CA1153162A

CA1153162A - Particulate bleach compositions

Info

Publication number: CA1153162A
Application number: CA000355510A
Authority: CA
Inventors: Roger Foret; Philippus Van Der Hoeven
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1979-07-06
Filing date: 1980-07-04
Publication date: 1983-09-06
Also published as: DE3024912A1; NL8003907A; DK290880A; IT8068064A0; FR2460997A1; JPS5655500A; YU175580A; GR69189B; SE437850B; IE801372L; FI66426C; CH643590A5; PT71502A; ATA348280A; BE884208A; AU536484B2; ES493151A0; FI66426B; SE8004977L; DE3024912C2

Abstract

C 573 (R) Abstract of the Invention Particulate bleach (and detergent) compositions with improved bleach efficiency are disclosed comprising a particulate peroxy bleach compound and tetraacetyl ethylene diamine (TAED), said TAED
having the following particle size distribution as determined by sieve analysis: 0 - 20% >150 µm 10 - 100% >100 µm < 150 µm 0 - 50% < 75 µm 0 - 20% < 50 µm, and being contained in granules in combination with a granulating agent, said granules having particle size ranging from 100-2000 µm and comprising 10-99% by weight of TAED. The particulate bleach composition does not suffer from significant sedimentation and/or dissolution problems and does not suffer from significant de-composition problems during storage.

Description

` 1153~62 -1- C 573 (R) PARTICULATE BLEACH COMPOSITIONS
This invention relates to particulate bleach compositions with improved bleach efficiency. More particularly it relates to par-ticulate bleach compositions which contain a peroxybleach compound and an organic activator for this peroxybleach compound. Such bleach compositions are also active at lower temperatures, i.e. in the range from ambient temperature to about 60C. Such bleach compo-sitions, also referred to as low-temperature bleach compositions, are known in the art. They normally comprise an inorganic persalt releasing active oxygen in solution, hereafter called for the pur-pose of this invention a peroxybleach compound, such as sodiumperborate and an activator therefor, which is usually an organic compound having one or more reactive acyl residues, which at relatively low temperatures react with the peroxybleach compound causing the formation of organic peracids, the latter providing for a more effective bleaching action at lower temperatures than the peroxybleach compound. These low-temperature bleach compositions are more fully described in e.g. British Patent Specifications 836,988, 855,735, 907,356, 907,358 an 1,003,310. The best-known organic activator of practical importance is N,N,N',N'-tetraacetyl ethylene diamine, normally referred to as simply tetraacetyl ethylene diamine and coded TAED.

The present invention is concerned with the use of N,N,N',N'-tetraacetyl ethylene diamine as the activator for peroxybleach compounds.
Although such bleach compositions can provide for acceptable bleach efficiency, it has been determined in fabric washing machine opera-tions that the bleach efficiency is generally less than one would expect on the basis of the relative amounts of peroxybleach and activator used. Further investigation has shown that in many instan-ces a substantial amount of the activator remains ineffective, due to sedimentation in the bleach/wash-liquor, and/or a relatively slow rate of dissolution. This phenomenon of material loss during the wash is referred to hereinafter as sedimentation mechanical loss. It concerns that part of the particulat~ product which is first dispersed in the water inside ~he machine but which sediments ~`, - ,~

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-2- C 573 (R) there and largely remains inef~fective during the whole washing/
bleaching process.

Also decomposition of the activator may occur during storage of the particulate bleach composition.

The present invention serves to mitigate the above problems ~ a substantial degree.

Some of these problems have been recognised in the art and various attempts have been made to solve them~without great success.

British patent specification 864,798 deals with the use of certain organic esters of carboxylic acids, e.g. sodium acetoxybenzene sul-phonate, in granular form as activator for inorganic persalts. Adisadvantage of these esters is that they tend to (per-)hydrolyse more readily than tetraacetyl ethylene diamine, the activator used in the present invention, and hence suffer from a more severe decom-position problem during storage.
In US patent specification 4,087,369 it is proposed to provide the activator in coarse crystalline form having a mean particle diameter in the range of 500-1800 micrometers or as agglomerates of the same mean particle diameter. Though this may reduce the decom-position problem of tetraacetyl ethylene diamine, it does not solveand may even increase the more severe problem of sedimentation loss and/or insolubility.

In British patent specification 1,459,974 a bleach composition is described, comprising a mixture of sodium perborate and activator in finely divided form so as to provide for rapid dissolution there-of. Such a composition, however, will suffer from a serious decom-position problem during storage. Being a mere mixture of f1ne mate-rials, it tends to give handling, segregation and storage decompo-sition problems when used in a particulate detergent composition.

US patent specification 4,064,062 discloses a bleaching composition comprising a mechanical mixture of a finely divided sodium perborate .
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- 3 - C 573 (R) tetrahydrate, a finely divided activator; e.g. "BHADT", and finely divided solid fatty acid of average particle diameter in the 44 to 149 micrometer range, and a molecular sieve zeolite. A bleaching com-position of this description comprising TAED has poor storage stability.

British patent specification 1,395,006 discloses particulate bodies, each comprising a dispersible composite particle containing finely divided activator material, e.g. tetraacetyl ethylene diamine (TAED) passing mesh size of 0.10 mm provided with a coherent protective layer.
The activator according to this patent is desirably of as small a particle size as possible and should preferably pass a mesh of 0.05 mm (50/um). Such fine TAED would be very difficult to handle during pro-cessing and does not give satisfactory granules when granulated accord-ing to the simple granulation techniques. Moreover, products of this description, while possibly being protected from the environment9 will tend to sediment in the washing machine due to their solid and heavy construction.

It is therefore an object of the present invention to provide an improved low-temperature bleach composition comprising a peroxy bleach compound and tetraacetyl ethylene diamine as the activator therefor, which does not suffer from significant sedimentation and/or dissolution problems, and simultaneously does not suffer from signifi-cant decomposition problems during storage.
This and other objects, which will be apparent in the further des-cription of the invention, have now been found possible to achieve by using tetraacetyl ethylene diamine (TAED) in granular form, the granules containing TAED of a critical, special particle size as defined hereinafter.

In its broadest sense, the invention therefore relates to a parti-culate bleach composition comprising a particulate peroxybleach compound and tetraacetyl ethylene diamine as activator therefor, the latter being contained in granules with a granulating agent, the granules containing said tetraacetyl ethylene diamine of a critical particle size which will be defined in more detail hereafter.

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-4- C 573 (R) It has been found that if the average particle size of the TAED
is less than 150/um (micrometer), a very significant improvement in bleach efficiency is obtained. The sedimentation losses, when using TAED with an average particle size of less than 150/um, are S substantially decreased. Even better bleach performance is obtained if the average particle size of the TAED is <1~0/um. However, too small a particle size entails certain drawbacks, such as a certain decomposition, dust-formation and handling problems, and although particle sizes below 100/um can provide for an improved bleaching efficiency, the TAED fraction should not contain more than 50% by weight of particles with a size of less than 30/um. Advantageously the TAED fraction should contain not more than 50%, preferably not more than 30~ by weight of particles with a size of less than 75jum and not more than 20%, preferably not more than 10% by weight of particles of a size less than 50 ~m. TAED becomes very difficult to handle during processing if a major proportion of it is very fine (40-50 ~ or less). Also control of the granulation process and of the resulting granule size distribution is difficult if the TAED particle size distribution is very wide. On the other hand, the TAED fraction used may contain a certain amount of particles of a size, >150/um, but it should not contain more than 20% by weight of particles >150/um. It is to be understood that these particle sizes refer to the TAED present in the granules, and not to the granules themselves.
The latter have a particle size ranging from 100-2000 ~m, the major part of it ranging from 100 to 1000 ~m, preferably 500 to 900/um.
Though up to 5% by weight of granules with a particle size of <100/um may be tolerable, a lower limit of 100/um on the granule size is set by storage stability so as to exclude ungranulated material.
Accordingly, the activator granules of the present invention contain tetraacetyl ethylene diamine (TAED) of the following particle size distribution as determined by sieve analyses:

115316~
- - 5 - C 573 (R) O - 20% >150/um 10 - 100% >100/um < 150/um O - 50% < 75/um O - 20~ < so/um Preferred TAED has particle size distribution:
O - 10% >150/um 15 - 85% >100/um < 150/um ~ 30% ~ 75/um O - 10% < 50/um.
The granules may be obtained by granulation with a suita~ble carrier material, such as granular sodium triphosphate/potassium triphosphate mixtures with TAED particles of the required size. Other granulation methods using organic and/or inorganic granulation agents can also be usefully applied,such as tetrasodium pyrophosphate, disodium orthophosphate~gelatin, dextrin, sodium carboxymethyl cellulose, nonionic ethylene oxide condensation products, each alone or in combination. A preferred granulation/binder system is a mixture of sodium triphosphate and potassium triphosphate, which is applied by preparing a pre-mix of solid finely divided sodium triphosphate with TAED, on to which potassium triphosphate is sprayed ~s a saturated aqueous solution during the granulation process, e.g.
in a rotating pan granulator. The granules can be subsequently dried, if required. Basically, any granulation process is applicable, as long as the granule contains TAED of the required particle size, and as long as the other materials, present in the granule, do not negatively affect the activator. Suitable granulation equipments are e.g. rotating pan granulators and the Schugi Flexomix, both equipments working on a principle of spraying a liquid agent on to a moving mass of solid particles to effectuate granulation of the particles.

It is to be observed here that in US patent specification 4,087,369 it is proposed to use a particulate crystalline peroxybleach activator having a much greater mean particle size, i.e. in the range from about 500-1800/um. It is stated in this US patent that the lower particle diameter appears to be critical inasmuch as ... .

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llS31~2 - 6 - C 573 (R) particle sizes of less than 500 ~m are prone to a markedly decreased storage stability.

In contrast to this teaching, it is highly surprising that this problem does not occur when using TAED of a substantially smaller mean particle size according to the invention.

The peroxybleach compound, used in the present invention, need not have the same particle size as that of the activator, and in fact it is preferable that the peroxybleach has a different, bigger particle size than the activator in order to prevent segr`egation.

The granules, which contain the TAED of the required particle size, will contain said TAED in an amount of 10 to 99% by weight, preferably 40 to 90% by weight. The bleach composition will contain the granules in an amount, calculated as TAED, of 0.25 to 50% by weight, preferably 1 to 40% by weight.

The peroxybleach compound will be used in the present invention in an am~unt of 3 to 99.5% by weight, preferably 4 to 80% by weight.
Typical examples of suitable peroxybleach compounds releasing active oxygen in aqueous solution are the alkalimetal perborates, -per-carbonates, -persilicates and -perpyrophosphates. Particularly preferred are the alkalimetal perborates, such as sodium perborate tetrahydrate and sodium perborate monohydrate, because of their commercial availability.

Accordingly, in a more specific embodiment of the invention a bleaching composition will comprise 3 to 99.5%, preferably 4 to 80% by weight of a particulate peroxy bleach compound, and 0.25 to 50%, preferably 1 to 40% by weight of TAED, having the following particle size distribution as determined by sieve analysis:
0 - 20% >150/um 10 - 100% >100lum < 150/um ~ 50% < 75lum 0 - 20% < 50/um, , il53~;2 - 7 - C 573 (R) said TAED being contained in granules, in combination with a granul-atins age~t, said granules comprising 10-33%, preferably 40-~0% by weight of said TAED.

Preferably the bleach composition of the invention comprises a stabilising agent for peracids. Suitable stabilising agents include the organic phosphonic aciu compourlds such as ethylene diamine tetra(methylene phosphonic acid), and diethylene tri amine penta-(methylene phosphonic acid). They can be used as such or as their water-soluble salts or as their complexes with calcium, magnesium, zinc or aluminium. These stabilising agents may be incorporated in the detergent slurry before spray-drying or, as desired, be dry mixed with the bleach composition or coOgranulated with the TAED. The amount of stabilising agent used in the present invention is usually 0.05-5% by weight, preferably 0.1 to 3% by weight based on the total composition.

The bleach composition of the invention may consist solely of the peroxy bleach compound in admixture with the TAED granules, or preferably it may in addition thereto contain other ingredients so as to form a detergent bleach composition suitable for use in household and industrial washing machines. Thus it may contain from 2-20% by weight of one or more of a detergent active compound selected from the group consisting of fatty acid soaps, anionic, nonionic, amphoteric and zwitterionic detergent active materials and mixtures thereof.

Examples of anionic detergent compounds are alkylaryl sulphonates (e.g. sodium dodecylbenzenesulphonate), products of the sulphona-tion of olefins, so-called olefinsulphonates; fatty alcohol sul-phonates; alkylether sulphates, in the form of their alkali metal salts, and alkali metal salts of long chain C8-C22 fatty acids.

Nonionic detergent compounds can be broadly defined as compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic compound which may be aliphatic or alkylaromatic l~S~16Z

- 8 - C 573 (R~

in nature. The length of the polyalkylene oxide group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Examples of suitable nonionic detergent compounds are the conden-sation products of C6-C12 alkylphenols with 5-25 moles of ethylene oxide per mole of alkylphenol; the water-soluble condensation products of C8-C22 aliphatic alcohols, either straight or branched chained, with 5-30 moles of ethylene oxide per mole of alcohol.
Amphoteric detergents include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic moiety can be straight-chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.

Zwitterionic detergents include derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic moieties can be straight-chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.

Other detergent-active materials are described in the books "Surface-Active Agents and Detergents" Vol. I and II by Schwartz, Perry and Berch (published by Interscience).

Furthermore, the composition of the invention may contain from 10 to 60% by weight of one or more of a detergency builder material.
Examples of such detergency builders are sodium and potassium tri-phosphate, sodium orthophosphate, sodium and potassium pyrophosphate, sodium carbonate, sodium silicate, zeolites and other organic non-phosphate builders, such as nitrilotriacetate acid and its water-soluble salts, sodium ethylene diamine tetraacetate, carboxy-methyloxymalonate, carboxymethyloxysuccinate, sodium citrate~poly-electrolytes, etc. In addition and if desired further ingredients commonly used in such compositions may be incorporated, such as ~153~62 - - 9 - C 573 (R) buffers, hydrotropes, corrosion inhibitors, soil-suspending ~nd anti-redeposition agents, e.g. sodium carboxymethylcellulose, poly-vinylpyrrolidon, lather boosters, lather depressors, sequestering agents, bactericides, softening agents, perfumes, colouring agents and enzymes, particularly proteolytic enzymes, such as those known under the tradenames Alcalase ~ ex Novo Industri A/S Copenhagen;
Maxatase ~ ex Gist-Brocades N.V. Delft; and high-alkaline proteases such as those described in British Patent Specification 1,243,784.
Examples of high alkaline_proteases are sold under the tradenames Esperase ~ and Savinase ~ .

In such detergent bleach composition the proportion of TAED~ will generally be in the range of 0.25-15% by weight, preferably from 1-10% by weight.
The proportion of peroxybleach compound will generally be in the range of 3-30% by weight, preferably from 4-20% by weight.

The invention will now be illustrated by way of the following Examples.

Example 1 Bleaching tests were carried out with a composition given below in a commercial washing machine under the following conditions:
Wash temperature: 60C (main wash only) Wash load : Clean loads (4 kg of cotton) Water hardness : 7-8 GH (tap water) Dosage of composition: 100 9 per cycle.
Number of repeats:
a) Mechanical loss of activator: 3 repeats b) Bleaching efficiency on tea-stained test-cloths: 5 repeats.

The bleaching efficiency (~R) was measuredby reflectance measure-ments, using an Elrephometer with a 420 nm filter, and the mechani-cal loss was measured by standard concentration measurement.

- 10 - C 573 (R) Composition % by weight C12-alkylbenzene sulphonate 7 Tallow fatty alcohol, condensed with 25 moles of ethylene oxide 1.35 11-13 Fatty alcohol, condensed with 13 moles of ethylene oxide Sodium stearate 4 Sodium tripolyphosphate 36 Sodium silicate 6 10 Sodium carboxymethylcellulose Magnesium ethylenediamine tetraacetate 0.12 Fluorescer 0.25 Sodium sulphate 16.23 Sodium perborate 12 lS Tetraacetyl ethyl.ene diamine (TAED) 3 Ethylene diamine tetramethyl phosphonic acid0.3 Enzyme noodles 1.6 Perfume 0.15 Water 10.
The TAED was added to this composition by dry mixing in the form of granules.

These granules were prepared batchwise in an 0.5 metre rotating pan granulator by charging a premix of TAED and sodium triphosphate (STP), on to which a hot (50C) potassium triphosphate (KTP) solution (48% W/W) was sprayed. The granules were then dried off in a fluid bed drier at approximately 55C.

TAED granules A were of mean particle size of 700-900 ~m and contained TAED of which the main portion has particle size~ 104 ~, having the following sieve analysis:
Sieve size (~m) % retained on each sieve 150 0.5 125 9.8 40.2 63 20.1 26.1 < 45 3.3 ' ' ' ; : ' :
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- 11 - C 573 (R) Granule A composition:
TAED 60.0%
STP 18.1%
KTP 18.0%
Water 3.9% (as bound water).

TAED granules B were of mean particle size of 700-900 m and ~I
containedTAED of average particle size between 104 ~ and 150/um and had the following composition:
TAED 61.4%
STP 21.1%
KTP 14.1%
Water 3.4% (as bound water).

TAED granules C were of mean particle size of 700-900 ~m and contained TAED, obtained from a mixture of 50% TAED as used in granules B + 50% TAED as used in granules A.

Granule C composition:
TAED 59.6%
STP 20.6%
KTP 14.9%
Water 4.9% (as bound water).

As control, TAED granules, havina a particle size of approximately 800 ~m (+ 100 ~). (15-20% >1000 ~m and about 20% ~ 400 ~m) and containing TAED of average particle size of about 250 ~m, were used.

Control granule composition:
TAED 65% `
STP 21%
KTP 8%
Water 6% (as bound water).

These granules were dosed in such an amount in the above detergent composition to provide for 3% TAED in the composition, yielding four compositions A, B, C and the control. The results of the ~ `

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- 12 - C 573 (R) experiments are given below.

A B CControl ~Total mechanical loss at 40C 42 45 5372 Total mechanical loss at end wash 37 4150 64 Sedimentation mechanical loss at 40C 27 2940 65 QR 15 4 13 5 14.7 9.6 These results show a reduced loss of TAED, and an improved bleach efficiency, compared with the control TAED granulate.

* Total mechanical loss is the sum of sedimentation loss and direct mechanical loss which concerns that part flowing directly from the dispenser to the drain of the washing machine at the very beginning of the water intake.

Example 2 The following compositions were tested in four different washing machines, under the following conditions:

Wash temperature : + 60C (main wash only) Wash load : Naturally soiled loads (4 kg of cotton) Water hardness : 7-8 GH
Dosage of composition: 150 9 per cycle.

The bleaching efficiency (QR) was determined as in Example 1, and the results are the average of those obtained in the 4 different washing machines. The control contained the control granules of Example 1, and the TAED granules A were those of Example l~

Results in soiled system (Average results in 4 different washing machine models).

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. , . : .-li53162 - 13 - C 573 (R) Composition I

% TAED in detergent: 1.47 1.85 2.60 2.98 ~ R control 5.1 4.8 10.2 10.8 % TAED in detergent: 1.31 1.64 2.31 2.65 ~ R TAED granules A 7.7 7.7 14.5 13.1 A comparison per column indicates that in spite of a lower TAED
content the formulation containing the granules A gave better bleaching results on tea stains than the control.

Composition II

% TAED in detergent 0.97 1.26 1.55 1.85 ~ R control 2.8 5.0 5.4 8.3 % TAED in detergent 0.86 1.17 1.64 1.90 ~ R TAED granules A 4.3 6.8 9.1 10.1 In spite of a lower TAED content (columns 1 and 2) the granules A gave a better bleaching efficiency than the control. A slightly higher TAED content gave a proportionally much higher bleach efficiency.

Composition I % by weight 25 C12-alkylbenzene sulphonate 7 Tallow fatty alcohol, condensed with 25 moles of ethylene oxide 1.35 C11-C13 alcohol condensed with 13 moles of ethylene oxide 30 Sodium stearate 4 Sodium tripolyphosphate 34.7 Alkaline sodium silicate 5.25 Fluorescer 0.17 Sodium carboxymethyl cellulose 0.7 35 Ethylene diamine tetraacetate 0.12 Sodium sulphate 11.41 Ethylene diamine tetra(methylene phosphonic acid) 0.3 :

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-- 14 - C 573 (R) Composition I (contd~ /0 by weight Water 10 Sodium perborate 6 Enzyme noodles 2.25 TAED (expressed as pure TAED) from 1.40 to 2.98%
(see Table of results) Na2S04 . ad 100.

Composition II % by weight .
C12-alkylbenzene sulphonate 7.5 Sodium stearate 5.0 Neutral sodium silicate ~ 6.0 Fluorescer 0.2 Sodium sulphate 15.66 Ethylene diamine tetraacetate 0.2 Tallow fatty alcohol condensed with 18 moles of ethylene oxide 3.0 Prehydrated sodium tripolyphosphate 34.1 Sodium carboxymethyl cellulose 1.0 Ethylene diamine tetra(methylene phosphonic acid) 0.36 Sodium perborate 6 Enzyme noodles 2.25 TAED (expressed as pure TAED) from 0.92 to 2.4%
(see Table of results) Sodium sulphate ad 100.
Example 3 Storage stabilities of TAED, sodium perborate and fluorescent agent were examined in a mixed active detergent base powder composition to which 3% TAED and 10% sodium perborate tetra-hydrate were added.
Mixed active detergent base powder composition Parts by weight C12-alkylbenzene sulphonate 5.2 C11_13 alcohol condensed with 12-18 moles of ethylene oxide 5.2 Sodium triphosphate 34.0 Alkaline sodium silicate 4.0 Sodium carboxymethyl cellulose 0.8 Magnesium silicate 0.5 liS3162 - 15 - C 573 (R) Mixed active detergent base powder compositionParts by weight (Contd.) Tetrasodium ethylene diamine tetraacetate 0.17 Fluorescer 0.14 Sodium sulphate 12.0 Water 8.3 Ethylene diamine tetra(methylene phosphonic acid) 0.3 The storage results using different types of TAED are given below:

TAED type: % residual after 4 weeks at 37C/70~ RH
TAED Perborate Fluorescer I (granulated) 87 92 84 II (ungranulated) 16 42 30 II (granulated')50 69 60 III (granulated)72 70 89 TAED type I was TAED of particle size distribution as used in granules A of Example 1.

20 TAED type II had the following particle size distribution:
8.2% >90 ~m 8.7% 63-90 ~m 13.3% 45-63 ~m 40.3% 38-45/um 29.6% ~38 ~m.

TAED type III was coarse TAED of mean particle size of 250-300 ~m.

From the above results it can be seen that the composition containing granulated TAED type I according to the invention shows an improved overall stability with respect to TAED, sodium perborate and fluorescer, as compared with the composi-tions outside the invention using granulated or ungranulated TAED type II and an at least equal overall stability as compared with the composition containing granulated TAED type III.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A particulate bleach composition comprising a particu-late peroxybleach compound and tetraacetylethylene diamine (TAED) as activator therefor, said TAED having the following particle size distribution as determined by sieve analysis:
0 - 20% > 150 µm 10 - 100% > 100 µm < 150 µm 0 - 50% < 75 µm 0 - 20% < 50 µm and being contained in granules in combination with a granulat-ing agent, said granules having a particle size ranging from 100 to 2000 µm and comprising 10 - 99% by weight of said TAED.

2. A particulate bleach composition according to claim 1, wherein said granules contain tetraacetyl ethylene diamine of the following particle size distribution:
0 - 10% > 150 µm 15 - 85% > 100 µm < 150 µm 0 - 30% < 75 µm 0 - 10% < 50 µm.

3. A particulate bleach composition according to claim 1 or claim 2, comprising a stabilising agent selected from the group consisting of ethylene diamine tetra(methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid) and water-soluble salts thereof.

4. A particulate bleach composition according to claim 1 or claim 2, comprising a stabilising agent selected from the group consisting of ethylene diamine tetra(methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid) and water-soluble salts thereof and wherein said stabilising agent is present in an amount of 0.05 - 5% by weight.

5. A particulate bleach composition according to claim 1 comprising 3 - 99.5% by weight of said particulate peroxybleach compound and 0.25 - 50% by weight of tetraacetyl ethylene diamine.

6. A particulate bleach composition according to claim 5 comprising 4 - 80% by weight of said particulate peroxybleach compound and 1 - 40% by weight of said tetraacetyl ethylene diamine.

7. A particulate bleach composition according to claim 1, wherein said granules contain 40 - 90% by weight of tetraacetyl ethylene diamine.

8. A particulate bleach composition according to claim 1 or claim 2 wherein said granulating agent is a mixture of sodium triphosphate and potassium triphosphate.

9. A particulate bleach composition according to claim 1 which includes one or more of a detergent active compound selected from the group consisting of fatty acid soap, anionic, nonionic, amphoteric and zwitterionic detergent active materials and mixtures thereof.

10. A particulate bleach composition according to claim 9, which includes one or more of a detergency builder material.

11. A particulate bleach composition according to claim 10, comprising:
(a) 2 - 20% by weight of detergent active compound;
(b) 10 - 60% by weight of detergency builder material:
(c) 3 - 30% by weight of peroxybleach compound, and (d) 0.25 - 15% by weight of tetraacetyl ethylene diamine.

12. A particulate bleach composition according to claim 11 comprising 0.05 - 5% by weight of a stabilising agent.