DE4209435A1 - Granular, non-ionic surfactants containing, phosphate-free additive for detergents and cleaners - Google Patents

Abstract

The aim is to produce an additive for granular and phosphate-free washing and cleaning agents, which contains non-ionic surface-active agents and which has both a better rinsing behaviour and a higher self-ignition temperature, i.e. lower combustibility. This is achieved with a granular, phosphate-free additive which contains: (A) 10-70 % by weight sodium perborate monohydrate with a mean granular size of between 0.2 and 1.2 mm; (B) 25-80 % by weight of a granular mixture with a mean grain size of between 0.2 and 1.2 mm, of which at least 75 % by weight is anorganic and free from peroxygen and contains 45-75 % by weight of synthetic, compact-grained zeolite (in relation to anhydrous substance in component B), 0-30 % by weight sodium sulphate and 1-12 % by weight homopolymer or copolymer carboxylic acid salts; (C) 5-30 % by weight non-ionic surface active agents bonded to the granular components (A) and (B), (B) containing 2-10 % by weight (in relation to the anhydrous substance in component B) of a layered silicate.

Description

The invention relates to a granular additive for washing and cleaning medium, the composition of two granular powder components defined consists of those liquid, semi-solid or solid non-ionic Surfactants are adsorbed. Both powder components have a porous Structure and can together up to 30 wt .-%, based on the Addi tive, take on such nonionic surfactants without the Flowability suffers.

Nonionic surfactants are known to have a very high Reinigungsver especially what they are for use in low temperature washing makes it suitable. Their share can be found in the usual Detergent production by spray drying but not significantly over Increase 8 to 10 percent by weight, otherwise it becomes excessive Smoke in the exhaust air of the spray towers as well as insufficient Rieseleigen the spray powder comes. Therefore, methods have been developed in which the liquid or molten nonionic surfactant on the previously Spray-dried powder or mixed onto a carrier is sprayed. The carrier substance used was both water-soluble buildersub in particular spray-dried phosphates, carbonates, bicarbonates, soluble silicates and borates as well as water-insoluble builder substances, such as sodium aluminosilicate (zeolite) and silica (Aerosil) However, the known means often have only a limited Adsorption and certain application disadvantages. In addition, phosphates are because of their eutrophic properties often undesirable. Fine powdery zeolites also have only one limited capacity for liquids, while special Ad sorbents, such as diatomaceous earth and Aerosil, as inert components none Contribute to the washing effect.  

From DE 24 18 294 detergents are known which consist of a hot spray drying powder component and granular sodium perborate tetra hydrate, the latter having a defined mixture nichtio nischer surfactants is impregnated. Due to the choice made nonionic surfactants, the granules are dust-free and flowable. According to EP 34 194, the perborate tetrahydrate with nonionic surfactants which handles both ethylene glycol ether groups and propylene glycol contain ether groups. The granules are characterized except by good Free-flowing especially by odor.

In DE 25 07 926 there are examples of the production of Vorge Mixing powder mixtures of aluminosilicate (zeolite), perborate and optionally also a bleach activator with nonionic surfactants be be sprayed. The resulting granules are then further Powder components, in particular tower spray powder mixed. This bothers a certain stickiness of the granules, which also affects the Gesamtge can transmit mixed, especially when the admixed tower spray powder contains no phosphates.

If you try in these granules, the sodium perborate tetrahydrate by To replace sodium perborate monohydrate, which is known to be replaced by a better solubility in cold water and therefore in the low peratur-Waschbereich has advantages, so there are additional Trouble. From a certain critical amount of adsorbed nonionic surfactant, the ignition range of the mixture so far down put it under unfavorable conditions to self-ignite the Mixtures can already come at room temperature.

From EP 168 102 a process for the production of detergents is higher Density is known in which nonionic surfactants are based on a powder mixture Sodium perborate monohydrate, zeolite and other builders be sprayed. In this spray mixing process occurs simultaneously Granulation of the base powder. Another part of the total turned Nonionic surfactants are added to a second powder component sprayed, which is free of sodium sulfate and from a spray-dried Granules consists of the usual surfactants, builders and others  Contains detergent ingredients. Both the perborate-based base powder as well as the spray-dried powder component contained in the compositions according to the examples, significant amounts of sodium tripolyphosphate. As be already executed, such a base powder of perborate and powder shaped zeolite, especially if it is free of tripolyphosphate, according to the application of larger amounts of nonionic surfactants for the formation sticky, poorly flowable granules. To still larger quantities To be able to incorporate these surfactants is proposed, not only that Base powder, but also the spray-drying product in a spray mixture system in the same way. This method is therefore ver cumbersome because a much larger product flow through the Spray mixing must be performed. The problem of auto-ignition By the way, this process does not arise because the proportion of Per borate monohydrate in the base powder is not very high and with the nonio nish surfactant is sprayed on water at the same time.

On the other hand, absorbent carrier grains are known which consist of several Be consist of components and are usually prepared by spray drying. Examples include the means according to US 3,849,327, US 3,886,098 and US 3,838,027 and US 4,269,722 (DE 27 42 683). This particular to Ad containing carrier grains developed by nonionic surfactants however, significant amounts of phosphates, indicating their potential uses limits. Phosphate-free carrier grains are known from DE 32 06 265 and DE 32 06 379 GB known. They consist essentially of sodium carbonate or hydrogencarbonate, zeolite, sodium silicate, bentonite and polyacrylate. The However, high proportion of carbonates favors the formation of calcium carbonate in hard water, while the sodium silicate in conjunction with Zeolite, the dispersibility of the grains in water significantly deteriorate tert.

From EP 184 794 a granular adsorbent is known, the high An parts of liquid to pasty detergent ingredients, in particular can absorb nonionic surfactants and (on anhydrous substance from 60 to 80 wt .-% zeolite, 0.1 to 8 wt .-% sodium silicate, 3 to 15 wt .-% of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18 wt .-% water and optionally up to 5  Wt .-% of nonionic surfactants and by spray drying he is fair. In practice, it has been shown that in washing machines with Inconveniently designed dispensers designed the products in course Do not completely dissolve the rinsing phase and leave residues. This worsened flushing behavior does not only show those in question Particles themselves, but they can also influence the solubility or the flushing behavior of the other powdered detergent com exercise their constituents. This has the consequence that a good einspülbares in itself Total powder mixture is poorly einspülbar, if there is an additional contains such powder component in the mixture.

From EP 425 804 is a granular, nonionic surfactants containing Additive for detergents and cleaners known that an improved Einspülverhalten and from a granular adsorbent (I) and nonionic surfactants (II) adsorbed thereon, wherein (I) is 50 to 75 wt .-% of finely crystalline zeolite, 2 to 10 wt .-% of a Schichtsi likates, 3 to 15 wt .-% of the sodium salt of a (co) polymer Carboxylic acid, optionally up to 10 wt .-% sodium sulfate and up to 3 Wt .-% of a surfactant and the balance water and minor constituents and the weight ratio of adsorbent (I) to nonionic Surfactants (II) is 2: 1 to 20: 1.

International Patent Application WO 90/14412 describes granular ad sorbent, which has a high adsorption capacity for nonionic Have surfactants and together with these an improved solution and Have flushing behavior. These granular, free-flowing and phosphate free detergent additives contain (A) 10 to 70 wt .-% Sodium perborate monohydrate, which has a mean particle size of 0.2 to 1.2 mm (B) 25 to 80% by weight of a granular, average grain size 0.2 to 1.2 mm mixture containing at least 75% by weight inorganic nature and is free of peroxygen and (on anhydrous Substance in component B) 45 to 75 wt .-% synthetic, fine crystalline zeolite, 0 to 30% by weight of sodium sulfate and 1 to 12% by weight Contains salts of homopolymeric or copolymeric carboxylic acids, (C) 5 to 30 % By weight of nonionic surfactants attached to the granular components (A) and (B) are attached.  

Optional, but with advantages, component (B) contains a water-soluble soap, reducing the flushing behavior in the washing machine is significantly improved. The disadvantage, however, is that the soap-containing Additive has a lower absorbency for nonionic surfactants and a lowered auto-ignition temperature or an increased combustible has.

The object of the invention was to provide an additive for granular and to provide phosphate-free detergents and cleaners that are not contains niche surfactants and both an improved Einspülverhalten than also an increased autoignition temperature or a decreased Flammability.

The invention accordingly relates to a granular and phosphate free additive for detergents and cleaners, containing

• (A) 10 to 70% by weight of sodium perborate monohydrate, which is a medium Grain size of 0.2 to 1.2 mm,
• (B) 25 to 80% by weight of a granular, average grain size of 0.2 to 1.2 mm mixture containing at least 75 Wt .-% of inorganic nature and free of peroxygen is and (based on anhydrous substance in component B) 45 to 75 Wt .-% synthetic, finely crystalline zeolite, 0 to 30 Wt .-% sodium sulfate and 1 to 12 wt .-% salts homopolymer or copolymeric carboxylic acids,
• (C) 5 to 30 wt .-% of nonionic surfactants, the granular Components (A) and (B) are bonded, wherein (B) 2 to 10 Wt .-%, based on the anhydrous substance in component (B), of a layered silicate.

The granular components (A) and (B) and the finished agent have in the Interest in a good flowability and trouble-free flushing behave a mean grain size of 0.2 to 1.2 mm, preferably from 0.3 to 1 mm. In particular, the proportion of the particles in the cum with a mean particle size of less than 0,05 mm less than 1  Wt .-%, preferably less than 0.1 wt .-%, the proportion with a grain size less than 0.1 mm less than 2 wt .-%, preferably less than 1 Wt .-%, the proportion with a grain size over 2 mm less than 5 wt .-%, preferably less than 1% by weight and the fraction having a particle size above 1.2 mm less than 10 wt .-%, preferably less than 5 wt .-%. Both Components can be within the specified limits the same or even have a different grain size. By the common mixing and treating with nonionic surfactants may be minor Agglomeration of the particles, in particular by the attachment of finely divided Ingredients to larger grains and thus a total of a minor Increase in mean grain size come.

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

The perborate monohydrate is preferably as loose, bloated Granu lat with a liter weight of 450 to 650 g / l, preferably 500 to 600 g / l used. Such granules are characterized by a good ad sorption capacity for liquid to lard-type nonionic surfactants out. By loading the granules with the nonionic surfactants the bulk density generally increases by about 50 to 200 g / l, which is in the Interest of a higher total bulk weight and a saving in Packaging and transport volume is.

Component (B) also preferably consists of a granular, porous material, such as by spray-drying aqueous slurries of water-insoluble or water-soluble salts or salt mixtures is fair. It contains synthetic zeolite of the type NaA in proportions from 45 to 75, preferably 50 to 72 wt .-% and in particular 55 to 70 Wt .-% (based on anhydrous substance). Also useful are mixtures from zeolite NaA and NaX, wherein the proportion of zeolite NaX in such Mixtures expediently less than 30%, in particular less than 20%. Suitable zeolites do not have particles larger than 30 μm in size  and consist of at least 80% smaller than size particles 10 μm. Their mean particle size (volume distribution, measurement method: Coulter Counter) is in the range of 1 to 10 μm. Your calcium binding capacity, the is determined according to the information of DE 24 12 837, is in the range of 100 to 200 mg CaO / g. The zeolites can still be produced from their preparation contain excess alkali. The water content of synthetic zeolites is usually 18 to 22 wt .-%.

Suitable phyllosilicates belonging to the group of water-swellable Smectite count are z. B. those of the general formula

(OH) ₄ Si _8-y Al _y (M _8x Al _4-x ) O ₂₀
montmorillonite
(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀
hectorite
(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀
saponite
with x = 0 to 4, y = 0 to 2, z = 0 to 6.

In addition, small amounts of iron may be incorporated into the crystal lattice of the phyllosilicates according to the above formulas. Furthermore, the phyllosilicates may contain hydrogen, alkali metal and alkaline earth metal ions, in particular Na ⁺ and Ca ^{+ +} , due to their ion-exchanging properties. The amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or on the type of processing. The particle size is in the range of 0.05 to 25 microns, usually less than 10 microns. Useful sheet silicates are known, for example, from US Pat. No. 3,966,629, US Pat. No. 4,062,647 (DE 23 34 899), EP 26 529 and EP 28 432. Preferably, phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment.

The content of the component (B) of phyllosilicates is preferably 3 to 7% by weight.  

Another advantageous ingredient of component (B) is sodium sulph fat, calculated as anhydrous substance, in proportions from 0 to 30 Wt .-%, preferably from 1 to 25 and in particular from 3 to 20 wt .-% is present. The sodium sulfate contributes to a significant improvement in the Grain structure of the component (B) and the Einspülverhaltens of Add detergent additive while increasing their bulk density, where the possibility of packaging and transport volume arises through it zusparen.

As another inorganic salt, which are combined with the zeolite is sodium carbonate, in proportions up to 20 wt .-%, based on the Component (B) may be present. With regard to the flushing behavior are However, such mixtures under the mixtures of zeolite and sodium sulfate lay.

The content of the component (B) of inorganic salts including Zeo Lith should be at least 75 wt .-%, preferably at least 85 wt .-% (relative to the component B) amount. In addition, component (B) contains or ganic salts, which are of particular advantage for the grain structure, the Grain stability and especially for the Einspülverhalten the granules and whose mixtures are with other detergent ingredients.

These organic salts contained in the component (B) include the sodium or potassium salts, preferably the sodium salts homo polymeric and / or copolymeric carboxylic acids. Suitable homopolymers are Polyacrylic acid, polymethacrylic acid and polymaleic acid, wherein the poly acrylic acid is 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 is not an acid their share is in the interest of sufficient Water solubility not more than 50 mole percent, preferably less than 30 mole percent. Particularly suitable are copolymers of acrylic acid or methacrylic acid with maleic acid, as shown for example in EP 25 551 are characterized in more detail. This is Copo lymerisate containing 40 to 90 wt .-% acrylic acid or methacrylic acid and 60 bis  10 wt .-% maleic acid. Particularly preferred are such copoly in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight Maleic acid are present.

The molecular weight of the homo- or copolymers is in general 2000 to 150 000, preferably 5000 to 100 000. Their share of the Component (B) is, for example, 1 to 12% by weight, preferably 1.5 to 8 wt .-% and in particular 2 to 5 wt .-%, calculated as the sodium salt. With Increasing proportion of polyacid or salts thereof decreases the resistance the grains against abrasion too. With a share from 1.5 wt .-% is already achieved sufficient abrasion resistance for many cases. Optimal Ab rubbing properties have mixtures with 2 to 5 wt .-% of sodium salt of Polyacid on.

In cases where the zeolite in the production of granular Component (B) not in powdery or spray-dried form, but As a wet filter cake is used, it can dispersion Stabilisa contained doors, as they are described in DE 25 27 388 in more detail. Ge suitable stabilizers are, in particular, nonionic surfactants with HLB Values below 12, such as ethoxylated tallow alcohol with 3 to 8 EO. The amount these additives to the powder component (B) may, depending on Zeolithan Part, up to 4 wt .-%, usually 0.3 to 3 wt .-% amount. In the final balance this proportion of component (C) is added.

The difference up to 100 wt .-% is attributable to water, in bound form and as moisture, the majority being bound to the zeolite that is. A proportion of the water, about 8 to 18 wt .-% (based on the Mean) is removable at a drying temperature of 145 ° C. Another proportion, depending on the zeolite content between 4 and 8 wt .-% is at the annealing temperature of about 800 ° C free and corresponds the embedded in the crystal lattice of the zeolite water.

The mean grain size of the component (B) is 0.2 to 1.2 mm, wherein the proportion of grains below 0.05 mm less than 1 wt .-%, preferably less than 0.5 wt .-% and above 2 mm not more than 5 wt .-% amount should. Preferably, at least 80 wt .-%, in particular at least 90  Wt .-% of the grains have a size of 0.1 to 1.2 mm, wherein the proportion of Grains between 0.1 and 0.05 mm, preferably not more than 3 wt%, in particular less than 1 wt .-%, the proportion of grains between 0.1 and 0.2 mm less than 20 wt .-%, in particular less than 10 wt .-% and the Proportion of grains between 1.2 and 2 mm not more than 10 wt .-%, esp especially not more than 5% by weight. The bulk density of the component (B) in the preferred embodiment is 400 to 680 g / L, preferably wise 450 to 650 g / l. By adsorption of nonionic surfactants it also increases by 50 to 200 g / l.

The nonionic adsorbed on the mixture of components (A) and (B) Surfactants are those commonly used in detergents and cleaners be used. Other suitable additives are organic solvents medium, with which the detergency of detergents and cleaners especially against greasy soiling is improved and the incorporated easily in this way a granular detergent can be. But also other substances, such as fragrances, softeners, optical brighteners and anionic or cationic surfactants can after previous dissolution or dispersion in organic solvents or the liquid or molten nonionic surfactants to the mixture of Kom components (A) and (B) are admixed. These substances penetrate together with the solvent or dispersant in the porous grains and are on this way against interactions with other powder constituents ge protects.

Preferred detergent ingredients bound to the granular mixture are and are present together with this as a free-flowing mixture are liquid to pasty nonionic surfactants from the class of polyglycol ether, derived from alcohols having 10 to 22, in particular 12 to 18 C Atoms. These alcohols can be saturated or olefinically unsaturated, li near or in the 2-position methyl branched (oxo radical). Your implementation Products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with difference level of alkoxylation. The number of EO or PO groups corresponds to technical alkoxylates the statistical average.  

Examples of suitable ethoxylated fatty alcohols are C _12-18 -Kokosalkohole having 3 to 12 EO, _C16-18 -Talgalkohol having 4 to 16 EO, oleyl alcohol containing 4 to 12 EO, and obtainable from other native fatty alcohol mixtures corresponding ethoxylation chain and EO-distribution , From the series of ethoxylated oxo alcohols, for example, those of the composition C _12-15 +5 to 10 EO and C ₁₄ -C ₁₅ +5 to 12 EO are suitable. By an increased detergency against both greasy and mineral stains are characterized mixtures of low and high ethoxylated alcohols, such as those of tallow with 3 to 6 EO and tallow with 12 to 16 EO or C _13-15 -oxo with 3 to 5 EO and C _12-14 oxo alcohol with 8 to 12 EO. Particularly favorable Einspüleigenschaften have agents in which the adsorbed nonionic surfactants have both long hydrophobic residues and higher degrees of ethoxylation.

The bulk density of the additives according to the invention is preferably between 600 and 950 g / l, in particular between 650 and 850 g / l.

The advantages of the additives according to the invention are, above all, that they compared to soap-containing additives of the prior art a he increased auto-ignition temperature or a reduced flammability have a comparable Einspülverhalten. Opposite additives of Prior art, the zeolite and (co) polymeric polycarboxylates, but contain neither soap nor phyllosilicates, they indicate depending on the amount of applied nonionic surfactant an analogous to better Autoignition temperature or flammability and a better Flushing behavior on. An additional advantage of these additives exists in that they are more free-flowing than the additives mentioned above State of the art.

In the preparation of component (B) in the preferred embodiment For example, starting from an aqueous mixture containing in total including 40 to 55 wt .-% of anhydrous calculated ingredients, with nozzles sprayed into a downdraft and by means of drying gases, the an inlet temperature of 150 to 280 ° C and an outlet temperature from 50 to 120 ° C, to a removable at 145 ° C moisture content of 8 to 18 wt .-% is dried.  

The aqueous batch can be prepared by mixing the dry or hydrous constituents with the addition of the water required for liquefaction. Instead of 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. An addition of alkali metal hydroxide, in particular NaOH, is also recommended in order to adjust the aqueous zeolite suspension or the slurry alkaline, ie to a pH of at least 8 and provide a sufficient excess of alkali, so that during the spray drying, the pH does not occur less than 8 drops. Such pH lowering, which would lead to a loss of activity of the zeolite Ak, can be effected by CO ₂ in the dry gas. The addition of NaOH, which ensures a sufficient alkali reserve, can for example be up to 3 wt .-%. In general, from 0.2 to 1 wt .-% of.

The content of the aqueous batch of anhydrous In is preferably Ingredients 43 to 50 wt .-%. Its temperature is expediently 50 to 100 ° C and its viscosity 2000 to 20 000 mPa · s, usually 8000 to 14,000 mPa · s. The atomization pressure is usually at 20 to 120 bar, before preferably at 30 to 80 bar. The drying gas, which is generally through Burning of heating gas or fuel oil is obtained preferably in Countercurrent guided. When using so-called drying towers, in which the aqueous batch sprayed in the upper part over several high-pressure nozzles is the input temperature, measured in the ring channel (ie unmit immediately before entering the lower part of the tower) 150 to 280 ° C, before preferably 170 to 250 ° C. Leaving the tower, with moisture be Charged exhaust gas usually has a temperature of 50 to 130 ° C, preferably 55 to 115 ° C. The spray drying is conducted so that the grain size of the spray product the distribution given above having. Existing fine grain and coarse grain is added before Further processing screened. It has been shown that with increasing An Part of the fine grain is the Einspülverhalten with nonionic surfactants impregnated adsorbent deteriorated.

Both powder components are combined to form a homogeneous mixture and then not liquefied with liquid or by heating  treated ionic surfactants or surfactant mixtures. In order to faster Distribution, the nonionic surfactant is expediently moved to the Mixture sprayed on. Heating the nonionic surfactant to tempera temperatures between 35 and 60 ° C, preferably 40 to 50 ° C, accelerates the Adsorption process. The abrasion resistance and dimensional stability of the grains is in compliance with the specified proportions or Herstellungsbedin conditions so high that even the freshly prepared, but especially the cooled and optionally reheated, mature grains under behan the usual spray mixing conditions with the liquid additives delt, mixed and promoted without causing the formation of Fines or coarser agglomerates comes.

The mixing of the two granular components and the subsequent Spraying with nonionic surfactants can be carried out in conventional mechanical Mixing devices, such as drum mixers, fluid bed mixers or Spray mixers are continuous or discontinuous. The mixed And spraying process can also in continuous operation in one single mixing apparatus, the union of the two powder components in a first mixing section and the mixing the nonionic component in a final mixing section he follows. A particular advantage of the invention is the fact that the Adsorption of liquid nonionic surfactants and their diffusion into the Korninnere takes place comparatively quickly. Already shortly after leaving In the mixing apparatus, the grain mixtures have their full flowability and can without intermediate storage or time consuming post-ripening process be further processed.

After application of the nonionic surfactant or optionally Supplied additives, the grains may optionally with fine Particulate powders dusted or surface-coated. hereby the flowability can be further improved and the bulk density ge be increased slightly. Suitable powdering agents have a particle size from 0.001 to the highest 0.1 mm, preferably less than 0.05 mm and may in proportions of 0.03 to 3, preferably 0.05 to 2 wt .-%, applied to the adsorbent loaded with additive become. In question come z. B. finely powdered zeolites, silica airgel  (Aerosil®), colorless or colored pigments, such as titanium dioxide and on dere, already proposed for powdering grains or detergent particles powdered materials such as finely powdered sodium tripolyphosphate, Natri umsulfat, magnesium silicate and carboxymethylcellulose. Both Products according to the invention is such a treatment in general not necessary, especially since the flushability does not improve becomes.

The with the nonionic surfactants or with the mixtures of nichtio nish surfactant and additive impregnated granular adsorbent can with other powdery to granular detergents or washing medium components, as for example by spray drying or Gra are available, or with bleach or with bleach telhaltigen detergents of known composition in any Ratio are mixed. Here is their good flowability as well their high grain stability of great advantage, as an undesirable formation from abrasion and dust is avoided. The powder mixtures are in turn storage stable and do not tend to clump or exudate the nonionic surfactant. In the application they are compared to be knew agents particularly well to be flushed. In contrast to the information in EP 168 102, the admixed spray powders and granules and Natri contain umsulfat, which is often advantageous for the grain properties is, especially in the absence of phosphates. Preferably, too these mixed detergent components therefore phosphate-free. Moreover, it is the absorption capacity of the granule mixture according to the invention for not ionic surfactants so high that an additional application of this Surfactants to other mixture components is unnecessary.

Examples

The additives A1 and A2 according to the invention and the comparative additives V1 to V4 were examined in particular for their combustibility and their tendency to flow. All additives contained 40.9 wt .-% perborate monohydrate having a bulk density of 460 g / l (sieve analysis: greater than 0.8 mm 0%, greater than 0.4 mm 48%, greater than 0.2 mm 47%, greater as 0.1 mm 5%, less than or equal to 0.1 mm 0%). The additives A1, V1 and V2 each contained 34.1. Wt .-% of component (B); the additives A2, V3 and V4 ent held each 46.5 wt .-% of component (B). In the additives A1, V1 and V2, the mixtures of perborate monohydrate and component (B) with 25 wt .-%, based on the sprayed additive, C ₁₂ -C ₁₈ fatty alcohol with 5 EO sprayed; in the additives A2, V3 and V4, the mixtures of perborate monohydrate and component (B) each with 12.6 wt .-%, based on the sprayed additive, C ₁₂ -C ₁₈ fatty alcohol sprayed with 5 EO.

The spray-dried component (B) had the additives in the table indicated composition.

To determine the combustibility in each case 50 g of the additives were on a Clock glass heaped up and with a Bunsenbrennerflamme from above in the angle touched from 45 ° C from 10 cm distance for 10 seconds.

The result shown in Table 2 after switching off the flame was determined visually.  

Table 1: Component (B) in A1 / A2 and V1 / V3 or V2 / V4

Table 2

The flushing behavior of A1 was roughly comparable to the behavior of V1 and better than V2's; the flushing behavior of A2 was comparable with that of V3 and better than that of V4.  

To determine the trickling behavior, 1 liter of the powder was used in one its outlet closed funnel with the following dimensions filled:

Diameter of upper opening | 150 mm Diameter of the lower opening 10 mm Height of the conical funnel area 230 mm Height of the lower cylindrical area 20 mm Tilt angle of the conical area 73 °

The reference substance was dry sea sand with the following grain spectrum selected:

The flow time of the dry sand after release of the outflow opening (51 Seconds) was set at 100%. The flowability of the additives is in%, based on this 100% value.

Claims (7)

1. Granular and phosphate-free additive for detergents and cleaners, containing

• (A) 10 to 70% by weight of sodium perborate monohydrate having a mean particle size of 0.2 to 1.2 mm,
• (B) 25 to 80 wt .-% of a granular, having a mean grain size of 0.2 to 1.2 mm mixture having at least 75 wt .-% of inorganic nature and free of peroxygen and (on anhydrous substance in component B) contains 45 to 75 wt .-% of synthetic fine crystalline zeolite, 0 to 30 wt .-% sodium sulfate and 1 to 12 wt .-% salts of homopolymeric or copolymeric carboxylic acids,
• (C) 5 to 30% by weight of nonionic surfactants bonded to the granular components (A) and (B), characterized in that (B) contains 2 to 10% by weight, based on the anhydrous substance in Component (B) of a layered silicate.

2. Composition according to claim 1, in which the proportion with a grain size below 0.05 mm less than 1 wt .-%, preferably less than 0.1 wt .-%, the Share with a particle size less than 0.1 mm less than 2 wt .-%, before preferably less than 1 wt .-%, the proportion with a grain size above 2 mm less than 5 wt .-%, preferably less than 1 wt .-% and the Share with a grain size over 1.2 mm less than 10 wt .-%, before preferably less than 5 wt .-% is. 3. Composition according to claim 1 or 2, containing 20 to 60 wt .-%, in particular dere 30 to 50 wt .-% of component (A), 35 to 70 wt .-%, in particular dere 40 to 60 wt .-% of component (B) and 7 to 25 wt .-%, esp in particular 10 to 20 wt .-% of component (C).   4. Composition according to one or more of claims 1 to 4, characterized ge indicates that the sodium perborate monohydrate used Bulk weight of 450 to 650 g / l, preferably from 500 to 600 g / l having. 5. Composition according to one or more of claims 1 to 5, characterized ge indicates that the component (B) to 50 to 72 wt .-% (based on anhydrous substance) of synthetic, bound water the, finely divided zeolite, 0 to 30 wt .-% of sodium sulfate, 1.5 to 8 wt .-% of homopolymeric or copolymeric polycarboxylic acids (berech net as the sodium salt) and 3 to 7 wt .-% of a layered silicate and bound water. 6. A process for the preparation of the agent according to one or more of the An Claims 1 to 6, characterized in that a homogeneous, troc kenes mixture of components (A) and (B) with a liquid or by heating liquefied component (B) under simultaneous Mi sprayed. 7. Powdered to granular, phosphate-free to low-phosphate washing medium, characterized by a content of the detergent additive according to one or more of claims 1 to 5.