CZ243095A3 - Particulate bleaching or cleansing agents containing aluminosilicates - Google Patents

Abstract

Particulate detergent, bleaching or cleaning compositions containing moisture-sensitive ingredients, for example bleach ingredients, and also containing crystalline aluminosilicate (zeolite), show significantly enhanced stability of moisture-sensitive ingredients, especially sodium percarbonate or certain bleach catalysts, if the exchangeable cations of the crystalline aluminosilicate include cations of a weak monoacidic base, for example, ammonium, lithium or hydrogen ions.

Description

Technical field

The present invention relates to particulate detergent, bleach or detergent compositions containing crystalline aluminosilicates (zeolites) and also containing moisture sensitive components, in particular bleach components, for example inorganic persalts such as sodium percarbonate, organic or inorganic peroxyacids, bleach precursors or bleach catalysts.

BACKGROUND OF THE INVENTION

The ability of crystalline aluminosilicates (zeolites) to trap calcium ions from aqueous solutions by an ion exchange mechanism has made them well known replacements for phosphates as detergency builders. Many of the particulate detergent compositions currently available on the market in Europe, Japan and the US contain zeolites.

Although some crystalline forms of zeolites are known, the preferred zeolite for use in detergents has always been zeolite A used in sodium form.

Examples of prior art documents describing detergent compositions containing zeolites are EP 456515A (Procter & Gamble), EP 87035A (Union Carbide), US 4604224 and CA 1072853 (Colgate). The use of zeolites Α, Χ, Β (P) and Y is described and their formulation is generally stated with a range of possible cations, but sodium 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and has been extensively described in the literature, although in recent years its use in commercial formulations has been replaced by sodium perborate. Sodium percarbonate is less stable than sodium perborate in the presence of moisture, and its stabilization in detergent compositions has long been considered difficult. This problem becomes particularly acute if sodium percarbonate is to be included in a detergent powder with a high moisture content because it tends to be deactivated upon storage. This situation is particularly true of zeolite-containing powders since these materials contain a large amount of relatively mobile water.

This problem is solved in GB 2013259A (Kao), which proposes as a solution the use of zeolite in which sodium cations have been partially exchanged for calcium or magnesium ions. This embodiment improves the stability of sodium percarbonate, but with reduced binding (calcium and magnesium ion exchange) efficiency.

An alternative solution to the problem of percarbonate stability in particulate, zeolite-containing compositions is described in EP 522726A (Unilever), according to which conventional zeolite A is replaced by the maximum aluminum aluminum P (zeolite MAP), a material as described and claimed in EP 384070A (Unilever). . The use of this zeolite provides substantially improved storage stability of sodium percarbonate.

Similar improvements in storage stability of sodium perborate monohydrate have been observed as described in EP 552053A (Unilever); bleach precursors as described in our related International Patent Application No. EP / 93/03369 filed November 29, 1993; and certain manganese bleach catalysts as described in our co-pending British patent application no.

05599.4 filed March 18, 1993.

The present invention is based on the discovery that further significant improvements in the stability of sodium percarbonate and other moisture-sensitive components in particulate, zeolite-containing, detergent and cleaning agents during storage can be achieved by using zeolites in which sodium ions have been completely or partially replaced by other cations This is surprising because the ion exchanged forms generally do not have lower moisture contents than their sodium forms and are used in the present invention in a fully hydrated form in an environment where there is no control of the mobile water content. Improvements are observed with both zeolite A and zeolite MAP.

EP 364184A (Unilever) discloses non-aqueous cleaning compositions comprising 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. Treatment reduces aluminosilicate catalyzed decomposition of bleach precursors such as tetraacetylethylenediamine in the liquid product. In contrast to the present invention, EP 364184A is directed to 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 present invention provides a particulate detergent, bleach or cleaning composition comprising a heat-sensitive component and a crystalline aluminosilicate having exchanged cations, wherein the exchanged aluminosilicate cations form cations derived from a weak monoacidic base.

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

The invention further provides the use of an aluminosilicate as defined above for improving the stability of the moisture sensitive component in a particulate detergent, bleach or detergent 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, having exchangeable cations, wherein the replaceable cations are derived from a weak monoacidic base.

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

Ion-exchanged zeolite

The compositions of the invention require, as an essential component, a crystalline aluminosilicate (zeolite) in which the exchangeable cations form at least a portion of the cations derived from a weak monoacidic base.

Such zeolite can be readily prepared by ion exchange sodium zeolite and will therefore be hereinafter referred to as ion-exchanged zeolite, although the invention could also include the use of directly synthesized, completely non-sodium ion exchanged zeolites, if such materials can be prepared.

Ion exchange capable zeolites have the following formula:

M _x (SiO ₂ ) y (Al ₂ O ₃ ) _x . zH ₂ O wherein M is a cation monovazný. The ratio of silicon to aluminum (y: x) may vary depending on the amount of water for hydration.

Partially exchanged zeolite may be represented as ^m1 x, ^m2 (x-x ') ^(Si0 2) y ^(A10 2) x · ^ZH 2 ° wherein M ¹ and M ² are two different exchangeable cations monovazné.

The (molar) percent exchange rate can then be defined as xi for the M ¹ cation. 100 X

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

Preferred M ¹ cations 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 particularly preferred. Potassium ions derived from a strong base have been found to have the opposite effect, potassium zeolites provide worse stability of the moisture-sensitive components than the corresponding sodium zeolites.

O

The preferred cation M is sodium.

If M ^{1 is a} hydrogen ion, x 'is best determined by the difference between the aluminum content (x) and the second cation content (M ² ).

The zeolite may be in any crystalline form suitable for use in detergents. As mentioned above, zeolite A is the most popular detergent zeolite. The use of zeolites X, Y and P (B) is also described in the art, although they have not been found to be appropriate in practice because their calcium ion exchange is either inadequate or too slow.

Zeolite A has the advantage of having a maximum aluminum structure containing a maximum possible ratio of aluminum to silicon (or a minimum possible ratio of Si: Al of 1.0) so that its calcium ion uptake capacity from the aqueous solution is significantly higher than that of zeolite X, Y and P, which generally contain a lower 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 completely ion-exchanged zeolite may be zeolite MAP as described and claimed in EP 384070B (Unilever) as mentioned above.

It is zeolite P having a maximum aluminum content, i.e. zeolite P having a Si: Al ratio not exceeding 1.33, preferably not more than 1.15 and most preferably not more than 1.07. Zeolite MAP has various advantages over zeolite A, and one of them is that even in sodium form it improves the storage stability of sodium percarbonate and various other bleaching ingredients as mentioned above.

Ion exchanged zeolites are described in the literature, for example by D.W.Brech and E.M.Flanagan,

Molecular Sieves, Soc. (London), 1968, pp. 47-61; US

No. 4346067 (Exxon Corporation) discloses ammonia exchanged zeolites and EP 223396A (Mobil 011 Corporation) discloses hydrogen exchanged zeolites, both of which are useful as catalysts in hydrocarbon conversion reactions.

However, zeolite MAP in ion-exchanged form is believed to be a new material and is required to be protected as part of the present invention.

Scope of exchange

It appears that the zeolites should be in an ion-exchange form in the range of at least 5%, preferably at least 10% and more preferably at least 20% by weight, in order to realize a contribution to improving the stability of the moisture sensitive component. Larger ion exchange rates do not appear to bring further improvement, but there is also a decrease in benefit.

Accordingly, the zeolites used according to the present invention should preferably be in an ion exchange form in the range 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 an ion exchange form of 10 to 50%, more specifically in an ion exchange form of 20 to 50%, while zeolite MAP has been found to provide good results when an ion exchange form of from 10 to 90%, more particularly in an ion exchange form of from 20 to 90%.

The lower bounds mentioned are specifically applicable to ammonium exchanged zeolites. The corresponding boundary for other cations can be the same, but can be readily determined by one of ordinary skill in the art by the methods described herein in the Examples.

Preparation of ion-exchanged zeolite

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 can be similarly prepared by immersion in an aqueous solution of a strong acid, such as hydrochloric acid.

Percent exchange rates can be controlled by varying the salt or acid concentration and the amount of zeolite added as described in more detail in D. W. Breck et al in JACS 78 5963 et seq (1956).

Compositions of the invention

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

Bleach ingredients sensitive to moisture

Examples of moisture-sensitive bleach components include peroxy bleach compounds, for example, inorganic or organic persalts and peroxyacids, bleach activators (bleach precursors), and bleach catalysts.

Inorganic persoli

Inorganic persalts include alkali metal perborates, their percarbonates, perfosphates, persilicates, and persulphates. The moisture-sensitive inorganic persalts to which the present invention is particularly applicable include sodium perborate monohydrate and more specifically sodium percarbonate.

Inorganic persalts may be advantageously used in conjunction with a bleach precursor or activator thereof. The bleach precursors themselves may be susceptible to moisture and their stability is improved by the present invention.

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

Bleach precursors

Preferred bleach precursors are peroxycarboxylic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.

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

N, N, N ', N'-tetraacetylethylenediamine (TAED);

2- (N, N-N-trimethylammonium) ethyl n-sodium-4-sulfophenylcarbonate chloride (SPCC), also known as cholyl p-sulfophenyl carbonate (CSPC);

sodium nonanoyloxybenzenesulfonate (SNOBS);

sodium 4-benzoyloxybenzenesulfonate (SBOBS);

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

and glucose pentaacetate (GPA).

Peroxyacids

Peroxyacids useful in the present invention include organic or inorganic acids.

Organic acids commonly have the general formula Oit

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

Typical monoperoxyacids suitable for use in the compositions of the present invention include, for example:

i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, such as peroxy-alpha-naphthoic acid;

ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids such as peroxylauric acid, peroxystearic acid and N, N'-phthaloylaminoperoxycaproic acid (PAP;

iii) 6-octylamino-6-oxoperoxyhexanoic acid.

Typical diperoxy acids suitable for the compositions of the invention include:

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

v) 1,9-diperoxyazelaic acid;

vi) diperoxybrassilic acid, diperoxysebacic acid and diperoxyisophthalic acid;

vii) 2-decyldiperoxybutane-1,4-dioic acid; and viii) 4,4'-sulfonylbisperoxybenzoic acid, ix) N, N'-terephthaloyl-di (6-aminoperoxycaproic acid), also known as n, N'-di ( 5-percarboxypentyl) tetrephthalamide (TPCAP).

Bleach catalyst

The class of bleach catalysts useful in the present invention is described and claimed in EP 458397A and EP 458398A (Unilever).

A 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

- [NR ³ - (CR ¹ (R ² ) _u ) _t ] _s wherein t is an integer from 2 to 3, s is an integer from 3 to 4, u is zero or one and R ¹ , and R ³ are independently selected from the group consisting of H, alkyl, and aryl, both optionally substituted.

Examples of preferred ligands include:

1.4.7- triazacyclononane (TACN);

1,4,7-trimethyl-1,4,7-triazacyclononane (1,4,7-Me ₃ TACN);

2-methyl-1,4,7-triazacyclononane (2-MeTACN);

1,2.4.7-tetramethyl-1,4,7-triazacyclononane;

(l, 2,4,7-Me ₄ TACN);

1,2.2.4.7-pentamethyl-1,4,7-triazacyclononane (1,2,2,4,7-Me3TACN);

1,4,7-trimethyl-2-benzyl-1,4,7-triazacyclononane a

1,4,7-trimethyl-2-decyl-1,4,7-triazacyclononane.

Particularly preferred is 1,4,7-trimethyl-1,4,7-triazacyclononane (1,4,7-Me ₃ TACN).

The above ligands can be synthesized according to the methods described by K. Wieghardt et al., Inorganic Chemistry 1982, 21, p. 3086.

The iron and / or manganese ion source and the ligand may be prepared separately or in the form of mono-, di- or tetra-nuclear manganese or iron complexes. When added separately, the salt ligand may be an acid such as 1,4,7-Me ₃ TACN hydrochloride. The source of iron and manganese ions may be a water-soluble salt such as nitrate, chloride, sulfate or acetate of iron or manganese, or a coordination complex such as manganese acetylacetonate. The source of iron and / or manganese should be such that the ions are not too tightly bound, i. all of these sources from which the ligand of formula I as hereinbefore defined can extract Fe and Mn in the wash liquid.

Preferred mononuclear complexes have the formula [LMn ^IV (OR)] Y (a) wherein Mn is manganese in the +4 oxidation step, R is a radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl, and combinations thereof;

at least two R radicals may also be linked to each other so as to form a bridging unit between the two oxygen, which are coordinated with manganese;

L is a ligand of formula I above;

and Y is an oxidation-stable counterion or of the formula [LMnXp] ^of Y _q (b) wherein Mn may be either in the oxidation stage II, III or IV;

each X independently represents a coordinating species with the exception R0-, such as 01, Br ", I", F "NCS", N _"3, I ₃ 'RCOO_,

RSO ₄ ', wherein R is alkyl or aryl, both optionally substituted,

OH ", about ² " ₂ , HOO ", H ₂ 0, SH, CN", S ₄ ² "and mixtures thereof;

p is an integer from 1 to 3;

z represents the charge of the complex and is an integer which can be positive, zero or negative;

Y is a type-dependent counterion of a complex charge;

q = z / [charge Y];

Such mononuclear complexes are described in more detail in our related European patent application EP 549272A, filed September 18, 1992 and published June 30, 1993.

Preferred binuclear complexes have the formula

wherein Mn is manganese, which may be independently in oxidation stage II or IV;

each X independently of the other represents a coordination or bridging species selected from the group consisting of H ₂ O, OH -, O ^{2 -} 2 SH -, S ^{2 -} ,> SO, C 1 -, SCN -, s ^{4 2} , n _{3 -} , rso ₃ ", RCOO, nh ₂ " and NR ₃ , where

R is H, alkyl or aryl, both optionally substituted, and R ¹ COO, wherein R ¹ is an alkyl or aryl radical, both optionally substituted;

L is a ligand of formula I as defined above z is a complex charge and is an integer that can be positive or negative, or is zero;

Y is a monovalent or polyvalent counterion providing a charge neutrality which is dependent on the charge of the complex and q = z / [charge Y].

Such dual core complexes of this type are described in EP 458397A and EP 458398A (Unilever).

The bleach catalyst is preferably in the form of granules as described and claimed in our International Patent Application No. PCT / GB94 / 01904, filed Sep. 2, 1994.

These granules contain:

i) from 0.5 to 20% by weight, preferably from 1 to 15% by weight, of the catalyst itself; a soluble core material, preferably selected from sodium bicarbonate, magnesium nitrate, and an attached sheet of potassium and magnesium sulfate;

iii) from 5 to 91 wt. a binding agent selected from silicone oils, fatty acids, fatty esters, tri-, di and monoglycerides, waxes and solid hydrocarbons.

A particularly preferred binder is cetostearyl stearate.

Preferably, the granules will also contain an inert solid. Preferred inert materials include silicas such as Gasil, Aerosil and Sorbosil (Trade Mark); clays such as kaolin, alumina; and titanium dioxide.

Other preferred granules are described and claimed in British Patent Application No. 93 18295.4, filed Sep. 3, 1993.

Alternatively, the bleach catalyst may be in the form of granules as described and claimed in our co-pending application EP 544440A filed November 18, 1992 and published June 2, 1993. These granules comprise:

i) from 0.5 to 8 wt. ii) optionally from 0 to 90 wt. % of an inert salt selected from chlorides, carbonates and mixtures thereof; and iii) from 5 to 91 wt. a binder selected from water-soluble and non-oxidizable polymers, alkali metal silicates, saturated fatty acid soap mixtures, and combinations thereof.

The preferred binder is sodium silicate and the preferred inert salt is sodium carbonate.

Preferred granules include catalyst / sodium stearate / lauric acid granules and catalyst / sodium carbonate / sodium silicate / zeolite granules.

Preferably, the manganese catalyst in the granules has as small a particle diameter as possible, preferably below 250 microns, for suitable distribution and for rapid delivery to the washing process, although particles that are too small can also cause handling difficulties in the granulation process .

The preferred and optimum particle size of the manganese catalyst is in the range of 50 to 150 microns.

Bleaching composition

For example, the composition of the invention may be an additive detergent consisting of an aluminosilicate builder and one or more moisture sensitive components of the bleaching agent.

An additive of this type can be used in conjunction with a conventional product under conditions where high water hardness and / or heavy soiling require special building and / or extra bleaching capacity.

Such an additive may also be in the form of a building block system, for example as described in EP 419036A (Unilever), which may be used together with the substrate and / or the non-bleaching main laundry detergent.

Detergent composition

Alternatively, the composition of the invention may be a particulate detergent composition, which may suitably comprise the following ingredients:

(a) one or more organic detergent surfactants;

b) a builder system comprising a crystalline aluminosilicate as defined above;

(c) one or more moisture-sensitive components,

d) optionally, an additional detergent component.

The detergent ingredients of the invention containing moisture-sensitive bleaching ingredients may advantageously contain the following ingredients:

(a) one or more organic surfactants,

b) a builder system comprising a crystalline aluminosilicate as defined hereinabove;

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

d) optionally, an additional detergent component.

Preferred detergent ingredients of the invention may comprise the following ingredients in the following proportions:

a) from 2 to 60 wt. one or more detergent surfactants,

b) from 10 to 80 wt. one or more detergency builders, including zeolite in partially or completely ion exchange form

c) from 5 to 40 wt. a bleaching system comprising a moisture sensitive bleaching component; and

d) optionally, additional detergent ingredients up to 100 wt.

The moisture-sensitive bleach component may be, as previously mentioned, a persulfate, a bleach precursor, a percarbonate, a peroxyacid, or a bleach catalyst as defined above.

Detergent surfactants

The detergent compositions of the invention will contain as essential ingredients one or more surfactants, which may be selected from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds and mixtures thereof. Many suitable detergent-active compounds are available and are fully described in the literature, for example, Surface-Active Agents and Detergents, Vol. I and II, Schwartz, Perry and Berch.

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 alkyiový chain length of _C8-C15; primary and secondary alkyl sulphates, particularly ^C 12 ^-C 15 'Accept lsulf alkyl sulfates; alkyl ether sulfates; olefin sulfonates; alkylxylene sulfonates; dialkylsulfosuccinates and sulfonates of fatty acid esters. Sodium salts are generally preferred.

Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially ^C 8 ^C 20 primary and secondary aliphatic alcohols ethoxylated with an average of 1-20 moles of ethylene oxide per mole of alcohol, _{Cg-C 15} primary aliphatic alcohols ethoxylated with an average of 1 to 10 ml ethylene oxide per mole of alcohol.

Also of interest are nonethoxylated nonionic surfactants, for example alkyl polyglycosides; O-alkanoyl glucosides as described in EP 423968A (Unilever); and polyhydroxyamides.

The choice of detergent-active compound (surfactant) and amount present will depend upon the intended use of the detergent composition: various surfactant systems may be selected, as known to those skilled in the art of formulation, for hand wash products and for products intended for use in different types of washing machines. .

The total amount of surfactant present will also depend on the intended end use, but may generally be in the range of 2 to 60 wt%, east of 5 to 40 wt%.

Detergent compositions suitable for use in most automatic washing machines generally comprise an anionic non-soap surfactant or a nonionic surfactant or a combination of the two in any ratio, optionally together with a soap.

Detergent builder system

The detergent compositions of the invention also comprise one or more detergency builders. The total amount of detergency builder in the compositions will preferably be in the range of 10 to 80 wt%.

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

The amount of zeolite present may preferably be in the range of 5 to 60 wt. more preferably from 15 to 40% by weight, calculated on the anhydrous basis (corresponding to from 6 to 75% by weight, preferably from 19 to 50% by weight, calculated on the 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 crystallization primer for calcium carbonate, as described in GB 1437950 (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 alkenylmalonates and succinates; and salts of sulfated fatty acids. This list is not intended to be exhaustive.

Preferred supplementary builders for use in conjunction with zeolite include citric acid salts, more particularly sodium citrate, preferably used in amounts of from 3 to 20 wt%, more preferably from 5 to 15 wt%. The combination of zeolite MAP with citrate as a detergency builder system is described and claimed in EP 448297A (Unilever).

Preference is also given to polycarboxylate polymers, in particular acrylic / maleic acid copolymers, preferably used in amounts of from 0.5 to 15% by weight, in particular from 1 to 190% by weight, of the detergent composition; the combination of zeolite MAP with polymeric builders is described and claimed in EP 502675A (Unilever).

Bleaching system

As mentioned previously, the detergent compositions of the invention may comprise a bleaching system which comprises at least one moisture-sensitive component. The bleach system may generally comprise a peroxy bleach compound, for example an inorganic or organic persulf, optionally in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures; or inorganic or organic peroxyacids. A bleach stabilizer (heavy metal scavenger) may also be present. According to a preferred embodiment of the invention, a bleach catalyst as previously defined may also be present.

Preferred inorganic persalts are sodium perborate monohydrate and sodium percarbonate. As mentioned above, sodium percarbonate is particularly sensitive to moisture and is of benefit to the present invention.

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

Bleach precursors are preferably used in amounts of from 1 to 8 wt%, preferably from 2 to 5 wt%.

The organic or inorganic peroxyacids are normally used in an amount of from 2 to 10% by weight. preferably from 4 to 8 wt.

The amounts of the bleach catalyst described above are present in the detergent compositions of the invention in an amount of from 0.02 to 0.08% by weight.

Other folders

Other materials that may be used in the detergent compositions of the invention include sodium silicate; anti-deposition agents such as cellulose polymers; fluorescers; inorganic salts such as sodium sulfate, suds controlling agents or suds boosters as needed; pigments; and perfumes. This list is not intended to be limiting.

Preparation of detergent compositions

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

One suitable method involves spray drying a suspension compatible with the heat-sensitive ingredients and at least a portion of the detergent active compounds and then spraying on or postdosing those ingredients that are unsuitable for suspension processing, including sodium percarbonate and any other bleaching ingredients. The skilled artisan will have no difficulty in deciding which ingredients should be included in the suspension and which are not.

The compositions of the invention may also be prepared by fully non-tower processes, for example by dry blending and granulation, or by a so-called part-part process involving a combination of tower and non-tower process steps.

The benefit of the present invention is manifested in the bulk density of the powders, for example, 700 g / l or above. Such powders can be prepared either by post-tower compaction of spray-dried powder or by a fully non-tower process such as dry mixing and granulation; in both cases it is preferred to use a high speed mixer / granulator.

Methods using high speed mixer / granulators are described, for example, in EP 340013A, EP 367339A, EP 390251A and EP 4203 17A (Uhilever).

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. Examples indicated by numbers are according to the invention, while examples indicated 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 4A powder (Wessalith (Trade Mark) P from Degussa) was converted to a partially ammonium exchange as follows.

150 g of hydrated sodium zeolite 4A is slurried with 1 liter of a 0.2 molar sodium sulfate solution (adjusted to pH 9 with ammonium hydroxide) for 1 hour at 60 ° C. The suspension is then filtered and the filter cake is resuspended in a further 1 liter of fresh ammonium sulfate solution. This procedure is repeated and a total of three exchange steps are obtained. The zeolite is finally filtered off and washed with demineralized water and then dried in an oven at 100 ° C. The dried zeolite is crushed in a mortar and pestle and stored at ambient temperature for several days for full rehydration.

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

Example 2

Preparation of ammonium exchanged zeolite MAP

The 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 384070A (Unilever). The starting zeolite MAP had a silicon to aluminum ratio of 1.0.

The calculated ammonium content for the full zeolite MAP exchange 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 (partially) into a lithium exchanged form by a method similar to that described in Example 1 using 0.2 molar lithium chloride solution instead of ammonium sulfate solution.

Example 4

Preparation of lithium-exchanged zeolite MAP

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

Example 5

Preparation of hydrogen exchanged zeolites

150 g of hydrated sodium zeolites 4A are mixed in 3 liters of demineralized water. The pH of the suspension is monitored using a pH electrode and the pH is adjusted to 8.0 by slowly adding 0.1 molar hydrochloric acid. After addition of the acid, the zeolite is filtered off, washed with demineralized water and dried in an oven at 100 ° C. The dried zeolite is crushed in a mortar and pestle and stored at ambient conditions for several days for full rehydration.

Example 6

Preparation of hydrogen exchanged zeolites MAP

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

Comparative example

Preparation of potassium - exchanged zeolites

The partial potassium exchanged zeolite A is prepared from the sodium zeolites A used in Example 1 by the method described in Example 3, except that the lithium chloride solution is replaced by a 0.2 molar potassium chloride solution.

Comparative example

The partially potassium-exchanged zeolite MAP is prepared from the sodium zeolite MAP used in Example 2 by the method described in Example 4, except that the lithium chloride solution is replaced with a 0.2 molar potassium chloride solution.

Examples 7 to 10

Preparation of various partially exchanged sodium / ammonium zeolite 4A samples

150 g samples of hydrated sodium zeolite were mixed with ammonium sulfate solutions (1 liter) having different concentrations at pH 9 for 1 hour at 40 ° C. The zeolites were then filtered and dried in an oven at 100 C. The dried zeolite samples were then crushed in a mortar and pestle and allowed to hydrate fully under ambient conditions for several days. The resulting products were

analyzed to determine the achieved and ictal exchange with ammonium. Example concentration content range ammonium sulfate amonia exchange (molar) (% by weight) (%) 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 Preparation samples partially exchanged zeolite MAP sodium / ammonium

Four samples of partially exchanged zeolite MAP sodium / ammonium were prepared by the method described in Examples 7-10.

The preparative and analytical values are as follows

Example concentration ammonium sulfate (molar) content amonia (wt%; range exchange 1 (%) 11 0.11 1.13 11 12 0.21 2.47 24 13 0.42 5.89 57.5 14 0.84 8.74 85 Examples 15 to 30, comparative examples C to K Stability sodium percarbonate 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 (500-710 micrometer Oxyper sieve fraction (Trade Mark) from Interoxy) to give mixtures containing 75% w / w. % zeolite and 25 wt. percarbonate.

Example type of zeolite C sodium zeolite A (Wessalith P) 15 Dec 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 particularly harsh conditions, which is intended to determine differences over a short period of time than would be possible in a test using more realistic conditions and normal product packaging.

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

Example AvO (days) 0 3 6 10 14 C 100 ALIGN! 62.7 47.7 33.4 16.6 15 Dec 100 ALIGN! 92.3 86.4 78.0 68.6 16 100 ALIGN! 85.0 75.7 60.9 55.7 17 100 ALIGN! 85.0 67.0 50.0 36.6 D 100 ALIGN! 54.0 34.5 19.5 12.3

It should be noted that the ammonium exchanged, lithium exchanged and hydrogen exchanged zeolites all have improved storage stability of sodium percarbonate and the ammonium exchanged material provides the greatest improvement; while the potassium-exchanged material gives worse results than the entire sodium zeolite.

Examples 18 to 20, Comparative Examples E and F

Stability of sodium percarbonate in zeolite mixtures

MAP / percarbonate

Test samples were prepared as described in Examples to 17, each containing 3.75 g (75 wt%) of zeolite and 1.25 g (25 wt%) of sodium percarbonate.

Example zeolite

E and 4) 18

F sodium zeolite MAP (starting material for ammonium-exchanged zeolite MAP (Example 2) lithium-exchanged zeolite MAP (Example 4) hydrogen-exchanged zeolite MAP (Example 6 potassium-exchanged zeolite MAP (Comparative Example B)).

Storage stability at 37 ° C and 70% relative humidity in the above-opened glass containers was measured as described in Examples 15-17. The results are as follows:

AvO example after (days)

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

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

It should be noted that the use of ammonium zeolite MAP (Example 18) does not lead to almost any percarbonate loss even after 14 days of open storage under very unacceptable conditions.

As with zeolite A, the potassium exchanged material provides worse results compared to sodium zeolite.

Examples 21 to 24, Comparative Example G

Stability of sodium percarbonate in mixtures with samples of differently exchanged 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 is the starting fully sodium zeolite A.

Example Avo after (days) 3 5 10 17 G 68.2 54.6 29.8 12.7 21 mm (7) 94.6 89.8 73.9 56.4 22 mm (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

Obviously, a very significant benefit is achieved with only 11% exchange (Example 21).

*

Examples 25 to 28, Comparative Example 11

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

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

AvO example after (days)

3 5 10 17 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

The effect is similar to that observed for partially exchanged zeolite A with a maximum benefit achieved with an ammonium exchange range of 23% or greater (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 a zeolite with a nonionic surfactant in a laboratory scale granulator using in each case just a sufficient nonionic surfactant to achieve granulation. The nonionic surfactant was Synperonic (Trade Mark) A7 ex ICI, I2 ^{c -c} i5 primary alcohol ethoxylated with an average of 7 moles ethylene oxide per ol alcohol.

The zeolites used were the ammonium exchanged zeolites of Examples 1 and 2 and the corresponding sodium zeolites (starting materials used in Examples 1 and 2). The composition of the granules was as follows:

and

Example zeolite nonionic surfactant type (g / 200 g zeolite) J Na A 61.5 29 nh ₄ A (BC) 64.8 TO 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 below to determine the storage stability of the percarbonate.

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

Example zeolite Composition (wt. nonionic ) percarbonate J 66.9 20.6 12.5 29 66.1 21.4 12.5 TO 63.6 23.9 12.5 30 62.1 25.4 12.5

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

AvO example after (days)

0 6 9 14 J 100 ALIGN! 30.2 20.5 4.1 29 100 ALIGN! 83.9 77.7 51.6 TO 100 ALIGN! 50.0 42.0 10.5 30 100 ALIGN! 90.0 90.9 79.5

Examples 31 to 35, Comparative Examples L to O Stability of the bleach catalyst

Example 31, Comparative Example L

Detergent base powders were prepared by mixing zeolite A, in sodium or ion exchange form, with a liquid surfactant mixture - coconut sulfate (cocoPAS), coconut alcohol 3EO nonionic surfactant, coconut alcohol 7EO nonionic surfactant and water - in a laboratory scale granulator. The zeolites were used as in the previous examples: the ammonium zeolite A was the zeolite of Example 1 and the sodium zeolite was the raw material of Example 1. The differences in the formulation reflect the different carrying capacities of the two zeolites.

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

Example L Example 31 Zeolite A (Na) ^x 65.5 Zeolite A (NH ₄ ) ^x (BC) - 68.6 cocoPAS 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

x 30% neutralized mixture of ^C 12 -C ₁₈ saturated fatty acids (about 60% C ₃₂ , 17% C 18, 20% C 18, 3% C 14 + C ₁₄ ).

Samples of each powder were stored in containers above opened at 37 ° C and 70% relative humidity. After 28 days, samples were taken from stock and sample pairs were compared visually by eight assessors to evaluate relative discoloration. The results were as follows:

Evaluators preferring the presence of powder

Evaluators preferring the presence of L 0 powder

The powder of Example 31 shows a slight discoloration, while the powder of Comparative Example L was rapidly discolored. Based on a rating scale of 0 to 10, the evaluators used the following bleaching ratings:

powder 31 3 powder L 6

Example 32, Comparative Example M

Detergent base powders were prepared by mixing the zeolites MPA, in sodium or ion exchange form, with a mixture of liquid surfactants used in Example 31 and L in a laboratory scale granulator. The ammonium exchanged zeolite MAP was from Example 2 and sodium zeolite MAP was the raw material from 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 obtain powders having the following composition:

Example M Example 32 Zeolite A (Na) ^x 58.9 Zeolite A (NH ₄ ) ^x (Ex. 2) 63.6 cocoPAS 9.2 8.0 coco 7EO 9.2 8.0 coco 3E0 11.7 10.1 soap 3.5 3.1 water 2.5 2.2 total powder base 95.0 95.0 catalyst granules 5.0 5.0

^x hydrated base

Storage tests and staining evaluations were performed as described in Examples 31 and L. The results are as follows:

evaluators preferring powder 32 6 evaluators preferring powder M 2

The powder of Comparative Example M (containing sodium zeolite

MAP) was significantly less discolouring than the powder of Comparative Example L (containing sodium zeolite A), the discolouring stroke was 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 Cetostearyl stearate 31,0 Silicon dioxide * 26,4 Sodium bicarbonate 39,6 Titanium dioxide 1,0

100.0 ^x Gasil (Trade Mark) 200TP from Crosfield.

Example 33 contains 95 wt. of the base powder of Example 31 (ammonium exchanged zeolite A) and Comparative Example N contains 95 wt. of the base powder of Comparative Example A (sodium zeolite A). Each powder also contains 5 wt. catalyst granules. Storage tests were performed as in the previous examples and the results of the panel evaluation are as follows:

evaluators preferring powder 33 8 evaluators preferring powder N 0

The degree of decoloration was as follows: powder 33 0 powder N 8

Example 34, Comparative Example P

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

^for Example 34 contained 95 wt%. % of the base powder of the example (ammonium exchanged zeolite MAP) and Comparative Example P contains 95 wt. of the base powder of Comparative Example M (sodium zeolite MAOP). Each powder also contains 5 wt.

catalyst granules. Storage tests were performed as in the previous examples and the panel evaluation results were as follows:

evaluators preferring powder 34 7 evaluators preferring powder Ρ 1

The bleaching levels were as follows:

powder 34 0 powder P 3

Example 35, Comparative Example O

This example describes an accelerated storage test to demonstrate the effect of zeolite type on manganese catalyst decomposition Μη 1,4,7-Me ₃ TACN. In this test, the catalyst in non-granular form was directly in contact with the base zeolite powder.

The crystalline catalyst (0.26 g) was granulated with 7E0 nonionic surfactant (3 g) and zeolite (10 g) to give the following preparations:

Example 0 35 catalyst 1.96 1.96 zeolite A (Na) ^x 75.42 - Zeolite A (NH ₄ ) ^x (BC) - 75.42 non-ionic 7EO ^XX 22.62 22.62 100.00 100.00 ^x hydrated base ^xx C ^ 2-i5 ^oxo l ^ ^o h ° l '7EO: Synpertonic (Trade Mark) A7

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

The granules of Comparative Example Q show significant levels of brown discoloration after 24 hours of storage. However, the granules of Example 35 showed no discoloration even after 7 days of storage.

? l / 2-3Λ ~ 75 £ 364ο

Claims (14)

PATENT CLAIMS CLAIMS 1. A particulate detergent, bleach or detergent composition comprising a moisture-sensitive detergent, bleach or cleansing component and a crystalline aluminosilicate having exchangeable cations, characterized in that it contains cations derived from a weak monoacidic base as exchangeable aluminosilicate cations. A composition according to claim 1, wherein at least 5% of the exchangeable aluminosilicate cations comprise cations derived from a weak monoacidic base. Composition according to claim 1 or claim 2, characterized in that the cations derived from a weak monioacidic base comprise ammonium, lithium and hydrogen ions or combinations thereof. Composition according to any one of the preceding claims, characterized in that the aluminosilicate is zeolite A, wherein from 10 to 50% of the exchangeable cations are cations derived from a weak monoacidic base. 4 ^ Composition according to any one of claims 1 to 3, characterized in that the aluminosilicate is zeolite P having a silicon to aluminum ratio not exceeding 1.33 (zeolite MAP), wherein from 10 to 90 wt. exchangeable cations form cations derived from a weak monoacidic base. Composition according to any one of the preceding claims, characterized in that the moisture-sensitive component is an inorganic persulfate. ' 7. A composition according to claim 6, wherein the moisture-sensitive component is sodium percarbonate. Composition according to any one of claims 1 to 5, characterized in that the moisture-sensitive component is a bleaching catalyst comprising a source of Mn and / or Fe ions and a ligand which is a macrocyclic organic compound of formula I - [NR ³ - (CR ¹ (R ² ) _u ) _t ] _s wherein t is an integer from 2 to 3, s is an integer from 3 to 4, u is zero or one and R ¹ , and R ³ are independently selected from the group consisting of H, alkyl, and aryl, both optionally substituted. The composition of claim 8, wherein the moisture-sensitive component is a 1,4,7-trimethyl-1,4,7-triazacyclononane (1,4,7-Me ₃ TACN) bleach catalyst. 10. A composition according to any one of the preceding claims, _for which the particulate-containing detergent composition in a) from 2 to 60 wt.% Of one or more organic detergent surfactants, b) from 10 to 80 wt. a builder system comprising a crystalline aluminosilicate having exchangeable cations, c) from 5 to 40% by weight of a bleaching system comprising a moisture-sensitive bleaching component, d) optionally other components up to 100 wt. characterized in that the exchangeable cations of aluminosilicate (b) comprise cations derived from a weak monoacidic base. A zeolite P having a silicon to aluminum ratio not exceeding 1.33 (zeolite MAP) having exchangeable cations, characterized in that the exchangeable cations comprise cations derived from a weak monoacidic base. 12. Zeolite MAP according to claim 11, characterized in that from 10 to 90 wt. exchangeable cations form cations derived from a weak monoacidic base ₄ 13. The zeolite MAP of claim 11 or claim 12, wherein the cations derived from a weak monoacidic base are ammonium ions, hydrogen ions, or combinations thereof. 14. Use of a crystalline aluminosilicate having exchangeable cations for stabilizing a moisture-sensitive detergent, bleaching or cleaning component in a particulate detergent, bleaching or cleaning composition, characterized in that the exchangeable cations form cations derived from a weak monoacidic base.