

Sodium zeolite 4A was converted to the (partially) lithium exchanged form by a method similar to that used in Example 1 using 0.2 mol / L lithium chloride solution instead of ammonium sulfate solution.

Example 4

Preparation of lithium exchanged zeolite MAP

The lithium zeolite MAP was prepared from the sodium zeolite MAP used in Example 2 by the method described in Example 3.

Example 5

Preparation of hydrogen exchanged zeolite

150 g of hydrated sodium zeolite 4A was slurried with 3 liters of demineralized water. The pH of the slurry was monitored using a pH electrode and was adjusted to 8.0 by the slow addition of a 0.1 mol / L hydrochloric acid solution. After addition of the acid, the zeolite was filtered off, washed with demineralized water and then oven dried at 100 ° C.

The dried zeolite was crushed in a pestle and stored for several days at room temperature to completely rehydrate.

Example 6

Preparation of hydrogen exchanged zeolite MAP

The partially hydrogen exchanged zeolite MAP was prepared from the sodium zeolite MAP used in Example 2 by the method described in Example 5.

Comparative example

Preparation of potassium exchanged zeolite

The 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 with a 0.2 mol / L potassium chloride solution.

Comparative Example

Preparation of potassium exchanged zeolite MAP

The 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 with a 0.2 mol / L potassium chloride solution.

Examples 7 to 10

Preparation of samples of various partially exchanged sodium / ammonium zeolite

150 g of hydrated sodium zeolite 4A was slurried with ammonium sulfate solution (1 liter) having different concentrations at pH 9 for 1 hour at 40 ° C. The zeolites were then filtered off, washed with water and then oven dried at 100 ° C. The dried zeolite samples were then crushed in a mortar and pestle and allowed to fully hydrate under laboratory conditions for several days. The resulting products were analyzed to determine the actual level of ammonium exchange achieved.

Example ammonium sulfate concentration (mol / l) ammonium content 1 (% by weight) replacement range (% w / w) 7 0.10 1.31 13 8 0.21 2.35 23 9 0.41 3.60 35 10 0.82 4.74 46 Examples 11 to 13 Sample preparation various partially replaced sodium- no / ammonium zeolite MAP Four samples of partially exchanged sodium / ammonium zeolite MAP were prepared by the method described in examples 7 Details of preparation and analysis are as follows: Example concentration ammonium content range ammonium sulfate exchange (Mol / 1) (% by weight) (% by weight) 11 0.10 1.13 11 12 0.21 2.47 24 13 0.41 5.89 57.5 14 0.82 8.74 85

Examples 15 to 30

Comparative Examples C to K Stability of sodium percarbonate

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Examples 15 to 17

Comparative Examples C and D

Stability of sodium percarbonate in zeolite A / percarbonate mixtures

Test samples were prepared by mixing 3.75 g of each of the following zeolites with 1.25 g of sodium percarbonate (sieve fraction 500-710 micrometres of Oxyper (Trade Mark) ex Interox) to obtain mixtures containing 75% by weight zeolite and 25% by weight. percarbonate.

Example type of zeolite C sodium zeolite A (Wessalith P) 15 ammonium-exchanged zeolite A (Example 1) 16 lithium-exchanged zeolite A (Example 3) 17 Hydrogen-exchanged zeolite A (Example 5) D potassium exchanged zeolite A (Comparative Example A)

Storage stability was evaluated by the following accelerated storage test under extremely harsh conditions, which is designed to show differences in a shorter period of time than would be shown in a test using more realistic conditions and normal product packaging.

The samples were stored in open glass bottles at 37 ° C and 70% relative humidity. The bottles were withdrawn from storage at regular intervals and the powder mixtures analyzed for remaining active oxygen (AvO). The results were as follows:

Example 0 AvO after time (days) 14 3 6 10 C 100 62,7 47.7 33.4 16.6 15 100 92.3 86.4 78.0 68.6 16 100 85.0 75.7 60.9 55.7 17 100 85.0 67.0 50.0 36.6 D 100 54.0 34.5 19.5 12.3

It should be noted that ammonium-exchanged, lithium-exchanged and hydrogen-exchanged zeolite strongly improved the storage stability of sodium percarbonate, the ammonium-exchanged material provides the greatest gain; whereas the potassium exchanged material yielded relatively worse results than completely sodium zeolite.

Examples 18 to 20

Comparative Examples E and F Stability of sodium percarbonate in zeolite MAP / percarbonate mixtures

The test samples were prepared as described in Examples 15 to 17 and contained 3.75 g (75% by weight) of zeolite and 1.25 g (25% by weight) of sodium percarbonate:

Storage stability at 37 ° C and 70% relative humidity in open glass bottles was measured as described in Examples 15-17. The results were as follows:

AvO example over time (days)

0 3 6 10 14 E 100 73.7 59.1 37.7 27.3 18 100 94.3 91.4 90.2 90.9 19 100 92.1 90.9 83.0 73.6 20 100 93.4 84.0 73.3 62.1 F 100 61.5 40.9 24.5 14.1

Comparison of these results with those of Examples 15-17 shows how the stability of the present invention can be further improved by replacing zeolite A with zeolite MAP.

It should be noted that the use of ammonium zeolite MAP (Example 18) causes indeed no percarbonate losses even after 14 days of open storage under very unfavorable conditions.

As with zeolite A, the potassium exchanged material gave worse results than sodium zeolite.

Examples 21-24 Comparative Example G

Stability of sodium pro-carbonate in mixtures with differently exchanged samples of sodium / ammonium zeolite A

The procedure of Examples 15-17 was repeated using the partially exchanged sodium / ammonium zeolites of Examples 7-10. The results of the storage stability were as follows, Comparative Example G was the starting entirely sodium zeolite A.

Example AvO after time (days) 3 5 10 17 G 68.2 54.6 29.8 12.7 21 (7) 94.6 89.8 73.9 56.4 22 (8) 94.1 90.5 83.0 69.8 23 (9) 90.9 90.5 82.5 66.4 24 (10) 97.3 93.6 87.0 74.5

It can be seen that a very significant gain was achieved even with only 11% exchange (Example 21).

Examples 25-28 Comparative Example H

Stability of sodium percarbonate in mixtures with various exchanged samples of sodium / ammonium zeolite MAP

The procedure of Examples 21-24 was repeated using the partially exchanged sodium / ammonium zeolites MAP of Examples 11-14. The storage stability results were as follows, Comparative Example H was the starting completely sodium zeolite MAP.

Example of zeolite type

AvO example over time (days)

5 10 17

E sodium zeolite MAP (starting material for Examples 2 and 4) ammonium-exchanged zeolite MAP (Example 2) lithium-exchanged zeolite MAP (Example 4) hydrogen-exchanged zeolite MAP (Example 6)

F potassium exchanged zeolite MAP (Comparative Example B)

H 74.6 61.4 38.4 26.8 25 mm (11) 95.5 91.6 81.8 77.7 26 (12) 93.2 91.6 88.6 80.9 27 (13) 96.8 90.2 82.3 73.6 28 (14) 95.2 90.0 80.5 72.7

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The image is similar to that observed with partially exchanged zeolite A, with the maximum gain apparently achieved when the ammonium exchange range was 23% or more (Examples 26, 27 and 28).

Examples 29 and 30

Comparative Examples J and K Stability of sodium percarbonate in detergent granules

Detergent granules were prepared by granulating the zeolite with a nonionic surfactant in a laboratory granulator, using in each case a particularly necessary amount of the nonionic surfactant to achieve granulation. The nonionic surfactant was Synperonic (Trade Mark) A7 ex ICI, a primary C ₁₂ -C ₁₅ 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 (starting material used in Examples 1 and 2). The granule mixtures were as follows:

Example zeolite type nonionic surfactant (g / 200 g zeolite)

J Na A 61.5 29 NH ₄ A (Ex. 1) 64.8 The On MAP 75.3 30 NH ₄ MAP (Ex. 2) 82.0

The granules were sieved and a fraction of 250-700 microns was used in the assay described to determine the storage stability of the percarbonate.

All test samples were prepared by mixing detergent granules (8.75 g) with sodium percarbonate (1.25 g). The percentage composition of the test samples was therefore as follows:

Example Composition (% by weight)

Zeolite Non-ionic PAL Percarbonate

J 66.9 20.6 12.5 29 66.1 21.4 12.5 The 63.6 23.9 12.5 30 62.1 25.4 12.5

PAL - surfactant

As in the previous examples, the samples were stored in open glass bottles at 37 ° C and 70% relative humidity. The results were as follows:

AvO example over time (days)

6 9 14

J 100 30.2 20.5 4.1 29 100 83.9 77.7 51.6 The 100 50.0 42.0 10.5 30 100 90.0 90.9 79.5 Examples 31 to 35 Comparative Examples L to O

Stability of bleach catalyst

Example 31 Comparative Example L

The basic detergent powders were prepared by mixing zeolite A, in sodium or ion-exchanged form, with a cocoPAS sulfate, coconut-alcohol-3EO nonionic surfactant, coconut-alcohol 7EO nonionic surfactant, and water - in a laboratory granulator. Zeolites were used as in the previous examples: ammonium zeolite A was as in Example 1, and sodium zeolite was the raw material of Example 1. The differences in the preparations reflect the different working capacities of the two zeolites.

The base powders were mixed with manganese catalyst granules to obtain powders having the following composition:

Example L Example 31

Zeolite A (Na) ‘ 65.5 - Zeolite A (NH ₄ ) '(Ex. 1) - 68.6 COCOP 7.5 6.7 Coco 7EO 7.5 6.7 Coco 3EO 9.6 8.5 Soap 2.9 2.6 Water 2.0 1.8 Base powder total 95.0 95.0 Catalyst granules 5.0 5.0 100.0 100.0

* hydrated base

The catalyst granules had the following composition:

Catalyst (1,4η 1,4,7-Me ₃ TACN) 1.8

Zeolite MAP46.6

Soap / fatty acid 20.5

Citric acid22,2

Titanium dioxide 8.9% neutralized mixture of C ₁₂ -C ₁₈ saturated fatty acids (about 60% C ₁₂ , 17% C ₁₆ , 20% C ₁₈ , 3% C _{1 (} ) + C ₁₄ ).

The powder samples were stored in open glass containers at 37 ° C and 70% relative humidity. After 28 days, samples were removed from this environment and sample pairs Powders 31 and L were compared visually by a panel of eight evaluators to assess the relative stained change. The results were as follows:

Evaluators preferring powder

Evaluators preferring L 0 powder

The powder of Example 31 had a slight color change, while the powder of Comparative Example L was completely color poor. On a free scale of 0 to 10, the evaluators gave the following color change scores:

Powder 31 3

Powder L 6

Example 32

Comparative Example M

Base detergent powders were prepared by mixing zeolite MAP, in sodium or ion-exchanged form, with the liquid surfactant mixture used in Examples 31 and L in a laboratory granulator. The ammonium exchanged zeolite MAP was the zeolite in Example 2 and sodium zeolite MAP was the raw material of Example 2. Again, the differences in the formulations reflect the different working capacities of the two zeolites.

The base powders were mixed with manganese catalyst granules to obtain powders having the following composition:

Example M Example 32

Zeolite MAP (Na) ’ 58.9 - Zeolite MAP (NH ₄ ) '(Pr. 1) - 63.6 COCOP 9.2 8.0 Coco 7EO 9.2 8.0 Coco 3EO 11.7 10.1 Soap 3.5 3.1 Water 2.5 2.2 Base powder total 95.0 95.0 Catalyst granules 5.0 5.0

100.0 100.0 hydrated base

Storage tests and color change evaluation were performed as described in Examples 31 and L. The results were as follows:

Evaluators preferring powder 32 6

Assessors preferring M 2 powder

The powder of Comparative Example M (containing sodium zeolite MAP) had a significantly less discolored color than the powder of Comparative Example L (containing sodium zeolite A), with a color change score of 2.

Example 33

Comparative Example N

The procedure of Examples 31 and L was repeated using different catalyst granules having the following composition:

Catalyst (Mn 1,4,7-Me ₃ TACN) 2.0 Cetocetylstearát 31.0 silica * 26.4 Sodium bicarbonate 39.6 titanium dioxide 1.0

100.0 'Gasil (Trademark) 200TP ex Crosfield.

Example 33 contained 95% by weight of the base powder of Example 31 (ammonium exchanged zeolite A) and Comparative Example N contained 95% by weight of the base powder of Comparative Example A (sodium zeolite A). Each powder also contained 5% by weight of the catalyst granules. Storage tests were carried out as in the earlier examples and the panel evaluation results were as follows:

Evaluators preferring powder 338

Evaluators preferring NO powder

The color change scores were as follows:

Powder 330

Powder N8

Example 34

Comparative Example

The procedure of Examples 33 and N was repeated using ammonium exchanged zeolite MAP (Example 34) and sodium zeolite MAP (Example P).

Example 34 contained 95% by weight of the base powder of Example 32 (ammonium exchanged zeolite MAP) and Comparative Example P contained 95% by weight of the base powder of Comparative Example M (sodium zeolite MAP). Each powder also contained 5% by weight of the catalyst granules. Storage tests were carried out as in the earlier examples and the panel evaluation results were as follows:

Evaluators preferring powder 347

Evaluators preferring P1 powder

The color change scores were as follows:

Powder 340

Powder P3

Example 35

Comparative example Q

This example describes an accelerated storage test to show the effect of zeolite type on the decomposition of the Mn 1,4,7-Me ₃ TACN catalyst. In this test, a catalyst that was not in granular form directly contacted the zeolite base powder.

The crystalline catalyst (0.26 g) was granulated with 7EO nonionic surfactant (3 g) and zeolite (10 g) to give the following composition:

Example Q 35 catalyst 1.96 1.96 Zeolite A (Na) ’ 75.42 - Zeolite A (NH ₄ ) '(Ex 1) - 74,42 Non-ionic PAL 7EO 22.62 22.62

100,00 100,00 * hydrated base ** C ₁₂ . ₁₅ oxoalcohol, 7EO: Synperonic (Trade Mark) A7 ex ICI.

The granules were stored at 37 ° C and 70% relative humidity and their color was visually evaluated at regular time intervals.

The granules of Comparative Example Q had a significant brown color level after 24 hours of storage. However, the granules of Example 35 were not colored.

Claims (6)

PATENT CLAIMS A particulate detergent, bleaching or cleaning composition comprising a moisture-sensitive bleaching component and a crystalline aluminosilicate having exchangeable cations, characterized in that at least 5% by weight of the exchangeable aluminosilicate cations comprise ammonium, lithium or hydrogen ions or combinations thereof. A composition according to claim 1, wherein the aluminosilicate is zeolite A, wherein from 10 to 50% by weight of the exchangeable cations comprise ammonium, lithium or hydrogen ions or combinations thereof. The composition of claim 1, wherein the aluminosilicate is a zeolite P having a silicon to aluminum atomic weight ratio not exceeding 1.33 as the zeolite MAP, wherein from 10 to 90% by weight of the exchangeable cations comprises ammonium, lithium or hydrogen ions or combinations thereof. Composition according to any one of the preceding claims, characterized in that the moisture-sensitive bleaching component is an inorganic peroxy salt. 5. A composition according to claim 4 wherein the moisture-sensitive bleaching component is sodium percarbonate. A composition according to any one of the preceding claims, characterized in that it comprises: (a) from 2 to 60% by weight of one or more organic surfactants; (b) from 10 to 80% by weight of detergent builders, including zeolite in partially or totally ion-exchanged form; (c) from 5 to 40% by weight of a bleaching system comprising a whitening component sensitive to moisture; and d) optionally other detergent ingredients up to 100% by weight, wherein the exchangeable aluminosilicate cations (b) include ammonium, lithium or hydrogen ions or combinations thereof.