EP0473622A1

EP0473622A1 - Granular, phosphate-free additive for detergents, containing non-ionic tensides.

Info

Publication number: EP0473622A1
Application number: EP90906974A
Authority: EP
Inventors: Franz Hundgeburt; Dieter Jung; Fred Schambil; Guenther Vogt; Gerti Nienhaus
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1989-05-22
Filing date: 1990-05-14
Publication date: 1992-03-11
Anticipated expiration: 2010-05-14
Also published as: ES2055910T3; WO1990014412A1; DE59006321D1; DE3916629A1; ATE107957T1; PT94102A; EP0473622B1

Abstract

A granular, phosphate-free additive for detergents consists of (A) 10 to 70 wt.% of sodium perborate monohydrate, (B) 25 to 80 wt.% of a granular mixture of salts and (C) 5 to 30 wt.% of non-ionic tensides. Component (B) is a spray-dried, absorbent granulate containing 45 to 75 wt.% (calculated on the anhydrous basis) of fine crystalline zeolite, 0 to 30 wt.% of sodium sulphate, 1 to 12 wt.% of salts of (co)polymer carboxylic acids as well as bound water. In addition, (C) may contain traces of a water-soluble soap; the total content of inorganic compounds in (C) is at least 75 wt.%.

Description

"Granular, phosphate-free detergent additive containing nonionic surfactants"

The invention relates to a granular detergent additive consisting of two granular powder components of a defined composition, to which liquid, semi-solid or solid nonionic surfactants are adsorbed. Both powder components have a porous structure and can absorb up to 30% by weight, based on the additive, of such nonionic surfactants without the free-flowing properties suffering.

As is known, nonionic surfactants have a very high cleaning ability, which makes them particularly suitable for use in low-temperature detergents. However, their proportion cannot be increased significantly beyond 8 to 10 percent by weight in the generally customary production of detergents by spray drying, since this would otherwise result in excessive smoke formation in the exhaust air from the spray towers and poor giant properties of the spray powder. Methods have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried powder or sprayed onto a carrier substance. Both water-soluble builder salts, in particular spray-dried phosphates, carbonates, bicarbonates, soluble silicates and borates, and water-insoluble substances, such as sodium aluminosilicate (zeolite), were used as the carrier substance. and silicon dioxide (Aerosil) have been proposed, but the known agents often have only a limited adsorption capacity and certain technical disadvantages. In addition, phosphates are often undesirable because of their eutrophic properties. Fine powdered zeolites likewise have only a limited absorption capacity for liquid substances, while special adsorbents, such as diatomaceous earth and aerosil, do not contribute to the washing action as inert components.

DE 24 18 294 discloses detergents which consist of a powder component obtained by hot spray drying and granular sodium perborate tetrahydrate, the latter being impregnated with a defined mixture of nonionic surfactants. Due to the selection of nonionic surfactants, the granulate is dust-free and free-flowing. According to EP-A 34 194, the perborate tetrahydrate is treated with nonionic surfactants which contain both ethylene glycol ether groups and propylene glycol ether groups. In addition to good flowability, the granules are particularly characterized by being odorless.

DE-B 25 07 926 contains examples of the preparation of premixes, powder mixtures of aluminosilicate (zeolite), perborate and optionally also a bleach activator being sprayed with non-ionic surfactants. The resulting granules are then mixed with other powder components, in particular tower spray powder. Here, a certain stickiness of the granules disturbs, which can also be transferred to the overall mixture, especially if the admixed tower spray powder contains no phosphates. If one tries to replace the sodium perborate tetrahydrate in these granules with sodium perborate monohydrate, which is known to have better solubility in cold water and therefore has advantages in the low-temperature washing range, additional difficulties arise. Above a certain critical amount of adsorbed nonionic surfactant, the ignition range of the mixture is reduced to such an extent that, under unfavorable conditions, the mixtures can self-ignite even at room temperature.

EP-A 168 102 discloses a process for the production of high-density detergents in which nonionic surfactants are sprayed onto a powder mixture of sodium perborate monohydrate, zeolite and other builder salts. In this spray mixing process, granulation of the base powder occurs at the same time. Another part of the nonionic surfactants used overall is sprayed onto a second powder component which is free of sodium sulfate and consists of spray-dried granules which contain the usual surfactants, builder salts and other detergent components. Both the perborate-containing base powder and the spray-dried powder component contain considerable amounts of sodium tripolyphosphate in the agents according to the examples. As already stated, such a base powder of perborate and powdered zeolite, especially if it is free from tripolyphosphate, leads to the formation of sticky, poorly pourable granules after the application of large amounts of nonionic surfactants. In order nevertheless to be able to incorporate larger amounts of these surfactants, it is proposed to treat not only the base powder but also the spray drying product in the same way in a spray mixing system. This procedure is therefore comparatively cumbersome because it is a much larger one Product stream must be passed through the spray mixing system. The problem of spontaneous combustion does not arise in this process, since the proportion of perborate monohydrate in the base powder is not very high and water is sprayed on at the same time with the nonionic surfactant.

On the other hand, absorbent carrier particles are known, ^which consist of mehre¬ ren ingredients and are made mostly by spray drying her¬. Examples of these are the agents according to US 3 849 327, US 3 886 098 and US 3 838 027 and US 4 269 722 (DE 27 42 683). However, these carrier grains developed especially for the adsorption of nonionic surfactants contain considerable amounts of phosphates, which limits their possible uses. Phosphate-free carrier grains are known from DE-A 32 06265 (GB 20 97 419) and DE-A 32 06 379 (GB 20 95 274). They consist essentially of sodium carbonate or hydrogen carbonate, zeolite, sodium silicate, bentonite and polyacrylate. The high proportion of carbonates, however, favors the formation of calcium carbonate in hard water, while the sodium silicate in conjunction with zeolite considerably deteriorates the dispersibility of the grains in water.

EP-A 184794 (US 4707 290) discloses a granular adsorbent which is able to absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight zeolite, 0 , 1 to 8% by weight of sodium silicate, 3 to 15% by weight of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18% by weight of water and optionally up to 5% by weight % contains nonionic surfactants and can be obtained by spray drying. In practice it has been shown that in washing machines Machines with poorly designed induction devices do not completely detach the products in the course of the induction phase and leave residues. This worsened detergent behavior is not only shown by the particles themselves, but they can also have an influence on the solubility or detergent content of the other powdered detergent components. The consequence of this is that a powder mixture which is intrinsically easy to flush in becomes difficult to flush in overall if it additionally contains such a powder component in the mixture.

The object was therefore to develop a granular adsorption material which avoids the disadvantages listed, in particular the formation of highly flammable mixtures, and has a high adsorption capacity for nonionic surfactants and, together with them, has improved dissolving and flushing behavior . The invention accordingly relates to a granular, free-flowing, phosphate-free detergent additive containing

(A) 10 to 70% by weight sodium perborate monohydrate, which has an average grain size of 0.2 to 1.2 m,

(B) 25 to 80% by weight of a granular salt mixture having an average grain size of 0.2 to 1.2 m, which is at least 75% by weight inorganic in nature and free of peroxygen and (on anhydrous substance in component B related) 45 to 75% by weight of synthetic, finely crystalline zeolite, 0 to 30% by weight of sodium sulfate and 1 to 12% by weight of salts of homopolymeric or copolymeric carboxylic acids,

(C) 5 to 30% by weight of nonionic surfactants which are bound to the granular components (A) and (B).

The granular components (A) and (B) as well as the finished agent have one in the interest of good flowability an average grain size of 0.2 to 1.2 mm, preferably of 0.3 to 1 mm. In particular, the proportion of particles in the composite with a grain size below 0.05 mm is less than 1% by weight, preferably less than 0.1% by weight, and the proportion with a grain size below 0.1 m less than 2% by weight, preferably less than 1% by weight, the fraction with a grain size of more than 2 mm less than -5% by weight, preferably less than 1% by weight and the fraction with a grain size over 1.2 mm less than 10% by weight, preferably less than 5% by weight. Both components can have the same or a different grain size within the specified limits. The joint mixing and treatment with nonionic surfactants can result in a slight agglomeration of the particles, in particular in the connection of finely divided constituents to larger grains, and thus overall a slight increase in the average grain size.

The proportion of sodium perborate monohydrate (component A) is 10 to 70% by weight, preferably 20 to 60% by weight and in particular 30 to 50% by weight. The proportion of component (B) is 25 to 80% by weight, preferably 35 to 70% by weight and in particular 40 to 60% by weight. The proportion of the nonionic component (C) is 5 to 30% by weight, preferably 7 to 20% by weight and in particular 10 to 15% by weight.

The perborate monohydrate is preferably used as loose, expanded pellets with a liter weight of 450 to 650 g / 1, preferably 500 to 600 g / 1. Such grains are characterized by a good adsorption capacity for liquid to lard-like nonionic surfactants. Loading the grains with the nonionic surfactants generally increases the bulk density another 50 to 200 units, which is in the interest of a higher total bulk weight and a saving in packaging and transport volume.

Component (B) likewise preferably consists of a granular, porous material, as can be obtained by spray drying aqueous slurries of water-insoluble or water-soluble salts or salt mixtures. It contains synthetic zeolite of the NaA type in proportions of 45 to 75, preferably 50 to 70% by weight and in particular 55 to 68% by weight (based on anhydrous substance). Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being below 30%, in particular below 20%. Suitable zeolites have no particles larger than 30 μm and consist of at least 80% of particles smaller than 10 μm. Their average particle size (volume distribution, measurement method: Coulter Counter) is in the range from 1 to 10 μm. Their calcium binding capacity, which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g. The zeolites can still contain excess alkali from their production. Their water content of synthetic zeolites is usually 18 to 22% by weight.

Another advantageous component of component (B) is sodium sulfate, which is calculated as an anhydrous substance and is present in proportions of 0 to 30% by weight, preferably 1 to 25 and in particular 3 to 20% by weight. The sodium sulfate contributes to a considerable improvement in the grain structure of component (B) and the washing-in behavior of the detergent additive and at the same time increases its bulk density, which results in the possibility of saving packaging and transport volume. Another inorganic salt that can be combined with the zeolite is sodium carbonate, which can be present in proportions of up to 20% by weight, based on component (B). With regard to the flushing-in behavior, however, such mixtures are inferior to the mixtures of zeolite and sodium sulfate.

The content of component (B) in inorganic salts including zeolite should be at least 75% by weight, preferably at least 85% by weight (based on component B). In addition, component (B) contains organic salts which are particularly advantageous for the grain structure, the grain rod 1 and in particular for the washing-in behavior of the granules and their mixtures with other detergent constituents.

These organic salts which are contained in component (B) include the sodium or potassium salts, preferably the sodium salts of homopolymeric and / or copolymeric carboxylic acids. Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid, with polyacrylic acid being preferred. Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether. In such copolymeric acids, in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 50 mole percent, preferably less than 30 mole percent. Copolymers of acrylic acid or methacrylic acid with maleic acid, as described in more detail, for example, in EP 25 551-B1, have proven particularly suitable. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Such copolymers are particularly preferred, in which 45 to 85 percent by weight acrylic acid and 55 to 15 percent by weight maleic acid are present.

The molecular weight of the homo- or copolymers are generally employed is from 2000 to 150,000, preferably 5000 to 100 000. My An¬ part in the component attempts (B) is for example 1 to 12 wt .-% preferably 1.5 to _r 8% by weight and in particular 2 to 5% by weight, calculated as the sodium salt. The resistance of the grains to abrasion increases with an increasing proportion of polyacid or its salts. With a proportion from 1.5% by weight, sufficient abrasion resistance is achieved in many cases. Mixtures with 2 to 5% by weight of sodium salt of polyacid have optimal abrasion properties.

An optional, advantageous component of component (B), which in particular significantly improves the washing-up behavior in the washing machine, consists of a water-soluble soap, preferably a sodium soap, which is derived from saturated fatty acids with 10 to 24, preferably 12 to 22 C. -Atoms and mixtures thereof with oleic acid, the proportion of saturated fatty acids should be at least 50 wt .-%, preferably at least 75 wt .-%. Examples are soaps made from coconut oil, tallow oil and hardened rapeseed oil fatty acids, hardened fish oil fatty acids and mixtures thereof. Their proportion is 0 to 6, preferably 1 to 5 and in particular 2 to 4% by weight, based on component (B).

It has proven to be advantageous if the weight ratio of soap to polymeric acid Na salt is in the range from 2.5: 1 to 1: 5, in particular in the range from 1.5: 1 to 1: 4. These areas are characterized by good induction results. Stronger deviations, in particular higher soap contents at the expense of the polymer acid content lead to less favorable values. A readily usable granular component (B) accordingly contains (calculated as anhydrous constituents) 45 to 75% by weight, preferably 50 to 70% by weight, zeolite,

0 to 30% by weight, preferably 2 to 20% by weight, sodium sulfate,

1 to 12% by weight, preferably 1.5 to 8% by weight of polymer salt, 0 to 6% by weight, preferably 1 to 5% by weight of soap.

In cases where the zeolite is used in the production of the granular component (B) not in powdery or spray-dried form, but rather as a moist filter cake, it can contain dispersion stabilizers, as described in DE 25 27 388 in more detail are described. Suitable stabilizers are, in particular, nonionic surfactants with HLB values below 12, such as ethoxylated tallow alcohol with 3 to 8 E0. The proportion of these additives in the powder component (B) can, depending on the zeolite content, be up to 4% by weight, usually 0.3 to 3% by weight. In the final balance, this portion of component (C) is added.

The difference of up to 100% by weight is due to water, which is present in a bound form and as moisture, the major amount being bound to the zeolite. A proportion of the water, which is approximately 8 to 18% by weight (based on the agent), can be removed at a drying temperature of 145 ° C. A further fraction, which is between 4 and 8% by weight depending on the zeolite fraction, is released at the annealing temperature (800 ° C.) and corresponds to the water stored in the crystal lattice of the zeolite.

The average grain size of component (B) is 0.2 to 1.2 m, the proportion of the grains below 0.05 m less than 1% by weight, preferably less than 0.5% by weight and above 2 mm should not be more than 5% by weight. At least 80% by weight, in particular at least 90% by weight, of the grains preferably have a size of 0.1 to 1.2 mm, the proportion of the grains being between 0.1 and 0.05 mm, preferably not more than 3% by weight, in particular less than 1% by weight, the proportion of the grains between 0.1 and 0.2 mm less than 20% by weight, in particular less than 10% by weight and the proportion the grain between 1.2 and 2 mm is not more than 10% by weight, in particular not more than 5% by weight. The bulk density of component (B) in the preferred embodiment is 400 to 680 g / 1, preferably 450 to 650 g / 1. Adsorption of the nonionic surfactants also increases it by 50 to 200 g / 1.

The nonionic surfactants adsorbed on the mixture of components (A) and (B) are those which are usually used in washing and cleaning agents. Other suitable additives are organic solvents with which the cleaning ability of detergents and cleaning agents is improved, in particular in relation to greasy soiling, and which can be incorporated into a granular cleaning agent in this way without problems. However, other substances, such as fragrances, finishing agents, optical brighteners and anionic or cationic surfactants, can also be added to the mixture of components (A) and (after prior dissolving or dispersing in organic solvents or the liquid or molten nonionic surfactants). B) are added. These substances penetrate into the porous grains together with the solvent or dispersant and are thus protected against interactions with other powder components.

Preferred detergent ingredients which are bound to the granular mixture and together with it as a free-flowing mixture are liquid to pasty nonionic surfactants from the class of polyglycol ethers, derived from alcohols with 10 to 22, in particular 12 to 18, carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl branched in the 2-position (oxo radical). Their reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation. In the case of technical alkoxylates, the number of EO or PO groups corresponds to the statistical mean.

Examples of suitable ethoxylated fatty alcohols are C 1-10 coco alcohols with 3 to 12 EO, Ci6_ιs-tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures From the series of ethoxylated oxo alcohols, for example, those with the composition C12-15 ⁺ to 10 EO and C14-C15 + 3 to 12 EO are suitable. Mixtures are characterized by low and high levels of detergency against greasy and mineral soiling highly ethoxylated alcohols, for example those made from tallow alcohol + 3 to 6 EO and tallow alcohol + 12 to 16 EO or Ci3_ιs-0xoalkohol + 3 to 5 EO and Ci2-14-0x - alcohol + 8 to 12 EO. Particularly good washing-in properties have agents in which the adsorbed nonionic surfactants have both long hydrophobic residues and higher degrees of ethoxylation.

The preparation of component (B) in the preferred embodiment is based on an aqueous batch containing a total of 40 to 55% by weight of water-free ingredients, which is sprayed into a falling space by means of nozzles and by means of drying gases which have an inlet temperature of 150 to 280 ° C and have an outlet temperature of 50 to 120 ° C, is dried to a removable moisture content of 145 ° C of 8 to 18 wt .-%.

The aqueous batch can be prepared by mixing the dry or water-containing constituents with the addition of the water required for liquefaction. Instead of the soap or the salts of the polymeric carboxylic acids, the corresponding free acids can also be incorporated and the alkali required for salt formation can be added separately. The addition of alkali hydroxide, in particular NaOH, is also recommended in order to make the aqueous zeolite suspension or the slurry alkaline, i.e. adjust to a pH of at least 8 and provide a sufficient alkali excess so that the pH does not drop to less than 8 during the spray drying. Such a lowering of the pH value, which would lead to a loss of activity of the zeolite, can be caused by CO2 in the dry gas. The addition of NaOH, which ensures a sufficient alkali reserve, can be, for example, up to 3% by weight. In general, 0.2 to 1% by weight is sufficient.

The content of water-free ingredients in the aqueous mixture is preferably 43 to 50% by weight. Its temperature is expediently 50 to 100 ° C and its viscosity 2,000 to 20,000 mPa-s, usually 8,000 to 14,000 mPa-s. The atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar. The drying gas, which is generally obtained by burning heating gas or heating oil, is preferably conducted in countercurrent. When using so-called drying towers, into which the aqueous batch is sprayed in the upper part via several high-pressure nozzles, the inlet temperature, measured in the ring channel, is (ie immediately before entering the lower part of the tower) 150 to 280 ° C, preferably 170 to 250 ° C. The exhaust gas, which is laden with moisture and leaves the tower, has a temperature of 50 to 130 ° C, preferably 55 to 115 ° C. The spray drying is conducted in such a way that the particle size of the spray product has the distribution given above. Existing fine and coarse grains are screened before further processing. It has been shown that the flushing behavior of the adsorbent impregnated with nonionic surfactants deteriorates with increasing proportion of fine grain.

Both powder components are combined to form a homogeneous mixture and then treated with liquid or nonionic surfactants or surfactant mixtures liquefied by heating. For the purpose of faster distribution, the nonionic surfactant is expediently sprayed onto the agitated mixture. Heating the nonionic surfactant to temperatures between 35 and 60 ° C, preferably 40 to 50 ° C, accelerates the adsorption process. The abrasion resistance and constancy of shape of the grains is so high when the specified proportions or production conditions are met that the freshly prepared, but especially the cooled and, if necessary, reheated, ripened grains are treated with the liquid additives under the usual spray mixing conditions , can be mixed and conveyed without the formation of fine fractions or coarser agglomerates. There is also no risk of spontaneous combustion during processing and storage when using the mixtures according to the invention.

The mixing of the two granular components and the subsequent spraying with nonionic surfactants can be carried out in the usual way mechanical mixing devices, such as drum mixers, fluidized bed mixers or spray mixers, are carried out continuously or discontinuously. The mixing and spraying process can also be carried out with continuous operation of a single mixing apparatus, the two powder components being combined in a first mixing section and the nonionic component being added in a final mixing section. A particular advantage of the invention is that the adsorption of the liquid nonionic surfactants and their diffusion into the interior of the grain takes place comparatively quickly. Shortly after leaving the mixing apparatus, the grain mixtures have their full flow properties and can be processed further without intermediate storage or a time-consuming post-ripening process.

After the application of the nonionic surfactant or the additives that may have been added, the grains can optionally be dusted with finely divided powders or coated on the surface. As a result, the pourability can be improved even further and the bulk density can be increased slightly. Suitable powdering agents have a grain size of 0.001 to a maximum of 0.1 mm, preferably less than 0.05 mm and can be in proportions of 0.03 to 3, preferably 0.05 to 2% by weight ¬ applied to the adsorbent loaded with additive. For example, finely powdered zeolites, silica airgel (Aerosil ( ^R )), colorless or colored pigments, such as titanium dioxide, and other powder materials already proposed for powdering granules or detergent particles, such as finely powdered sodium tripolyphosphate, sodium sulfate, magnesium silicate and carboxylmethyl cellulose. In the products according to the invention, such a treatment is generally not necessary, especially since the washability is not improved thereby. The granular adsorbents impregnated with the nonionic surfactants or with the mixtures of nonionic surfactant and additive can be mixed with further powdery to granular detergents or detergent components, as can be obtained, for example, by spray drying or granulation, or with bleaches or with detergents containing bleach known composition can be mixed in any ratio. Here, their good flowability and their high grain stability are of great advantage, since an undesirable formation of abrasion and dust is avoided. The powder mixtures are in turn stable in storage and do not tend to clump or exude the nonionic surfactant. When used, they are particularly easy to flush in compared to known agents. In contrast to the information in EP-A 168 102, the admixed spray powders and granules can also contain sodium sulfate, which is often advantageous for their grain properties, especially in the absence of phosphates. These admixed detergent components are therefore preferably also phosphate-free. In addition, the absorbency of the granulate mixture according to the invention for nonionic surfactants is so high that an additional application of these surfactants to other mixture components is unnecessary.

B e i s p i e l e

1. Production of component B

The following constituents were mixed in a batch container equipped with a stirring device with the addition of water to form a slurry (GT = parts by weight) a) containing 67.4 GT of zeolite NaA (calculated as anhydrous)

0.4 GT free NaOH and

2.1 pbw of ethoxylated tallow fatty alcohol with 5 EO as a dispersion stabilizer b) 4.0 pbw of acrylic acid-maleic acid copolymer (Na salt) c) 2.5 pbw of Na soap (Ci2-i8 coconut tallow soap 1: 1 ) d) 4.4 pbw of sodium sulfate

The zeolite used had a calcium binding capacity of 165 mg CaO / g and an average particle size of 3 μm, with no proportions above 20 μm. It was used as an aqueous dispersion (filter cake) containing 48% by weight of anhydrous zeolite and the other additives mentioned under (a) and 50.2% by weight of water. A copolymer of acrylic acid and maleic acid with a molecular weight of 70,000 (Sokalan W) in the form of the sodium salt was used as the polycarboxylic acid.

The aqueous slurry, which had a temperature of 85 ° C. and a viscosity of 10 200 mPa * s, was sprayed with a pressure of 40 AT in a tower in which combustion gases at a temperature of 226 ° C. (measured in the ring channel) spray product were brought up to. The outlet temperature of the Dry gas was 63 ° C. The granular adsorbent leaving the spray tower contained e) 19.2 pbw of water.

The grain spectrum determined by sieve analysis gave the following weight distribution:

mm above 1.6 to 0.8 to 0.4 to 0.2 to -0.1 below 0.1% by weight 0 2 39 52 7 0

The bulk weight was 563 g / 1.

2. Preparation of the detergent additive

In a mixer equipped with rotating mixing elements (spray mixer), 40.9 pbw of sodium perborate monohydrate (average particle size 0.4 mm, bulk density 550 g / l) were premixed with 46.5 pbw of the spray-dried component (B) for 2 minutes. The temperature of the dry mixture was 28 ° C. Subsequently, 12.6 pbw of a mixture of coconut alcohol + 3 E0 and tallow alcohol + 5 E0 (mixing ratio 1: 4) heated to 50 ° C. were sprayed onto the still moving grain mixture within 1.5 minutes and the mixing continued for a further 2 minutes . The mixture removed from the mixer and having a temperature of 33 ° C. was free-flowing after cooling to room temperature and had a bulk density of 700 g / l. The grain size distribution was practically unchanged compared to the starting material. In contrast to an unblended perborate monohydrate treated in the same way with nonionic surfactant, the mixture was not self-igniting when heated to 38 to 45 ° C. To determine the flow behavior, 1 liter of the powder was filled in a funnel closed at its outlet opening with the following dimensions.

Upper opening diameter 150 mm

Diameter of the lower opening 10 mm

Height of the conical funnel area 230 m

Height of the cylindrical set below

Area 20 m

Inclination angle of the conical area 73 o

Dry sea sand with the following grain spectrum was chosen as the reference substance:

m over 1.5 to 0.8 to 0.4 to 0.2 to 0.1% by weight 0.2 11.9 54.7 30.1 3.1

The run-out time of the dry sand after opening the outflow opening was set at 100%. The free-flowing properties of the products according to the invention are given in%, based on this 100% value. Values above 75% are considered very good.

In a further series of experiments, the washing-in behavior was investigated, conditions being simulated that of a washing-in device operated under critical conditions

Household washing machine correspond. In each case, 100 g of product were introduced into the test device (ZANUSSI induction channel) and, after a rest period of 1 minute, 10 liters of tap water were fed in within 90 seconds. After flushing in 10 liters, the remaining residues were weighed out in the wet state and 30% of the weight was calculated as water. subtracted. The following ratings were assigned for the induction behavior: A = complete induction (the number gives the liters required)

Water on), B = residue less than 10 g (the number gives the

Residue amount in g an), C = more than 10 g residue (with the residue in g). A and B values are very good to satisfactory in practice. C values indicate inadequate induction behavior.

Two test series were carried out, namely (I) with the detergent additive without the addition of a detergent and (II) a mixture of 25 parts of the detergent additive and 75 parts of a detergent, consisting of 50 parts of tower spray powder and 25 parts of other granular constituents Defoamers, enzymes, fragrances and bleach activators.

The tower spray powder had the following composition (in% by weight):

17.6% n-dodecylbenzenesulfonate (Na salt)

2.5% tallow soap (Na salt) 4.0% tallow alcohol + 14 E0

20.5% Zeol th NaA (calculated anhydrous) 15.0% soda

5.0% copolymer (b)

0.5% Na hydroxyethane disphosphonate

3.0% sodium silicate 1: 3.3

1.6% carboxymethyl cellulose 18.0% sodium sulfate

12.3% water The trickle test gave a value of 79%, based on dry sand for the detergent additive (I) and 81% for the complete detergent mixture (II). The wash-in notes were B2 for the detergent additive (I) and A8 for the completed detergent mixture (II).

A base powder was used for comparison, consisting of (given in parts by weight):

8.5 T sodium perborate monohydrate

2.24 T sodium sulfate (anhydrous)

10.0 T zeolite (20% water content)

The zeolite was in powder form and corresponded to the product HAB 40 according to the information in EP-A 168 102. The above recipe differs from example 1 in that the tripolyphosphate (7 T) was replaced by zeolite.

After the powder had been homogenized, 4 parts of nonionic surfactant (C12-15 oxo alcohol + 7E0) and 1 part of water were sprayed on in a spray mixer, as described in the example cited. The granules formed proved to be slightly tacky and gave a value of less than 65% when determining the pourability, which is why the tower spray powder was not added.

Claims

Patent claims

1. Containing granular, phosphate-free detergent additive

(A) 10 to 70% by weight sodium perborate monohydrate, which has an average grain size of 0.2 to 1.2 mm,

(B) 25 to 80% by weight of a granular salt mixture which has an average crown size of 0.2 to 1.2 mm and which is at least 75% by weight inorganic in nature and free of peroxygen and (on anhydrous substance in component B) 45 to 75% by weight of synthetic, finely crystalline zeolite, 0 to 30% by weight of sodium sulfate and 1 to 12% by weight of salts of homopolymeric or copolymeric carboxylic acids,

2. Composition according to claim 1, in which the fraction with a grain size less than 0.05 mm less than 1 wt .-%, preferably less than 0.1 wt .-%, the fraction with a grain size less than 0.1 m less than 2% by weight, preferably less than 1% by weight, the fraction with a grain size over 2 mm less than 5% by weight, preferably less than 1% by weight and the fraction with a grain size over 1.2 mm is less than 10% by weight, preferably less than 5% by weight.

3. Composition according to claim 1 and 2, containing 20 to 60 wt .-%, in particular 30 to 50 wt .-% of component (A), 35 to 70 wt .-%, in particular 40 to 60 wt .-% of the component (B) and 7 to 20% by weight, in particular 10 to 15% by weight of the component

(C).

4. Composition according to one or more of claims 1 to 4, in which the sodium perborate monohydrate used has a bulk density of 450 to 650 g / 1, preferably from 500 to 600 g / 1.

5. Composition according to one or more of claims 1 to 5, wherein component (B) 45 to 75 wt .-% (based on anhydrous substance) of synthetic, bound water-containing, finely divided zeolite, 0 to 30 wt .-% Sodium sulfate, 1.5 to 8% by weight of homopolymeric or copolymeric polycarboxylic acids (calculated as the sodium salt and 1.0 to 6% by weight of a water-soluble soap derived from C24-24 fatty acids and bound water).

6. A process for the preparation of the agent according to one or more of claims 1 to 6, characterized in that a homogeneous, dry mixture of components (A) and (B) with ei¬ ner liquid or liquefied by heating component ( B) sprayed while mixing.

7. Powdery to granular, phosphate-free to low-phosphate detergent, characterized by a content of the detergent additive according to one or more of claims 1 to 5.