WO1993008254A1

WO1993008254A1 - Granular bleach-activator composition

Info

Publication number: WO1993008254A1
Application number: PCT/EP1992/002178
Authority: WO
Inventors: Reinhard Mueller; Guenter Oetter; Alfred Oftring; Volker Schwendemann; Wolfgang Trieselt
Original assignee: Basf Aktiengesellschaft
Priority date: 1991-10-22
Filing date: 1992-09-21
Publication date: 1993-04-29
Also published as: DE4134770A1; AU2577192A

Abstract

The invention concerns a granular bleach-activator composition containing: A) 30 to 95 parts by weight of one or more 4H-3,1-benzoxazin-4-one derivatives of the formula I, in which R is a C1-C4 alkyl or alkoxy group, a phenyl group, an o-, m- or p-tolyl group, a p-chlorophenyl group, a m-nitrophenyl group, a m-methoxyphenyl group or a m-methylsulphonylphenyl group, or a mixture of compounds of the formula I and other usual bleach activators, with the exception of mixtures of 90 % by wt. or less of compounds of the formula I with 10 % by wt. or more of pentaacetyl glucose, and B) 5 to 70 parts by weight of one or more additives selected from the following categories of compound: 1) anionic surfactants, 2) non-ionic surfactants, 3) zwitter-ionic surfactants, 4) polymers containing carboxylic groups, 5) polysaccharides, 6) poly(alkylene glycol) compounds.

Description

Granular bleach activator composition

description

The present invention relates to a new granular bleach activator composition comprising 4H-3, 1-benzoxazin-4-one derivatives, optionally further conventional bleach activators and additives. The invention further relates to a method for producing this bleach activator composition and to detergents and cleaning agents which contain this granular bleach activator composition.

Many bleach activators, including 4H-3, 1-benzoxazin-4-one derivatives, have insufficient water solubility, especially in the temperature range between 25 and 60 ° C, and are in

Washing powder not sufficiently stable in storage. It is therefore common practice to assemble these bleach activators to increase the rate of dissolution and the effectiveness in the wash liquor and to improve the shelf life.

US Pat. No. 4,483,778 (1) relates to a granular peroxy bleach activator composition which contains nonionic surfactants, polyethylene glycols, fatty acids, anionic surfactants or film-forming polymers such as homo- and copolymers of acrylic acid, hydroxyacrylic acid and methacrylic acid or cellulose derivatives as binders or enveloping material.

EP-A 062 523 (2) relates to a bleach activator granulate which is produced by extruding a mixture of a low-melting surfactant, a bleach activator such as N, N, N ', N'-tetraacetylethylene diamine and an additive.

EP-A 456 109 (3) relates to a process for the preparation of a granular bleach activator composition from pentaacetyl glucose, optionally further conventional bleach activators and additives by reacting glucose with acetic anhydride, removing the acetic acid formed by distillation, and mixing the pentaacetyl glucose thus obtained with the other components and packaging. Insofar as 4H-3, l-benzoxazin-4-one is also used, only a weight ratio of these compounds to pentaacetyl glucose of 1:99 to 90:10 is disclosed. The known agents of the prior art are also in need of improvement with regard to the rate of dissolution and effectiveness in the washing liquor and the storage stability in the washing powder; in particular, this also applies to 4H-3, l-benzoxazin-4-one derivatives.

The object of the present invention was therefore to remedy the disadvantages of the prior art described.

Accordingly, a granular bleach activator composition has been found which

A) 30 to 95 parts by weight of one or more 4H-3, 1-benzoxazin-4-one derivatives of the general formula I.

in which R is C 1 ~ to C 4 ~ al yl or alkoxy, phenyl, o-, m- or p-tolyl, p-chlorophenyl, m-nitrophenyl, m-methoxyphenyl or methylsulfonylphenyl, or a mixture of the Compounds I and other conventional ^" bleach activators, with the exception of mixtures of 90% by weight or less of the compounds I and 10% by weight or more of pentaacetyl glucose, and

B) 5 to 70 parts by weight of one or more additives from the substance classes

(1) anionic surfactants,

(2) nonionic surfactants,

(3) zwitterionic surfactants, (4) carboxyl group-containing polymers,

(5) polysaccharides,

(6) polyalkylene glycols,

contains.

Components A and B of the bleach activator composition according to the invention are distributed essentially homogeneously in the mixture. In addition to being a binder, additives B have above all a dispersing function, but can also have a protective function for the bleach activators against, for example, moisture or atmospheric oxygen in the form of coatings.

To improve the bleach activator effect, component A can contain, in addition to the compounds I, other conventional bleach activators. The

Weight ratio of the additional bleach activators to the compounds I is usually 1:99 to 90:10, preferably 1:99 to 50:50.

The following are additional bleach activators:

Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, e.g. Sodium p-isononanoyloxy-benzenesulfonate or sodium p-benzoyloxy-benzenesulfonate;

N-diacylated and N, '-tetraacylated amines, e.g. N, N, N ', N'-tetraacetyl-methylenediamine and -ethylenediamine, N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5, 5-dimethylhydantoin;

acylated sugars, e.g. Pentaacetyl glucose.

In addition, there are also additional bleach activators:

N-alkyl-N-sulfonyl-carbonamides, e.g. N-methyl-N-mesyl-acetamide or N-methyl-N-mesyl-benzamide;

N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. Monoacetyl maleic acid hydrazide;

- 0, N, N-trisubstituted hydroxylamines, e.g. O-benzoyl-N, - succinyl-hydroxyla in, 0-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetyl-hydroxylamine;

N, N'-diacyl-sulfurylamide, for example N, N'-dimethyl-N, N'-di-acetyl-sulfurylamide or N, N'-diethyl-N, N'-di-propionyl-sulfurylamide; Triacyl cyanurates, for example triacetyl cyanurate or tribenzoyl cyanurate;

Carboxylic anhydrides, e.g. Benzoic anhydride, m-chloro-benzoic anhydride or phthalic anhydride;

1,3-diacyl-4,5-diacyloxyimidazolines, e.g. 1,3-diacetyl-4,5-diacetoxy-imidazoline;

- tetraacetylglycoluril and tetrapropionylglycoluril;

diacylated 2,5-diketopiperazines, e.g. 1,4-diacetyl-2,5-diketopiperazine;

Acylation products of propylene diurea and 2,2-dimethylpropylene diurea, e.g. Tetraacetylpropylene diurea;

α-acyloxy polyacyl malonamides, e.g. α-acetoxy-N, '-diacetylmalonamide;

Diacyl-dioxohexahydro-1,3,5-triazines, e.g. 1,5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine.

A preferred granular bleach activator composition consists of

A) 40 to 90% by weight of compound I or a mixture of I with further customary bleach activators, B) 10 to 60% by weight of one or more additives B and C) 0 to 20% by weight of customary auxiliaries C.

Suitable anionic surfactants (1) for B are, for example, alkali metal salts of fatty acids, alkylbenzenesulfonates, alkanesulfonates, α-olefinsulfonates, hydroxyalkanesulfonates, α-sulfofatty acid esters, alkyl sulfates, alkyl ether sulfates or fatty alcohol ether sulfates. Alkylbenzenesulfonates, in particular the alkali metal and ammonium salts of linear C 1 -C ₃ -alkylbenzenesulfonates, for example sodium dodecylbenzenesulfonate, are preferred. Nonionic surfactants (2) for B are, for example, primary or secondary alcohol oxalkylates such as fatty alcohol ethoxylates and alkylphenoloxyalkylates, fatty acid alkylolamides and especially alkyl glycosides, especially Cβ- to Cie-monoalkyalkglucosides, for example Cio-monoalkylglucoside.

Suitable zwitterionic surfactants (3) for B are, for example, secondary and tertiary amine oxides.

Suitable carboxyl group-containing polymers (4) for B are, in particular, homopolymers of acrylic acid and methacrylic acid and copolymers containing acrylic acid and / or methacrylic acid, and the associated alkali metal or ammonium salts. Acrylic acid-maleic acid copolymers are particularly preferred, in particular in partially neutralized form, e.g. 50% acrylic acid-maleic acid copolymer present as sodium salt (weight ratio acrylic acid: maleic acid = 70:30).

The most advantageous polysaccharides (5) for B are starch, amylose and derivatives of these naturally occurring polysaccharides such as carboxymethyl cellulose, cellulose acetate hydrogen phthalate, ethyl cellulose or sulfated cellulose ethers. Of these, starch itself can best be used.

Particularly suitable polyalkylene glycols (6) for B are polyethylene glycols and ethylene oxide-propylene oxide copolymers.

Mixtures of several additives B from one of groups (1) to (6) or from different groups can also be used.

The granular bleach activator compositions can also contain customary auxiliaries C in the amounts customary for this, customary auxiliaries which, e.g. as disintegrants, dispersants or

Packaging aids are used, for example, polymers such as polyvinylpyrrolidone or inorganic salts such as sodium sulfate or sodium triphosphate. Complexing agents such as phosphonates, EDTA or NTA can also be present. In a preferred embodiment, the granular bleach activator composition according to the invention additionally contains 0.1 to 30% by weight, in particular 0.1 to 5% by weight, based on the total amount of the composition, of an aliphatic di- or tricarboxylic acid or an aromatic mono- or Dicarboxylic acid, which may additionally contain hydroxyl groups in the molecule, or a mixture thereof. The carboxylic acids mentioned are usually distributed essentially homogeneously in the bleach activator composition according to the invention. This brings about an improvement in color stability when stored in washing powders.

Suitable aliphatic di- or tricarboxylic acids and aromatic mono- or dicarboxylic acids, which can additionally contain hydroxyl groups in the molecule, are, for example, Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, maleic acid, fu aric acid, tartaric acid, malic acid, citric acid, benzoic acid, salicylic acid, phthalic acid, α- and ß-naphthoic acid and naphthalic acid. Adipic acid, tartaric acid, citric acid and benzoic acid are preferred.

The invention further relates to a method for producing the granular bleach activator composition according to the invention, which is characterized in that

in which R represents C 1 -C 1 -alkyl or -alkoxy, phenyl, o-, m- or p-tolyl, p-chlorophenyl, m-nitrophenyl, m-methoxyphenyl or m-methylsulfonylphenyl, or a mixture of the compounds I and other customary bleach activators, with the exception of mixtures of 90% by weight or less of the compounds I and 10% by weight or more of pentaacetyl glucose, in the molten state with B) 5 to 70 parts by weight of one or more additives from the substance classes

(1) anionic surfactants,

(2) nonionic surfactants,

(3) zwitterionic surfactants,

(4) polymers containing carboxyl groups,

(5) polysaccharides,

(6) polyalkylene glycols,

and, if desired, further additives and auxiliary substances are mixed (step a) and the resulting mixture is converted into a granular form by packaging (step b).

The pure compounds I usually melt in the temperature range from 100 to 200 ° C. If mixtures of the compounds I are used with other conventional bleach activators, this mixture can also melt at lower temperatures. If further bleach activators are used, these can be added to the compounds I before or simultaneously with the additives B. The mixing step (a) of the molten bleach activator component A with the additives B is thus advantageously carried out at temperatures from 60 to 180 ° C., preferably 80 to 150 ° C. The additives B are clearly dissolved or finely dispersed in the melt of A.

For the mixing of components A and B, all devices customary for this can be used, which can be operated in the above-mentioned temperature range of the melt; In particular, stirring and kneading equipment and extruders should be mentioned here.

From an economic point of view, it is particularly advantageous to carry out the process according to the invention directly after the preparation or purification of the compounds I, because in this case the compounds I are generally obtained in the molten liquid state and do not have to be melted with an additional supply of energy. The assembly step (b) can in principle be carried out using all customary assembly methods. However, some embodiments have proven to be particularly advantageous.

In a preferred embodiment, the preparation (b) is carried out by grinding the solidified melt from bleach activators A and additives B to the desired particle size. All devices customary for this purpose can be used for grinding; are here in particular

Hammer mills, pin mills and impact plate mills. To achieve good grinding results, the melt should be cooled to temperatures below approx. 25 ° C.

In a further preferred embodiment, the

Preparation (b) by extrusion of the molten mixture of bleach activators A and additives B and subsequent mechanical comminution to the desired particle size. All common extruder types can be used for this; Continuous running in the same direction are preferred

Twin-shaft extruder used, they advantageously have a cleaning profile.

The use of extruders offers the additional advantage that the mixing step (a) and the finishing step (b) can be carried out in one device.

The product crystallized through nozzles to a certain toughness is expediently shaped into continuous filaments in the extruder and, after cooling, comminuted on a cooling belt. The cooling of the melt consisting of components A and B in the extruder is preferably carried out with cooling water of 30 to 70 ° C., so that the toughness of the melt is not too high and thus a good distribution of the individual components after mixing is possible. On the other hand, the cooling must be sufficient to generate enough crystals of germs and to achieve a minimum toughness which only allows extrusion of dimensionally stable threads. Additional cooling and comminution devices can be connected downstream of the extruder. In a further preferred embodiment, the preparation (b) is carried out by spraying the molten mixture of bleach activators A and additives B to the desired particle size. All the usual devices for this purpose can be used for spraying; Spray towers are particularly worth mentioning here.

The embodiments of the preparation by extrusion and by spraying additionally offer the advantage that the melt from components A and B solidifies plastically by supercooling, so that a high rate of dissolution of the grains obtained in water, that is to say also in the washing liquor, can be achieved.

In a preferred embodiment of the production process according to the invention for the granular bleach activator composition, the granules are additionally coated with one or more of the additives B or an aliphatic di- or tricarboxylic acid or an aromatic mono following the confectioning (b) - Or dicarboxylic acid, which may additionally contain hydroxyl groups in the molecule, or a mixture thereof. Coating is carried out either by spraying the additives B meltable at low temperature or the carboxylic acids mentioned or by spraying the aqueous solution of these substances over the grains.

If necessary, the coated grains must then be dried.

For the coating of the grains after the confectioning step (b), preferably fatty alcohol ethoxylates, polysaccharides such as especially starch, polyethylene glycols, alkylbenzenesulfonates such as especially sodium dodecylbenzenesulfonate and acrylic acid-maleic acid copolymers such as, in particular, about 50% of which are present as the sodium salt of the acrylic acid Maleic acid copolymer (weight ratio acrylic acid: maleic acid = 70:30) as additives B and

Adipic acid, tartaric acid, citric acid and benzoic acid are used as carboxylic acids.

In the optimal case, the grains of the composition should have an average diameter of approximately 0.1 to approximately 1 mm, in particular 0.5 to 1 mm. Depending on the packaging method, the grains have a prill, granulate, pellet or compact shape. The grains are usually white. They dissolve easily in lukewarm water within a short time and release the bleaching actuator in finely dispersed form.

The present invention furthermore relates to washing and cleaning agents which contain 0.5 to 20% by weight, preferably 1 to 10% by weight, of the granular bleach activator composition according to the invention and the customary bleaching agents in the customary amounts. In particular, these are textile detergents in powder form, to which the granular bleach activator composition according to the invention is admixed during or after its manufacture, and conventional constituents and compositions of detergents and cleaning agents are known to the person skilled in the art and therefore do not need to be discussed in more detail here.

The granular bleach activator composition according to the invention, together with the bleach, has a sufficiently high bleaching effect in the wash liquor. The composition dissolves very finely dispersed in the wash liquor in the shortest possible time, even at low temperatures in the range between 20 and 40 ° C, and can thus quickly develop its effect. The disadvantages frequently observed with bleach activator compositions which are too coarse-grained (fixation of the grains in the tissue, irregular and spotty bleaching action, destruction of the textile fibers) do not occur.

Furthermore, the granular bleach activator composition according to the invention in washing powder is sufficient, i.e. for several months, stable in storage; essentially no discoloration or decomposition processes can be observed.

Examples

example 1

100 g of solid sodium dodecylbenzenesulfonate were dispersed in 800 g of melted 2-phenyl-4H-3, l-benzoxazin-4-one at 130 ° C. The melt, which had cooled to room temperature, was comminuted in a hammer mill to an average particle size of 0.5 to 1 mm. In game 2

100 g of solid sodium dodecylbenzenesulfonate were dispersed in 800 g of melted 2-phenyl-4H-3, l-benzoxazin-4-one at 130 ° C. The melt, which had cooled to room temperature, was comminuted in a hammer mill to an average particle size of 0.5 to 1 mm. The granules were then coated by spraying on 330 ml of a 30% strength by weight sodium dodecylbenzenesulfonate solution at 80 ° C. and then dried in a fluidized bed dryer at 60 ° C. to a water content of <1%.

Example 3

100 g of solid sodium dodecylbenzenesulfonate and 5 g of benzoic acid were dispersed in 800 g of melted 2-phenyl-4H-3, l-benzoxazin-4-one at 130 ° C. The melt, which had cooled to room temperature, was comminuted in a hammer mill to an average particle size of 0.5 to 1 mm.

Example 4

100 g of solid sodium dodecylbenzenesulfonate and 5 g of benzoic acid were dispersed in 800 g of melted 2-phenyl-4H-3, l-benzoxazin-4-one at 130 ° C. The melt, which had cooled to room temperature, was comminuted in a hammer mill to an average particle size of 0.5 to 1 mm. The granules were then coated by spraying on 330 ml of a 30% strength by weight sodium dodecylbenzenesulfonate solution at 80 ° C. and then dried in a fluidized bed dryer at 60 ° C. to a water content of <1%.

Example 5

400 g of solid sodium dodecylbenzenesulfonate were dispersed in 500 g of melted 2-phenyl-4H-3, l-benzoxazin-4-one at 130 ° C. The melt, cooled to 60 ° C., was extruded in a continuous twin-screw extruder running in the same direction and then mechanically crushed in a baffle plate mill to an average particle size of 0.5 to Brought 1 m. The granules were then coated by spraying on 330 ml of a 30% by weight sodium dodecylbenzenesulfonate solution at 80 ° C. and then dried in a fluidized bed dryer at 60 ° C. to a water content of <1%.

Example 6

100 g of water-soluble starch were dispersed in 800 g of melted 2-phenyl-4H-3, l-benzoxazin-4-one at 130 ° C. The melt was sprayed in a spray tower to an average grain size of 0.5 to 1 mm. The granules were then coated by spraying 330 ml of a 30% strength by weight starch solution at 80 ° C. and then dried in a fluidized bed dryer at 60 ° C. to a water content of <1%.

Example 7

300 g of solid n-decyl glucoside were dissolved in 600 g of melted 2-phenyl-4H-3, l-benzoxazin-4-one at 130 ° C. The melt, cooled to room temperature, was brought to an average grain size of 0.5 to 1 mm in a hammer mill. The granules were then coated by spraying on 330 ml of a 30% by weight n-decyl glucoside solution at 80 ° C. and then dried in a fluidized bed dryer at 60 ° C. to a water content of <1%.

Example 8

100 g of solid acrylic acid / maleic acid copolymer, approximately 50% of which is present as the sodium salt (weight ratio of acrylic acid: maleic acid = 70:30), were dissolved in 900 g of molten 2-phenyl-4H-3, l-benzoxazin-4- solved at 130 ° C. The melt was sprayed in a spray tower to an average grain size of 0.5 to 1 mm.

Example 9

100 g solid sodium dodecylbenzenesulfonate and 200 g solid acrylic acid-maleic acid copolymer, approximately 50% of which is present as the sodium salt (weight ratio of acrylic acid-maleic acid = 70:30) were dissolved in 700 g of molten 2-phenyl-4H-3, l-benzoxazin-4-one at 130 ° C. The melt, which had cooled to room temperature, was comminuted in a hammer mill to an average particle size of 0.5 to 1 mm.

To test the storage stability of the bleach activator compositions from Examples 1 to 9, 5 g each of the granules obtained were mixed with 95 g of a customary bleach activator-free powder detergent composition containing 16% by weight sodium perborate tetrahydrate as bleach. After storage for six weeks at 38 ° C. and 76% relative atmospheric humidity, there was neither discoloration of the washing powder nor a noticeable loss of activity during washing in all cases.

Examples of use

Detergent preparations were produced with the granular bleach activator compositions described in Examples 1 to 9, with which just as good or in part even better overall bleaching effects could be achieved as with the same preparations which, instead of the bleach activator composition according to the invention, had the same amount of an agent of the prior art contained.

To measure the total bleaching effect (degree of bleaching), the mixture of the 2-phenyl-4H-3, l-benzoxazin-4-one-containing granules from Examples 2 and 5 to 9 and the powder detergent composition described below was determined for its suitability for textile washing examined, the granules and the powder detergent being mixed so that the bleach activator content of the entire detergent preparation was 4.0% by weight.

Composition of the powder detergent used:

6.25 parts by weight of sodium dodecylbenzenesulfonate

4.7 parts by weight of ethoxylated C1 ₃ -C15 oxo alcohol with 7 mol of ethylene oxide

2.8 parts by weight of taig fat soap

0.6 parts by weight of a commercially available water-soluble cellulose ether 2.0 parts by weight copolymer of maleic acid and acrylic acid (weight ratio 30:70, average molecular weight 70,000) 4.5 parts by weight sodium disilicate 1.0 part by weight Magnesium silicate 25.0 parts by weight of zeolite A 10.0 parts by weight of sodium perborate monohydrate 12.0 parts by weight of sodium carbonate 27.15 parts by weight of sodium sulfate

8 g / l of wash liquor were used in each case from this test detergent.

The following washing conditions were used:

The Launder-O-meter from Atlas was used as the washing device.

The water hardness of the wash water was 16.8 ° d = 3 mmol Ca2 ⁺ / 1 (Ca ⁺ : Mg ²⁺ = 3: 1).

The washing time including heating up time was 30 minutes and the liquor ratio was 1: 14.3.

The following test fabrics were used:

A: Cotton 11 fabric with immediate black as test soiling (test fabric EMPA 115)

B: Polyester fabric with carotene / cooking oil soiling

C: Cotton nettle fabric with tea / red wine soiling. The degree of bleaching was determined in each case on the basis of photometric measurement of the reflectance levels of the fabrics before and after washing in Elrepho (Datacolor) from Zeiss at a wavelength of 460 nm (barium white standard according to DIN 5033).

The following relationship applies to the calculation of the bleaching degree BG (in%): v ^"F n BG = - x 100

^F v ^" ^ 0 where the Kubelka-Munk relationship applies to the color strength F (= dirtiness of the fabric):

(1-R) 2

F =

2R mean

R: reflectance (measured variable) v: before washing the soiled test fabric n: after washing the soiled test fabric o: before soiling the fabric.

The table shows the calculated degrees of bleaching of the test fabrics, each as an average of 3 measured values after washing at 20 ° C., 38 ° C. and 60 ° C. As a comparison, a detergent preparation which contained 4.0% by weight of the listed bleach activator of the prior art was prepared under the same conditions.

table

Claims

1. Granular bleach activator composition containing

A) 30 to 95 parts by weight of one or more

4H-3, l-benzoxazin-4-one derivatives of the general formula I.

in which R is C 1 -C 1 -alkyl or -alkoxy, phenyl, o-, m- or p-tolyl, p-chlorophenyl, m-nitrophenyl, m-methoxyphenyl or m-methylsulfonylphenyl, or a mixture of the compounds I and other customary bleach activators, with the exception of mixtures of 90% by weight or less of the compounds I and 10% by weight or more of pentaacetyl glucose, and

B) 5 to 70 parts by weight of one or more additives from the substance classes

(1) anionic surfactants,

(2) nonionic surfactants,

(3) zwitterionic surfactants,

(4) polymers containing carboxyl groups,

(5) polysaccharides, (6) polyalkylene glycols.

2. Granular bleach activator composition according to claim 1, containing as additive B at least one anionic surfactant (1) from the group of alkylbenzenesulfonates.

3. Granular bleach activator composition according to claim 1, containing as additive B at least one nonionic surfactant (2) from the group of alkyl glucosides.

4. Granular bleach activator composition according to claim 1, containing as additive B at least one carboxyl-containing polymer (4) from the group of acrylic acid-maleic acid copolymers.

Granular bleach activator composition according to claim 1, containing as additive B starch as a polysaccharide (5).

Granular bleach activator composition according to Claims 1 to 5, additionally containing 0.1 to 30% by weight, based on the total amount of the composition, of an aliphatic di- or tricarboxylic acid or an aromatic mono- or dicarboxylic acid, which may additionally contain hydroxyl groups in the molecule, or a mixture of these.

7. A process for the preparation of a granular bleach activator composition according to claims 1 to 6, characterized in that

A) 30 to 95 parts by weight of one or more

4H-3, l-benzoxazin-4-one derivatives of the general formula I.

in which R is C 1 -C ₄ -alkyl or -alkoxy, phenyl, o-, - or p-tolyl, p-chlorophenyl, m-nitrophenyl, m-methoxyphenyl or m-methylsulfonylphenyl, or a mixture of the compounds I and other conventional bleach activators, with the exception of mixtures of 90% by weight or less of the compounds I and 10% by weight or more of pentaacetyl glucose, in the molten state with

B) 5 to 70 parts by weight of one or more additives from the substance classes

(1) anionic surfactants,

(2) nonionic surfactants,

(3) zwitterionic surfactants,

(4) polymers containing carboxyl groups, (5) polysaccharides,

(6) polyalkylene glycols, and, if desired, further additives and auxiliary substances are mixed (step a) and the resulting mixture is converted into a granular form by packaging (step b).

8. A process for the preparation of a granular bleach activator composition according to claim 7, characterized in that the assembly (b) is carried out by grinding the solidified melt from bleach activators A and additives B to the desired particle size.

9. A process for the preparation of a granular bleach activator composition according to claim 7, characterized in that the assembly (b) is carried out by extrusion of the molten mixture of bleach activators A and additives B and subsequent mechanical comminution to the desired particle size.

10. A process for the preparation of a granular bleach activator composition according to claim 7, characterized in that the assembly (b) is carried out by spraying the molten mixture of bleach activators A and additives B to the desired particle size.

11. A process for the preparation of a granular bleach activator composition according to claims 7 to 10, characterized in that, after the confectioning (b), the grains additionally with one or more of the additives B or an aliphatic di- or tricarboxylic acid or an aromatic mono- or dicarboxylic acid, which may additionally contain hydroxyl groups in the molecule, or a mixture thereof.

12. washing and cleaning agents containing 0.5 to 20 wt .-% of the granular bleach activator composition according to claims 1 to 6.