NO820164L - Particulate detergent mixture - Google Patents

Description

The invention relates to detergent compositions which are particularly, but not essentially, adapted for laundry, and more particularly to phosphate-based detergent compositions which include a bleaching system.

It is known to mix in peracid bleaches, e.g. sodium perborate, together with peracid bleach<*>precursors or peroxy bleach activator in detergent mixtures. Such detergent compositions conventionally include, in addition to a detergent active material, a phosphate detergency builder, e.g. sodium tripolyphosphate. Under some circumstances, it is believed that the use of phosphates in detergent mixtures can lead to environmental problems in waste water. There is therefore a desire to reduce the level of phosphorus in detergent mixtures.

Water-insoluble aluminosilicate ion exchange materials have been proposed as alternative builders instead of phosphates. It is referred to e.g. to British Patent No. 1 429 143. However, it has been shown that in aluminosilicate-based products the performance of this bleaching system is significantly reduced.

It has also been found that if a detergent composition is based on aluminosilicate as the sole builder, or on sodium tripolyphosphate as the sole builder, the bleaching performance of the product decreases as the final water hardness increases. Thus, the bleaching performance of a product is reduced, when it comes to a fixed product dosage where the level of the building material in the product is intentionally reduced, possibly as a price-saving action, or if the product is used in a dosage that is lower than what is recommended.

However, we have now surprisingly found that the bleaching performance can be largely maintained and that the reduction in bleaching performance with increasing water hardness can be largely overcome if only a specific portion of the tripolyphosphate is replaced by the aluminosilicate and if the peroxybleach and activator therefor are present in specific relative ratios .

According to the invention, a particulate alkaline detergent mixture is therefore provided which comprises: from approx. 5 to approx. 40% by weight of at least one synthetic detergent active material;

from approx. 12.5 to approx. 25% by weight of an alkali metal tripoly-

phosphate calculated on an anhydrous basis;

from approx. 7.0 to approx. 36% by weight of a water-insoluble aluminosilicate detergency building material, calculated on an anhydrous basis;

from approx. 5 to approx. 30% by weight of a peroxy bleach; and

up to approx. 15% by weight of an activator for said peroxy bleach,

as the weight ratio between the peroxy bleach and the activator is between approx. 2:1 and approx. 15:1.

It is particularly advantageous if the percentage amount of the alkali metal tripolyphosphate (T) and the percentage amount of the aluminum silicate material (A) are in such a ratio to each other that the sum

lies between approx. 25 and approx. 37, preferably between approx. 28

and approx. 34.

The detergent mixture according to the invention necessarily includes from approx. 5 to approx. 40%, preferably approx. 10 to approx. 25%, by weight of a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or a mixture thereof. Many suitable detergent active compounds are commercially available and are fully described in the literature, e.g. in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

In general, laundry detergent compositions also contain fluorescent agents to improve the bleaching activity of the products on laundry washed with them. The fluorescent agents that are usually used are derivatives of 4,4'-di(sym-triazinylamino)-stilbene-2,2'-disulfonic acid or salts thereof. Other fluorescent agents that have also been used are e.g. derivatives of diphenyldistyryl compounds, e.g. 4,4'-di(3-sulfostyryl)-diphenyl; derivatives of 4,41-di(triazolyl)-stilbene-2,2'-disulfonic acid and derivatives of diphenyl-2-pyrazoline. Such fluorescent agents are, however, when incorporated

in bleach/detergent mixtures, prone to cleavage with consequent loss of fluorescence activity, possibly due to interaction with the bleach system therein.

We have now surprisingly found that fluorescence stability can largely be maintained if a major part of the detergent-active material is made up of an anionic material. It is thus preferred that the detergent active material is selected from among anionic synthetic detergent active materials and mixtures thereof, with a smaller amount of one or more non-anionic synthetic detergent active materials.

The. synthetic anionic detergent compounds are usually water-soluble alkali metal salts of organic sulfates and sulfonates that have alkyl radicals containing from approx. 8

to approx. 22 carbon atoms, the term alkyl being used to include the alkyl part in higher aryl radicals. Examples of suitable synthetic anionic washing compounds are sodium-pg potassium alkyl sulphates, especially those obtained by sulphating higher (Cg-C^g)-alcohols such as e.g. is made from tallow or coconut oil; sodium and potassium alkyl (C 8 -C 20 )benzene sulfonates, especially sodium linear sec alkyl (C 10 -C 20 )benzene sulfonates; sodium alkyl glyceryl ether sulfates, especially such ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium and potassium salts of sulfuric acid esters of higher (Cg-C^g) fatty alcohol-alkylene oxide, especially ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids, esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulfonates, e.g. those originating from the reaction of α-olefins (C0-C0n) with sodium bisulphite and those originating from the reaction of paraffins with SO2 and Cl2 and then hydrolysis with a base to produce a randomized sulfonate; and olefin sulfonates, this term being used to describe the material obtained by reacting olefins, especially C^0-C20-a-olefins, with SO^ and then neutralizing and hydrolyzing the reaction product. The preferred anionic detergents are sodium (C 2 -C 3 ) alkylbenzene sulfonates and sodium (C 2 -C 3 ) alkyl sulfates.

Examples of suitable non-ionic washing compounds which can be used, preferably together with the anionic washing compounds, include in particular the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 8 -C 22 ) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; the condensation products of aliphatic (Cg-C^g) primary or secondary, linear or branched alcohols with ethylene oxide, generally 6-30 EO. and products produced by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergents include long-chain tert-amine oxides, long-chain tert-phosphine oxides and dialkylsulfoxides.

Mixtures of the anionic washing compounds with e.g. non-ionic compounds can be used in the detergent mixture, especially for providing regulated low foaming properties. This is beneficial for products that are intended to be used in automatic washing machines that are foam-intolerant. The presence of some non-ionic washing compounds in the products can also help to improve the solubility characteristics of the washing powder. A preferred anionic:nonionic ratio is at least approx. 2:1, preferably from approx. 3:1 to approx. 10:1.

Amounts of amphoteric or zwitterionic detergent compounds can also be used in the products according to the invention, but this is not normally desired due to their relatively high price. If any amphoteric or zwitterionic detergents are used, this generally takes place in small amounts in products based on the much more commonly used synthetic anionic and nonionic detergents.

Some soaps can also be used in the products according to the invention, but not as the only washing compounds. They are particularly useful at low levels in binary (soap/anionic) or ternary mixtures together with nonionic or mixed synthetic anionic and nonionic detergents, which have low foaming properties. The soaps used are preferably the sodium or, less desirable, the potassium salts of C₂₂-C₂₂ fatty acids. It is particularly preferred that the soaps must be mainly based on the longer chain fatty acids within this range, i.e. with at least half of the soap having a carbon chain length of 16 or more. This can be accomplished most conveniently by using soaps from natural sources such as tallow, palm oil or rapeseed oil, which can be hardened if desired, together with smaller amounts of other short-chain soaps, made from nut oils, e.g. coconut oil or palm kernel oil. The quantity of such soaps can be varied between approx. 0.5 and approx. 25% by weight, the lower amounts of approx. 0.5% to approx. 5% is generally satisfactory for foam control. Amounts of soap between approx. 2 and approx. 20%, especially between approx. 5 and approx. 15%, is preferably used to give a beneficial effect on washing ability. This is particularly valuable in products used in hard water when the soap serves as a supplementary builder. Furthermore, we have found that the addition of soap helps to reduce the tendency of the products to form inorganic deposits in the sink, and for this purpose it is preferable to use approx. 2 to approx. 15%, especially approx. 2.5 to approx. 10%, by weight of soap in the mixture. When soap is present, it is preferred that the total level of detergent active material, including the soap, is between approx. 5 and approx. 40% by weight, preferably between approx. 10 and approx. 25% by weight. Furthermore, if both the soap and a non-ionic detersive material are present together with a synthetic anionic detersive material, it is preferred that the weight ratio of the synthetic anionic material to the soap, and the non-ionic. material is at least approx. 2:1, preferably approx. 3:1 to approx. 10:1.

The alkali tripolyphosphate is preferably sodium tripolyphosphate, advantageously present in an amount of from more than about 15 to approx. 22% by weight. Although it is desirable that the only phosphate material present is the tripolyphosphate, up to approx. 5% by weight, calculated on the mixture, of other phosphate materials is also added, e.g. orthophosphate or pyrophos-f at. Low levels of these other phosphate materials, even over 5% by weight of the mixture, may in each case be present in mixtures which have been prepared by spray drying, as a consequence of a hydrolysis of sodium tripolyphosphate. Thus, e.g. a spray-dried product nominally containing 25% sodium tripolyphosphate (STP) may in reality contain up to approx. 10% by weight of other phosphates originating from the breakdown of the tripolyphosphate. The resulting sodium orthophosphate and sodium pyrophosphate both contribute to fabric ashing and should be kept to a minimum.

Although careful control of process conditions can reduce this STP degradation, it is preferred to prevent all degradation in the spray drying tower by post dosing all STP. There may still be some ortho- and pyrophosphate in the final powder due to the fact that the raw material STP may contain approx. 5% of them, and some further degradation may occur during storage.

The aluminosilicate building material is preferably crystalline or amorphous material having the general formula: where Z and Y are integers of at least 6; the molar ratio Z:Y is in the range of 1.0 to 0.5, and X is an integer of 15-264 so that the moisture content is 10-28% by weight. The preferred range of aluminosilicate is from approx. 12 to approx. 30% on an anhydrous basis. The aluminosilicate preferably has a particle size of 0.1-100 nm, ideally between 0.1 and 10 nm, and a calcium ion exchange capacity of at least 200 mg calcium carbonate/g. In a preferred embodiment, the water-insoluble aluminosilicate cation exchange material has the following formula: where x is an integer of 20-30, preferably approx. 27. This material is commercially available as Zeolite A.

The used bleaching system essentially comprises a peroxy-bleaching compound which is an inorganic persalt, and an activator for this. The activator makes bleaching more effective at lower temperatures, i.e. in the range from ambient temperature to approx. 60°C, so that such bleaching systems are commonly known as low-temperature bleaching systems and are well known in the field. The inorganic persalt, e.g. sodium perborate, both the monohydrate and the tetrahydrate, serves to release active oxygen in solution, and the activator for this is usually an organic compound having one or more reactive acyl residues, causing the formation of peracids, the latter providing a more effective bleaching action at lower temperatures than the peroxy bleach compound. The weight ratio between the peroxy bleach compound and the activator is approx. 15:1 to approx. 2:1, preferably approx. 10:1 to approx. 3.5:1.

Although the amount of the bleaching system, i.e. the peroxy bleaching compound and the activator, can be varied between approx. 5 and approx. 35% by weight of the detergent mixtures, it is preferred to use approx. 6 to approx. 30% of the ingredients that make up the whitening system.

Thus, it is the preferred level of the peroxy bleach compound

in the product between approx. 5.5 and approx. 27% by weight, while the preferred level of the activator is between approx. 0.5 and approx. 10%, preferably between approx. 0.5 and approx. 3.2%, by weight.

Typical examples of suitable peroxy bleaching compounds are alkali metal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred. The peroxy bleach compound is normally added separately to the washing base powder, and it is desirable to avoid segregation by having the particles of both in generally the same order of magnitude.

Activators for peroxy bleach compounds are duly described in the literature, including British patents no.

836,988, 855,735, 907,356, 907,358, 970,950, 1,003,310 and 1,246,339, US Patent Nos. 3,332,882 and 4,128,494, Canadian Patent No. 844,481 and South African Patent No. 68/6 344. Specific suitable activators include: (a) N-diacylated and N,N-polyacylated amines, e.g.

N,N,N',N<1->tetraacetylmethylenediamine and

N,N,N',N<1->tetraacetylethylenediamine,

N,N-di'acetylaniline, N,N-diacetyl-p-toluidine;

1,3-diacylated hydantoins, e.g.

1,3-diacety1-5,5-dimethylhydantoin and

1,3-dipropionylhydantoin; α-acetoxy-fj,N,N') - polyacylmalonamide, e.g. α-acetoxy-(N,N<1>)-diacetylmalonamide;

(b) N-alkyl-N-sulfonylcarbonamides, e.g. the compounds N-methyl-N-mesyl-acetamide, N-methyl-N-

mesylbenzamide, N-methyl-N-mesyl-p-nitrobenzamide,

and N-methyl-N-mesyl-p-methoxybenzamide;

(c) N-acylated cyclic hydrazides, acylated triazones or

urazoles, e.g. monoacetylmaleic hydrazide; (d) 0,N,N-trisubstituted hydroxylamines, e.g.

0-benzoyl-N,N-succinylhydroxylamine,

0-acetyl-N,N-succinylhydroxylamine,

"O-p-methoxybenzoy1-N,N-succinylhydroxylamine,

O-p-nitrobenzoyl-N,N-succinylhydroxylamine and O,N,N-triacetylhydroxylamine;

(e) N,N'-diacyl-sulfuryl amides, e.g. N ,N' -

dimethyl-N,N'-diacetylsulfurylamide and N,N'-diethyl-N,N'-dipropionylsulfurylamide;

(f) triacylcyanurates, e.g. triacetyl cyanurate and

tribenzoyl cyanurate;

(g) carboxylic anhydrides, e.g. benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride, 4-chlorophthalic anhydride; (h) sugar esters, e.g. glycosepentaacetate; (i) 1,3-diacyl-4,5-diacyloxy-imidazolidine, e.g. 1,3-diformyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacety1-4,5-dipropionyloxy-imidazoline; (j) tetraacetyl glycoluril and tetrapropionyl glycoluril; (k) diacylated 2,5-diketopiperazine, e.g. 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine and 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine; (1) acylation products of propylenediurea or 2,2-dimethylpropylenediurea (2,4,6,8-tetraaza-nicyclo-(3,3,1)-nonane-3,7-dione or its 9,9-dimethyl derivative), especially tetraacetyl- or tetrapropionyl-propylenediurea or their dimethyl derivatives; (m) carboxylic acid esters, e.g. the sodium salts of p-(ethoxycarbonyloxy)benzoic acid and p-(propoxycarbonyloxy)benzenesulfonic acid;

(n) acyloxy-(NjN<1>)polyacymalonamides, e.g.

α-acetoxy(N,!^)diacetylmalonamide.

The N-diacylated and N,N'-polyacylate diamines mentioned under (a) are of particular interest, especially N,N,N',N'-tetraacetylethylenediamine (TAED).

It is preferred to use the activator in granular form, preferably where the activator is finely divided as described in our British Patent Specification No. 80219^79. Specifically, it is preferred to have an activator with an average particle size of less than 150 nm, which provides significant improvement in bleaching efficiency. The sedimentation losses, when used

of an activator with an average particle size of less than 150 nm is lowered to a significant extent. Even better bleaching performance is achieved if the average particle size of the activator is less than 100 Mm. However, too small a particle size results in increased splitting, dust formation and handling problems, and although particle sizes below 100 nm can ensure improved bleaching efficiency, it is desirable that the activator has no more than 20% by weight of particles with a size smaller than 50 Mm. On the other hand, the activator may have a certain amount of particles with a size above 150 µm, but it should not contain more than 5% by weight of particles larger than 300 nm, and no more than 20% by weight of particles that are greater than 200 Mm, preferably over 150 pm. It should be understood that these particle sizes refer to the activator present in the granules, and not to the granules themselves. The latter has a particle size where the main part varies from 100 to 2000 Mm, preferably 250-1000 Mm. Up to 5% by weight of granules with a particle size above 1700 Min and up to 10% by weight of granules below 250 Mm can be tolerated.

The granules incorporating the activator, preferably in this finely divided form, can be obtained by granulating a suitable carrier material, e.g. sodium tripolyphosphate and/or potassium tripolyphosphate, with activator particles of the required size. Other granulation methods, e.g. using organic and/or inorganic granulation aids, can also be used in a useful way. The granules can then be dried, if required. Basically, any granulation process is applicable, when only the granule contains the activator, and when only the other materials present in the granule do not have a negative effect on the activator.

It is particularly preferred to include in the detergent mixtures a stabilizer for the bleaching system, e.g. ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate. These activators can be used in acid form or salt form, especially in calcium, magnesium, zinc or aluminum salt form, as described in our British Patent Application No. 7 912 141. The stabilizer can be present at a level of up to approx. 1% by weight, preferably between approx. 0.1 and approx. 0.5% by weight.

Apart from the components already mentioned, the detergent mixtures according to the invention can contain any of the conventional additives in the quantities in which such materials are normally used in laundry detergent mixtures. Examples of these additives include foam enhancers, e.g. alkanolamides, especially the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, foam depressants, e.g. alkyl phosphates and silicates, antigen deposition agents, e.g. sodium carboxymethyl cellulose, and alkyl or substituted alkyl cellulose ethers, other stabilizers such as ethylenediaminetetraacetic acid, fabric softeners, inorganic salts, e.g. sodium sulfate and sodium carbonate, and usually present in very small amounts fluorescent agents, perfume, enzymes, e.g. proteases and amylases, germicides and coloring agents. In particular, the products according to the invention can include the salt of an alkyl phosphoric acid as a foam suppressant and a wax as a hydrophobic material, as described in BRD official publication no. 2 701 664.

The fluorescent agents which can be used in the bleach/detergent mixtures according to the invention are well known, and many such fluorescent agents are commercially available. Specific fluorescent agents which may be mentioned as examples are: (a) 4,4-di(2"-anilino-4"-morpholinotriazin-6"-ylamino)-stilbene-2,2'-disulfonic acid and its salts, (b) 4,4'-di(2"-anilino-4"-N-methylethanolaminotriazin-6"-ylamino)-stilbene-2,2'-disulfonic acid and its salts, (c) 4,4'-di(2"- anilino-4"-diethanolaminotriazin-6"-ylaminoph-stilbene-2,2'-disulfonic acid and its salts, (d) 4,4-di(2"-anilino-4"-dimethylaminotriazin-6"-ylamino)-stilbene -2,2<1->disulfonic acid and its salts, (e) 4,4'-di(2"-anilino-4"-diethylaminotriazin-6"-ylamino)-stilbene-2,2'-disulfonic acid and its salts , (f) 4,4'-di(2"-anilino-4"-monoethanolaminotriazin-6"-ylamino)-stilbene-2,2'-disulfonic acid and its salts, (g) 4,4'-di(2 "-anilino-4"-(1-methyl-2-hydroxy)ethyl-aminotriazin-6"-ylamino)-stilbene-2,2'-disulfonic acid and its salts, (h) 4,4'-di(2" -methylamino-4"-p-chloroanilinotriazine-6"-ylamino)-stilbene-2,2'-disulfonic acid and its salts, (i) 4,4'-di(2"-diitolamine-4"-sulfanilinotriazine-6" -ylamino)-stilbene-2,2'-disulfonic acid and its salts,

(j) 4,4'-di(3-sulfostyryl)diphenyl and its salts,

(k) 4,4'-di(4-phenyl-1,2,3-triazol-2-yl)-stilbene-2,2'-disulfonic acid and its salts, (1) 1-(p-sulfonamidophenyl)- 3-(p-Chlorophenyl)-A<2->pyrazoline.

The salt of the acid defined under (a) above is referred to below as "fluorescent agent X".

Usually these fluorescent agents are obtained, and they are used in detergent mixtures, in the form of their alkali metal salts, e.g. the sodium salts. In addition to these fluorescent agents, the detergent mixture according to the invention can contain other types of fluorescent agents if desired. The total amount of the fluorescent agent or the like

agents used in a detergent mixture are generally 0.02-2% by weight.

It is desirable to include one or more anti-deposition agents in the detergent mixtures according to the invention, in order to reduce the tendency to form inorganic deposits on washed laundry. The amount of any such anti-redeposition agent is normally from approx. 0.1 to approx. 5% by weight, preferably from approx. 0.2 to approx. 2.5% by weight, calculated on the mixture. The preferred redeposition agents are anionic polyelectrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.

It may be desirable to include in the mixtures a quantity of an alkali metal silicate, especially sodium ortho-, -meta- or preferably neutral or alkaline silicate. The presence of such alkali metal silicates at levels at least approx. 1%,

and preferably from approx. 5 to approx. 15%, by weight of the mixtures, is advantageous with regard to reducing corrosion of metal parts in washing machines, in addition to providing processing advantages and generally improved powder properties. The stronger alkaline ortho- and metasilicates would normally only be used in smaller quantities within this range, in admixture with the neutral or alkaline silicates.

The products according to the invention are required to be alkaline, but not too strongly alkaline, as this could result in damage to clothes and also be dangerous for household use. In practice, the mixtures should give a pH value of from approx. 8.5 more

about. 11 in use in an aqueous washing solution. It is particularly preferred for household products that they have a pH value of from approx.

9.0 to approx. 10.5, as lower pH values tend to be less effective for optimal detergency building, and stronger alkaline products can be dangerous if used incorrectly. The pH value is measured at the lowest normal use concentration of 0.1 wt/vol.% of the product in water of 12°H (Ca), (French permanent hardness, calcium only) at 50°C so that

a satisfactory degree of alkalinity can be ensured in use at all normal product concentrations.

The detergent mixtures according to the invention should be in free-flowing particle form, e.g. powdered or granulated, and they can be produced by any of the techniques commonly used in the production of such detergent mixtures, but preferably by slurry and spray drying processes, so that a detergent base powder is formed as the ingredients of the bleaching system, and optionally also the alkali tripolyphosphate is added to. It is preferred that the method used to make the mixtures results in a product having a moisture content of no more than approx. 12%, more preferably from approx. 4 to approx. 10%,

in weight, as the lower humidity levels have been shown to be beneficial for the stability of the used bleaching systems.

In the following, the invention will be illustrated by means of the non-limiting examples.

EXAMPLE 1

The following base powders were produced by spray-drying a seeding containing the specified constituents:

The following ingredients were post dosed to these base powders:

These powders were then tested using the following method: A Miele W484 automatic washing machine was used, set to the 60°C main wash only program. The laundry load consisted of 4 kg of unsoiled cotton and 4 standard soiled bleach-sensitive test pieces that were stained by tea. 100 g of the test powder was introduced using the machine's dispenser. The machine's water intake (hardness 15°FH)

was 20 litres. Each powder was tested three times.

During the wash, samples were taken of the wash bath when the wash bath first reached 40°C. The content of peracetic acid and active oxygen was determined in each sample using conventional analytical techniques. • At the end of each wash, the bleaching performance of the standard test pieces was determined by measuring the reflectance at 460 nm on a Zeiss Elrepho photometer with a 420 nm UV interference filter (R 460<*>). The average reflectance of the samples before washing was 32.6 and the bleaching effect is indicated as a change in the fabric's reflectance, AR460<*.>

The results obtained were as follows:

This example shows that the performance of the STP/zeolite product is surprisingly similar to the performance of the STP only product (Comparative Example A), despite the lower total phosphorus level.

IO

EXAMPLE 2

The experiments from example 1 were repeated with powders made according to the following recipes:

The procedure from example 1 was modified in that the experiment was carried out in a Tergotometer with a heating from 16° to 60°C during 34 minutes. A product dosage of 5 g/l was used. The water hardness was 40°FH.

The results obtained were as follows:

This example shows that the bleaching performance of the STP/zeolite product is significantly better than the product with only zeolite (Comparison example B).

EXAMPLE 3

To the base powders described in example 2 and

comparative example B, the following ingredients were post-dosed:

Using the same method as stated in Example 2, modified only by the hardness of the water being 35°FR, the following results were obtained:

EXAMPLE 4

For the base powders described in examples 2 and i

comparative example B, the following ingredients were post-dosed:

Using the same procedure as stated in Example 3, the following results were obtained:

EXAMPLES 5 and 6

Washing powders were prepared according to the following approximate recipes, and these proved to give excellent results in comparison with similar recipes where sodium tripolyphosphate (STP) was the only building material.

The suds suppressing material used was a 1:3 mixture of C 1-4 -alkyl phosphoric acid ester and petroleum jelly with a dripping melting point of 54°C.

EXAMPLE 7

The experiments from example 1 were repeated with powders prepared according to the following recipes (parts by weight):

The procedure from example 1 was modified in that the experiment was carried out in a Tergotometer with heating from 16°C to 55°C within 30 minutes. With a further 30 minutes at 55°C, a product dosage of 5 g/l was used. Water with a hardness of 35°FH and 60°FH was used.

The results obtained were as follows:

This example shows that the bleaching performance of the product according to the invention (example 7) is improved with increased water hardness, while the bleaching performance of the products based only on STP and zeolite (comparative examples E and F) is reduced with increased water hardness.

EXAMPLE 8

The experiments from example 1 were repeated with powders made

according to the following recipes (parts by weight):

The procedure from example 1 was modified in that the experiment was carried out in a Tergotometer with a heating from 1.6_°-C to 55°C within 60 minutes. A product dosage of 5 g/l was used. Water with a hardness of 35°FH and 60°FH was used.

The results obtained were as follows:

This example shows that the bleaching performance of the product according to the invention (example 8) is improved with increased water hardness, while the bleaching performance of the product containing perborate without TAED is reduced with reduced water hardness.

EXAMPLE 9

The following recipe represents a further example of a detergent mixture according to the invention:

In the above examples, the anionic detergent material used was the sodium salt of alkyl-(about C-j^)-benzenesulfonate and the nonionic material used was a mixture of Dobanol 4 5-18 and Lutensol 12E0. The soap used was a mixture of hardened tallow soap and hardened rapeseed soap. The zeolite used was zeolite A (from Degussa).

Claims (6)

1.P article-form alkaline detergent mixture comprising at least one synthetic detergent active material, an alkali metal tripolyphosphate, a water-insoluble aluminosilicate detergency building material, a peroxy bleach and an activator for said peroxy bleach, characterized in that it contains: from approx. 5 to approx. 40% by weight of it. synthetic detergent material; from approx. 12.5 to approx. 25% by weight of the alkali metal tripolyphosphate calculated on an anhydrous basis; from approx. 7.0 to approx. 36% by weight of the water-insoluble aluminosilicate detergency building material calculated on an anhydrous basis; from approx. 5 to approx. 30% by weight of a peroxy bleach; and up to approx. 15% by weight of an activator for the bleach, as the weight ratio between the peroxy bleach and the activator is between approx. 2:1 and approx. 15:1. 2. Detergent mixture as stated in claim 1, characterized in that the sum of the percentage amount of the alkali metal tripolyphosphate and half of the percentage amount of the aluminosilicate material lies between approx. 25 and approx. 37. 3. Detergent mixture as stated in claim 1, characterized in that the synthetic detergent active material is selected from among anionic synthetic detergent active materials and mixtures thereof, together with a smaller amount of one or more non-anionic synthetic detergent active materials. 4. Detergent mixture as stated in claim 1, characterized in that the synthetic detergent-active material includes an anionic detergent-active material and a non-ionic detergent-active material in a relative weight ratio of at least 2:1. 5. Detergent mixture as stated in claim 1, characterized in that there. also contains a stabilizer for the bleaching system. 6. Detergent mixture as specified in claim 1, characterized in that it contains: from approx. 10 to approx. 25% by weight of a mixture of anionic detergent-active material together with synthetic non-ionic detergent-active material, the weight ratio between the anionic material and the non-ionic material being between approx. 3:1 and approx. 10:1> in that the anionic material is a mixture of a synthetic anionic detergent active material and soap; from approx. 15 to approx. 22% by weight sodium tripolyphosphate; from approx. 12 to approx. 30% crystalline alumino-silicate washability builder; from approx. 5.5 to about 27% by weight sodium perborate; from approx. 0.5 to approx. 10% by weight tetraacetylethylenediamine, as the weight ratio between the sodium perborate and the tetra-acetylethylenediamine is between approx. 3.5:1 and approx. 10:1; the remainder of the mixture, if any, being water, and optionally conventional detergent mixture ingredients.