WO1993016161A1

WO1993016161A1 - Granular bleaching activator composition with variously shaped grains

Info

Publication number: WO1993016161A1
Application number: PCT/EP1993/000181
Authority: WO
Inventors: Reinhard Mueller; Guenter Oetter; Alfred Oftring; Volker Schwendemann; Wolfgang Trieselt; Raimund Felder
Original assignee: Basf Aktiengesellschaft
Priority date: 1992-02-05
Filing date: 1993-01-27
Publication date: 1993-08-19
Also published as: DE4203169A1; AU3451793A

Abstract

Granular bleaching activator composition with variously shaped grains containing as the core: A) 30 to 98 wt %, in relation to the total quantity of granular bleaching activator composition, of one or more 4H-3,1-benzo-oxazin-4- one derivatives of general formula (I) in which R is C1 to C4-alkyl, C1 to C4-alkoxy, chloromethyl, methoxy methyl, dimethylamino phenyl, o-, m- or p-tolyl, p-chlorophenyl, m-nitrophenyl, m-methoxy phenyl or m-methyl sulphonyl phenyl and R' is hydrogen, methyl, chloro, nitro, acetoxy or hydroxy, or a mixture of compounds (I) and other usual bleaching activators; and as the casing: B) 2 to 70 wt %, in relation to the total quantity of the granular bleaching activator composition, of one or more additives from the classes of substances: (1) anionic tensides; (3) non-ionic tensides; (3) hybrid ionic tensides; (4) carboxyl-group-containing polymers; (5) polysaccharides; (6) polyalkylene glycols; (7) acid alkaline and alkaline earth metal salts of inorganic acids; (8) aliphatic C8 to C18-monocarboxylic acids, aliphatic di and tricarboxylic acids, aromatic mono and dicarboxylic acids, the aforementioned carboxylic acids possibly also containing hydroxyl and amino groups in the molecule, and aliphatic C3 to C7-monohydroxycarboxylic acids.

Description

Granular bleach activator composition from heterogeneously structured grains

description

The present invention relates to a new granular bleach activator composition composed of heterogeneously structured grains based on 4H-3, l-benzoxazin-4-one derivatives, optionally mixed with other 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-benzoxazine-4-one derivatives, have insufficient water solubility, especially in the temperature range between 25 and 60 ° C and are not sufficiently stable in the washing powder. It is therefore common practice to assemble these bleach activators to increase the dissolution rate and the effectiveness in the wash liquor and to improve the shelf life.

German patent application P 41 34 770.6 (1) describes a granular bleach activator composition composed of 4H-3, 1-benzoxazine-4-one derivatives, optionally mixed with other conventional bleach activators, and additives from the classes of substances anionic surfactants, nonionic Surfactants, zwitterionic surfactants, carboxyl-containing polymers, polysaccharides and polyalkylene glycols are described. The bleach activators and the additives are distributed essentially homogeneously in this mixture.

WO 90/01535 (2) describes granular bleaching aids containing bleach activators from the class of the N-acyl and O-acyl compounds and water-soluble, film-forming polymers which serve as pelletizing aids; these bleaching aids additionally contain 2 to 15% by weight of a polyvalent carboxylic acid, hydroxycarboxylic acid or ether carboxylic acid with 3 to 6 C atoms in the molecule as stabilizer. For the preparation of the agents, a homogeneous, dry premix is first used prepared which contains the bleach activator, the acid and part or all of the polymeric granulating aid. This mixture is sprayed with water or an aqueous solution of the remaining granulating aid and granulated.

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 of heterogeneously structured grains has been found, the core

A) 30 to 98% by weight, based on the total amount of the granular bleach activator composition, of one or more 4H-3, l-benzoxazin-4-one derivatives of the general formula I

in the R for C ~ to C alkyl, C ~ to C ^ alkoxy, chloromethyl, methoxymethyl, dimethylamino, phenyl, o-, m- or p-tolyl, p-chlorophenyl, m-nitrophenyl, m-methoxy phenyl or m-methylsulfonylphenyl and R ^f denotes hydrogen, methyl, chlorine, nitro, acetoxy or hydroxy, or a mixture of the compounds I and other customary bleach activators

and as a wrapper

B) 2 to 70% by weight, based on the total amount of the granular bleach activator composition, 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,

(7) acidic alkali and alkaline earth metal salts of inorganic acids,

(8) aliphatic Cs ~ to Cis monocarboxylic acids, aliphatic see di- and tricarboxylic acids, aromatic mono- and

Dicarboxylic acids, where the aforementioned carboxylic acids can additionally contain hydroxyl and amino groups in the molecule, and aliphatic C ₃ - to C ₇ -monohydroxycarboxylic acids

contain.

As C 1 -C ₄ -alkyl radicals for R are ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and especially methyl. Suitable Ci to C alkoxy groups for R are n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy and especially methoxy and ethoxy. However, the aromatic radicals mentioned are preferred for R.

The radical R ', which can be in the 5-, 6-, 7- or 8-position, denotes in particular 5- or 6-methyl, 6- or 7-chlorine and 7-nitro. R 'particularly preferably denotes hydrogen.

The cores from component A ("primary grains") should

Have grain sizes of 1 to 50 μm, preferably 5 to 40 μm, in particular 10 to 30 μm, grain size here being the xsother of a Q ₃ distribution; this means that weighted by mass, 50% of the particles are each larger than the specified value. The fineness of the primary grains described is one of the factors determining the advantageous effect of the bleach activator composition according to the invention. Bleach activator grains from component A of the grain sizes described can even be used as a coating in detergent preparations without additives B to achieve the necessary bleaching effect, without serious defects of any other kind occurring due to the lack of assembly of the bleach activator.

Coating is primarily understood to mean agglomerating coatings in which several primary grains are embedded in a bed of additives B. The coating of the primary grains need not necessarily be complete. However, there may also be insulating sheaths of individual primary grains in the sense of a core-shell model. Several enveloping layers can also be present, for example an additional surface coating ("coating") from component B via an agglomerate of several primary particles and additives B between and around these primary particles.

In addition to the binder function, the additives B have above all a dispersing function, but can also have a protective function for the bleach activators against, for example, moisture, alkali or atmospheric oxygen in the form of surface 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, N'-tetraacylated amines, e.g. N, N, N ', N'-tetraacetyl-methylenediamine and -ethylenediamine, N, N-diacetylaniline, N, N-diacetyl-ρ-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5,5- dimethylhydantoin;

acylated sugars, for example 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. 0-

Benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or 0, N, N-triacetylhydroxylamine;

N, N'-diacylsulfurylamides, e.g. N, N'-dimethyl-N, N'-diacetyl-sulfurylamide or N, N'-diethyl-N, N'-dipropionyl-sulfurylamide;

Triacylcyanurates, e.g. Triacetyl cyanurate or tribenzoyl cyanurate;

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

1,3-diacyl-4,5-diacyloxy imidazolines, e.g. 1,3-di-acetyl-4,5-diacetoxyimidazoline;

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, N'-diacetylmalonamide;

Diacyl-dioxohexahydro-1,3,5-triazines, e.g. 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazine. A preferred granular bleach activator composition consists

A) 40 to 90 wt .-% of compound I or a mixture of I with other conventional bleach activators in the core and

B) 10 to 60% by weight of one or more additives B and

C) 0 to 20% by weight of customary auxiliaries C in the coating.

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. Alkyl benzenesulfonates, in particular the alkali metal and ammonium salts of linear Cn ~ to Ci ₃ alkylbenzenesulfonates, for example sodium dodecylbenzenesulfonate, are preferred.

The nonionic surfactants (2) used for B are, for example, primary or secondary alcohol oxalkylates such as fatty alcohol ethoxylates and alkylphenoloxyalkylates, fatty acid alkylol amides and especially alkyl glycosides, especially C _ß to Cie monoalkyl glucosides, for example Cιo monoalkyl glucoside.

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

Suitable carboxyl group-containing polymers (4) for B are, above all, 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 ether. Of these, starch itself can best be used.

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

The acidic alkali and alkaline earth metal salts of inorganic acids (7) for B are, above all, sodium hydrogen carbonate and sodium hydrogen sulfate, but also potassium hydrogen carbonate, potassium hydrogen sulfate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium or potassium hydrogen phosphate, calcium phosphate and phosphate.

As aliphatic Cβ- to Cis-monocarboxylic acids, aliphatic di- or tricarboxylic acids, aromatic mono- or dicarboxylic acids, where the aforementioned carboxylic acids can additionally contain hydroxyl and amino groups in the molecule, and as aliphatic C ₃ - to C -monohydroxycarboxylic acids (8 eig¬) for B NEN, for example, fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid, oxalic acid, malonic acid, Bern¬ acid, glutaric acid, adipic acid, pimelic acid, Korksäu- ^'re, nensäure maleic acid, fumaric acid, tartaric acid, malic acid, citric acid, benzoic acid , Salicylic acid, anthranilic acid, sulfanilic acid, phthalic acid, α- and ß-naphthoic acid, naphthalic acid and lactic acid. Of these, palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tartaric acid, citric acid and benzoic acid are preferred. The carboxylic acids mentioned mainly improve the color stability when stored in washing powders.

Mixtures of several additives B from one of groups (1) to (8) or from different groups can also be used.

The granular bleach activator compositions can also contain conventional auxiliaries C in the amounts customary for this in the coating. Usual auxiliaries, e.g. as

Disintegrants, dispersants or finishing aids are used, for example polymers such as polyvinylpyrrolidone or inorganic salts such as sodium sulfate or sodium triphosphate.

The addition of 0.1 to 30% by weight, in particular 0.5 to 15% by weight, of sodium sulfate, based on the total amount of the granular bleach activator composition, brings about a particularly good dispersion of the composition according to the invention in the wash liquor.

The invention further relates to a process for the production of the granular bleach activator composition according to the invention, which is characterized in that grains are made from

in the R for C ~ to C alkyl, C ~ to C ₄ alkoxy, chloromethyl, methoxymethyl, dimethylamino, phenyl, o-, m- or p-tolyl, p-chlorophenyl, m-nitrophenyl, m-methoxy phenyl or m-methylsulfonylphenyl and R 'denotes hydrogen, methyl, chlorine, nitro, acetoxy or hydroxy, or a mixture of the compounds I and other customary bleach activators

With

B) 2 to 70% by weight, based on the total amount of the granular bleach activator composition, 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,

(7) acidic alkali and alkaline earth metal salts of organic acids,

(8) - Aliphatic Cg to Cι ₈ -monocarboxylic acids, aliphatic di- and tricarboxylic acids, aromatic mono- and dicarboxylic acids, where the aforementioned carboxylic acids can additionally contain hydroxyl and amino groups in the molecule, and aliphatic C ₃ - to C -mono - hydroxycarboxylic acids

encased according to the usual procedures.

To produce the cores from component A (“primary granules”), 4H-3, l-benzoxazin-4-one derivatives or mixtures thereof with other conventional bleach activators as solids in devices customary for this purpose, such as pin mills, jet mills, counter-jet mills or impact plate mills can be ground to the desired grain size. However, the primary grains can also be produced by spraying the molten bleach activators A to the desired particle size, for example in a spray tower.

In principle, the granular bleach activator composition according to the invention is produced from components A and B by means of customary assembly methods and assemblies.

In a preferred embodiment, fine-grained bleach activator A and fine-grained additive B are mixed dry, the mixture is then agglomerated in water and then dried.

In a further preferred embodiment, an aqueous solution of the additives B is sprayed onto fine-grained bleach activator A, then agglomerated and then dried.

A combination of the two preferred embodiments described can also be carried out. Furthermore, the packing can be carried out dry by means of compaction on roller presses with subsequent shredding of the slugs to the desired agglomerate size. Furthermore, coarse-grained bleach activator A and coarse-grained additive B can also be dry mixed, ground together to the desired grain size in one of the devices specified above, and then agglomerated in water.

All conventional mixing devices which ensure intensive mixing are suitable for dry mixing of components A and B, for example ploughshare mixers, Eirich intensive mixers or Ruberg twin-shaft intensive mixers.

When drying, the water content of the made-up composition is reduced to less than 5% by weight, preferably less than 2% by weight and in particular less than 0.5% by weight. The

Drying takes place in suitable devices, for example fluidized bed, vacuum or tray dryers. Drying is preferably carried out at temperatures below 95 ° C.

In a further preferred embodiment, the granular bleach activator composition according to the invention is additionally provided with a second coating (coating) from the additives B. To produce this surface coating, the grains of the bleach activator composition according to the invention are coated with one or more additives B either by spraying an additive which melts at a low temperature or by spraying the aqueous solution of an additive over the grains. If necessary, the grains coated in this way must then be dried.

To coat the grains in the manner described, 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 approximately 50% of acrylic acid-maleic acid copolymer present as sodium salt sat (acrylic acid-maleic acid weight ratio = 70:30) and adipic acid, tartaric acid, citric acid and benzoic acid are used as additives B. In the optimal case, the grains of the bleach activator composition according to the invention should have an average diameter of about 0.1 to about 1 mm, in particular 0.5 to 1 mm. Depending on the packaging method used, 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 bleach activator in finely dispersed form.

The present invention furthermore relates to detergents 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 bleaches 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. The usual constituents or compositions of detergents and cleaners 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 in the wash liquor very finely dispersed in a very short 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 fabric, irregular and spotty bleaching action, destruction of the textile fibers) do not occur.

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

example 1

2-phenyl-4H-3, l-benzoxazin-4-one was ground in a pin mill to an average grain size of 20 μm. The grain proportion greater than 80 μm was less than 5%.

70 g of the 2-phenyl-4H-3, l-benzoxazin-4-one primary grains obtained in this way were mixed with 30 g of an acrylic acid-maleic acid copolymer present to approximately 50% as sodium salt (weight ratio of acrylic acid: maleic acid = 70:30) with an average molar mass of 70,000 in a ploughshare mixer. 14 ml of water were sprayed onto this mixture, which was kept in motion, within 10 minutes. The still moist granules were dried in a tray dryer at 60 ° C. to a water content of <1% by weight.

To test for storage stability, 5 g 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 six weeks of storage at 38 ° C. and 76% relative humidity, there was no discoloration of the washing powder or a noticeable loss of activity during washing.

Example 2

80 g of the 2-phenyl-4H-3, l-benzoxazin-4-one primary grains obtained in this way were mixed with 10 g of an acrylic acid / maleic acid copolymer which was approximately 50% sodium salt (weight ratio of acrylic acid: maleic acid = 70:30) with an average molecular weight of 70,000 and 10 g of sodium sulfate intimately mixed in a ploughshare mixer. 15 ml of water were sprayed onto this mixture, which was always kept in motion, within 10 minutes. The still moist granules were dried in a tray dryer at 60 ° C. to a water content of <1% by weight. To test for storage stability, 5 g 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 six weeks of storage at 38 ° C. and 76% relative humidity, there was no discoloration of the washing powder or a noticeable loss of activity during washing.

Example 3

80 g of the 2-phenyl-4H-3, l-benzoxazin-4-one primary grains thus obtained were intimately mixed with 20 g of citric acid in a ploughshare mixer. 12 ml of water were sprayed onto this mixture, which was always in motion, within 10 minutes. The still moist granules were dried in a tray dryer at 60 ° C. to a water content of <1% by weight.

Example 4

2-phenyl-4H-3, l-benzoxazin-4-one was ground in a pin mill to an average grain size of 20 μm. The grain fraction larger than 80 μm was less than 5%.

70 g of the 2-phenyl-4H-3, l-benzoxazin-4-one primary grains thus obtained were intimately mixed with 10 g of citric acid, 12 g of sodium sulfate and 11 g of starch in a ploughshare mixer. 14 ml of water were sprayed onto this mixture, which was always kept in motion, within 10 minutes. That still wet Granules were dried in a tray dryer at 60 ° C to a water content of <1 wt .-%.

Examples of use

Detergent preparations were produced with the granular bleach activator compositions described in Examples 1 to 3, 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 Technology included.

In order to measure the overall bleaching effect (degree of bleaching), the mixture of the 2-phenyl-4H-3,1-benzoxoxazin-4-one-containing granules from Examples 1 to 3 and the powder detergent composition described below was tested for its suitability for the Textile laundry was 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:

7.5 parts by weight of sodium dodecylbenzenesulfonate

4.0 parts by weight of ethoxylated Cχ ₃ -Ci ₅ oxo alcohol with 7 mol of ethylene oxide

2.8 parts by weight of taig fat soap

1.0 part by weight of carboxymethyl cellulose

2.0 parts by weight copolymer of maleic acid and acrylic acid

(Weight ratio 30:70, average molecular weight 70,000)

3.0 parts by weight of sodium disilicate (a ₂ θ: Siθ ₂ = l: 3.3)

25.0 parts by weight of zeolite A

10.0 parts by weight of sodium carbonate 10.0 parts by weight of sodium perborate monohydrate 30.7 parts by weight of sodium sulfate minus the additives of the coating.

For this purpose, 4.0 parts by weight (based on 100%) of the bleach activator granules were added.

8 g / l of wash liquor were used from each of these test detergents, namely 3 times a series after the detergent mixtures had been stored in the closed carton overnight at room temperature (20 ° C.), 3 times a series after the same mixtures had been stored for two weeks in the climate cabinet at 38 ° C and 76% relative humidity and 3 times a series after six weeks of storage in the climate cabinet.

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 Ca ²⁺ / 1 (Ca ²⁺ : Mg ²⁺ = 4: 1).

The washing time including heating-up time was 30 minutes and the liquor ratio was 1: 12.5.

The following test fabrics were used:

A: Cotton fabric with immediate black as a test soil (test fabric EMPA 115)

B: Cotton nettle fabric with red wine soiling

C: Cotton nettle fabric with tea staining

D: Polyester fabric with carotene / cooking oil 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 the 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%):

Fri

BG = x 100

Fv - F _n

the Kubelka-Munk relationship applies to the color strength F (= dirtiness of the fabric):

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 45 ° C. after storing the detergent mixtures overnight, after 2 weeks and after 6 weeks. As a comparison, detergent preparations which contained 4.0% by weight of the listed bleach activators of the prior art were prepared under the same conditions.

It can be clearly seen from the table that the examples according to the invention give bleaching effects which are at least equally good in all tested fabrics and, in the case of prolonged storage, significantly better than the prior art. table

10

15

20th

TAED = N, N, N ', N' -Tetraacetylethylenediamine RLF = relative humidity

25

Claims

1. Granular bleach activator composition from heterogeneously structured grains, which form the core

in the R for Cι ~ to Cj-alkyl, Ci _. - to C <j-alkoxy, chloromethyl, methoxymethyl, dimethylamino, phenyl, o-, m- or p-tolyl, p-chlorophenyl, m-nitrophenyl, m-methoxyphenyl or m-methylsulfonylphenyl and R ^{r is} hydrogen, methyl, chlorine , Nitro, acetoxy or hydroxy, or a mixture of the compounds I and other customary bleach activators

and as a wrapper

(1) anionic surfactants,

(2) non-ionic surfactants, (3) zwitterionic surfactants,

(4) polymers containing carboxyl groups,

(5) polysaccharides,

(6) polyalkylene glycols,

(7) acidic alkali and alkaline earth metal salts of inorganic acids,

(8) aliphatic Cβ ~ to C- _X8 monocarboxylic acids, aliphatic di- and tricarboxylic acids, aromatic mono- and dicarboxylic acids, the above mentioned carboxylic acids may additionally contain hydroxyl and amino groups in the molecule, and aliphatic C ₃ - to C -monohydroxycarboxylic acids

contain.

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

3. Granular bleach activator composition according to claim 1 or 2, containing in the coating as additive B as an acidic alkali or alkaline earth metal salt of an inorganic acid (7) sodium hydrogen carbonate or sodium hydrogen sulfate.

4. Granular bleach activator composition according to claims 1 to 3, containing in the coating at least one carboxylic acid (8) from the group palmitic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, tartaric acid, citric acid acid and benzoic acid.

5. Granular bleach activator composition according to claims 1 to 4, in which the cores from component A have grain sizes of 1 to 50 μm.

6. A process for the preparation of a granular bleach activator composition according to claims 1 to 5, characterized in that grains are made from

^]

in the R for Ci _. - to C ₄ alkyl, C; - to C ^ alkoxy, chloromethyl, methoxymethyl, dimethylamino, phenyl, o-, m- or p-tolyl, p-chlorophenyl, m-nitrophenyl, m-methoxyphenyl or m-methylsulfonylphenyl and R 'denotes hydrogen, methyl, chlorine, nitro, acetoxy or hydroxy, or a mixture of the compounds I and other conventional bleach activators

With

(1) anionic surfactants,

(2) nonionic surfactants,

(3) zwitterionic surfactants,

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

(6) polyalkylene glycols,

(7) acidic alkali and alkaline earth metal salts of organic acids,

(8) aliphatic Cs to Cis monocarboxylic acids, aliphatic di- and tricarboxylic acids, aromatic mono- and dicarboxylic acids, where the aforementioned carboxylic acids can additionally contain hydroxyl and amino groups in the molecule, and aliphatic C ₃ to C monohydroxycarboxylic acids

encased according to the usual procedures.

7. A process for the preparation of a granular bleach activator composition according to claim 6, characterized in that fine-grained bleach activator A and fine-grained additive B are dry mixed, the mixture is agglomerated in water and dried.

8. A method for producing a granular bleach activator composition according to claim 6, characterized gekenn¬ characterized in that an aqueous solution of additives B sprayed onto fine-grained bleach activator A, agglomerated and dried.

9. A process for the preparation of a granular bleach activator composition according to claims 6 to 8, characterized in that the granular bleach activator composition is additionally provided with a second coating made from additives B.

10. Detergents and cleaning agents containing 0.5 to

20% by weight of the granular bleach activator composition according to claims 1 to 5.