WO1997003181A1

WO1997003181A1 - High bulk density granulated washing or cleaning product

Info

Publication number: WO1997003181A1
Application number: PCT/EP1996/002905
Authority: WO
Inventors: Kathrin Schnepp; Josef Markiefka; Adolf Wiche; Eric Schumacher; Manfred Greger
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-07-12
Filing date: 1996-07-03
Publication date: 1997-01-30
Also published as: ES2153114T3; DE19524722A1; ATE197606T1; DE59606146D1; EP0840780A1; EP0840780B1

Abstract

A high bulk density, granulated washing or cleaning product contains extruded components and at least 15 % by weight anionic and/or non-ionic surfactants. The disclosed product contains at least two different granulated components of which at least one is extruded and at least one is not extruded. The amount of extruded component(s) contained in the product equals 30 to 85 % by weight, in relation to the total product, and the amount of the at least one non-extruded granulated and surfactant-containing component is such that the amount of surfactants contributed to the product by said component equals at least 1 % by weight, in relation to the total product. The extruded component(s) should have as high a bulk density as possible and very stable grains, so that the bulk density of the washing or cleaning product be also as high as possible. For that purpose, an extruded component contains 0 to 35 % by weight surfactants, is free from destructuring agents and non-surfactant organic plasticisers, and has at least 760 g/l bulk density.

Description

"Granular detergent or cleaning agent with high bulk density"

The invention relates to a detergent or cleaning agent composed of several granular components with a high bulk density.

The increasing bulk density of commercial detergent granules is mainly achieved by an increasingly compact grain structure of the granules, whereby the porosity of the granules decreases to an almost complete elimination of the connected pore system. In general, however, the decrease in porosity is also associated with an undesirable delay in dissolution, which in extreme cases can lead to deposits of detergent granules on textiles.

This undesirable delay in dissolution is also caused by the fact that many surfactants, both anionic and nonionic, and especially surfactant mixtures, tend to form gel phases when redissolved in water. Even with surfactant contents of 15% by weight and above, based on the agent, undesirable and dissolving gels can occur when the agents are redissolved in water.

European patent EP-B-0 486 592 discloses granular or extruded washing or cleaning agents with bulk densities above 600 g / l, which contain anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about 35% by weight .-% contain. They are produced by a process in which a solid, free-flowing premix, which contains a plasticizer and / or lubricant, is extruded at high pressures between 25 and 200 bar and the extrudate is extruded onto the extrusion from the hole shape by means of a cutting device predetermined granule size is cut and then rounded using a rounding device. The extrudates produced in this way can be subsequently mixed with other granules, in an advantageous embodiment the proportion of extrudates in the finished washing or cleaning agents is more than 60% by weight. From German patent application DE 41 24 701 it is known that the dissolving speed of extruded agents can be improved by mixing liquid nonionic surfactants in intimate admixture with structural breakers, in particular polyalkylene glycols, their mono- or disulfates and / or sulfosuccinates, for the Extrusion provided premix. However, this measure is not sufficient in all cases in order to increase the dissolving speed of the entire agent. To solve this problem, German patent application 195 19 139 proposes building a washing or cleaning agent with a bulk density above 600 g / l from at least two different granular components, at least one of which is extruded and at least one is not extruded, where the extruded component (s) in amounts from 30% by weight to 85% by weight, based on the total composition in which the composition is (are) present, the content of the extruded component (s) Surfactant is less than 15% by weight and at least one non-extruded granular and surfactant-containing component is contained in the amounts on average that this component contains at least 1% by weight, based on the total agent, of surfactants provided.

In order to achieve the highest possible bulk densities of the entire agent, it is necessary that the individual components, such as, in particular, the granular components and also the fine grain fractions that may be present, already have very high bulk densities.

In this connection it was found that, in particular in the case of the relatively low-surfactant extruded components of the above-mentioned German patent application 195 19 139, the bulk density can only be increased above a value of about 750 g / l if a lower grain stability of the extruded component is purchased want to take. This lower grain stability manifests itself in the fact that when mixed with the other granular components or, in extreme cases, in the rounding step directly after the extrusion, the extruded component disintegrates and - possibly through the loss of its approximately spherical shape to form irregular granules and thus - leads to a reduction in the bulk weight of the entire composition as well as to a deterioration in its pouring and pouring behavior.

The object was therefore to increase the bulk density of the extruded component without loss of grain stability and thus to increase the pourability and pourability of the detergent or cleaning agent consisting of several granular components, as well as its bulk density, without causing any deterioration in the dissolving properties of the agent comes.

Surprisingly, it was found that this problem can be solved by dispensing with structure breakers and non-surfactant organic plasticizers in the premix to be extruded.

The invention accordingly relates to a granular washing or cleaning agent with a bulk density above 600 g / l, comprising an extruded component and anionic and / or nonionic surfactants in amounts of at least 15% by weight, at least two different granular ones Components of which at least one is extruded and at least one is not extruded, the extruded component (s) being contained in amounts of 30 to 85% by weight, based on the total composition, in the composition and at least one non-extruded granular and surfactant-containing component is contained in the amounts on average that this component provides at least 1% by weight, based on the total composition, of surfactants, which is characterized in that the surfactant content of the extruded component (s) is from 0 to less than 35% by weight, in particular from 5% to 24% by weight, based on the particular extruded component, and min at least one extruded component is free from structural breakers and non-surfactant organic plasticizers and has a bulk density of at least 760 g / 1, preferably in the range from 770 g / 1 to 870 g / 1 and in particular in the range from 790 g / 1 to 850 g / 1. The definition of the term “structure breaker” follows from the use of this term used in German patent application DE 41 24 701, with the exception that water is not understood as a structure breaker in the sense of the present invention. However, in the case of the extruded components present here, one is also possible low free water content sought.

Another object of the invention is an extruded preliminary product, suitable for the production of granular detergents and cleaning agents with a bulk density above 600 g / 1, the surfactant content of which is 0 to less than 35% by weight, and which is free of structure breakers and is non-surfactant organic plasticizer and has a bulk density of at least 760 g / 1, preferably in the range from 770 g / 1 to 870 g / 1 and in particular in the range from 790 g / 1 to 850 g / 1.

In the production of the above-mentioned detergents or cleaning agents, in which a mixture of ingredients is extruded, which contains spray-dried mercury component powder (“tower powder”) as already proposed in EP-B-0 486 592, it has been observed that a further improvement The grain stability of the extruded component and a further increase in the bulk density of the finished compositions can be achieved if not all of the inorganic neutral salt, such as sodium chloride and / or sodium sulfate, contained in the premix intended for extrusion is introduced via the tower powder, but instead is at least partly added separately to the premix. Another object of the invention is therefore an extruded preliminary product, suitable for the production of granular detergents and cleaning agents with a bulk density above 600 g / 1, the surfactant content of which is 0 to less than 35% by weight, and which is free from structural breakers and non-surfactants is organic plasticizer and has a bulk density of at least 760 g / 1, preferably in the range from 770 g / 1 to 870 g / 1 and in particular in the range from 790 g / 1 to 850 g / 1, which is preferably by extrusion ¬ sion of a powder mixture containing tower powder is produced and which is characterized in that the inorganic neutral salt contained therein at least partially, preferably in amounts of 10% by weight to 100% by weight, in particular 30% by weight up to 65% by weight, based in each case on the neutral salt content in the extruded product, can be added to the premix by separate admixing. Separate admixing in this context means that the neutral salt is incorporated as a single component, for example as a powder, or as a powdery mixture of several neutral salts and not as a component of granular components that contain other ingredients, for example surfactants. The amounts of neutral salt mixed separately in this way are preferably 1% by weight to 5% by weight, based on the premix to be extruded.

In the context of the description of the washing or cleaning agents according to the invention, extruded components are also counted among the granular components. In cases where it is irrelevant whether a component is extruded or not, the overarching term of the granular component is chosen.

The total surfactant content of the agents, including the soaps, is preferably 15% by weight to 40% by weight and in particular 18% by weight to 30% by weight.

Suitable surfactants in the granular components and in particular in the extruded components are both anionic surfactants and mixtures of anionic and nonionic surfactants. As anionic surfactants of the sulfonate type, preference is given to Co- to C 13-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C ₂ -C 8 -monoolefins with an end or internal double bond by sulfonation gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C ₂ -C alk alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and their salts. So come too sulfated fatty acid glycerol esters into consideration. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of glycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol . Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. The sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with an α-position and / or internal sulfonic acid grouping. Sulphonated fatty acid salts, glyceride sulphates, glycerol sulphates, glycerol and soaps are formed as by-products. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the α-sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ to cig fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cio to C ₂ o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on fatty chemical raw materials. Ci6- to Cιg-alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ciβ- to Ci8-alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower force point and a relative one low washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C ₂ to C ₄ fatty alkyl sulfates or C ₂ to C ₁₈ fatty alkyl sulfates with de to Cig fatty alkyl sulfates or C ₂ to Ci6 fatty alkyl sulfates with Ci6 to C _i8 fatty alkyl sulfates. In a further embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably Ciβ to C ₂₂ are used. Mixtures of saturated sulfated fatty alcohols consisting predominantly of Ci6 and unsaturated sulfated fatty alcohols consisting predominantly of Ciβ are particularly preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol® type (commercial product of the applicant). Weight ratios of alkyl sulfates to alkenyl sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred.

2,3-Alkyl sulfates, which are produced, for example, in accordance with US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂ -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Co-Cπ alcohols with an average of 3.5 mol of ethylene oxide (EO) or Cι ₂ -C ₈ fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cg to Cig fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants as described by unteen. Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is the same possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

The particularly preferred anionic surfactants include alkylbenzenesulfonates and / or straight-chain as well as branched alkylsulfates.

In addition to the synthetic anionic surfactants, soaps are also suitable, preferably in amounts of 0.1 to 5% by weight, based on the total agent. For example, saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2- Position can be methyl branched or can contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ to C ₄ alcohols with 3 EO or 4 EO, C ₉ to C _n alcohols with 7 EO, C ₃ to C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cπ to Cig alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₂ to C ₄ alcohol with 3 EO and C ₂ to Cig alcohol 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, C. -Atoms means and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which reflects the statistical distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably Hegen x at 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkylglycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as are described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533 .

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of such nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them. Other suitable surfactants are fatty acid polyhydroxyamides of the formula (I),

R ³

I.

R ² -CO-N- [Z] (I)

in the R ² CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.

According to the invention, the compositions contain at least 2 different granular components, the only difference of which can be that one component is extruded while the other component was produced by a different process. Advantageously, the extruded component (s) and the non-extruded component (s) also differ in their composition.

In a preferred embodiment of the invention, the compositions contain one or more extruded component (s), the proportion of the extruded component (s) being 50 to 80% by weight, based on the overall composition. It is further preferred that at least one of the extruded components present or, in the event that only one extruded component is present, that the extruded component then contains surfactants, the surfactant content in each extruded component being less than 15% by weight. , in particular not more than 14% by weight and preferably 6 to 13% by weight, in each case based on the extruded component. In a further preferred embodiment of the invention, the compositions contain extruded components containing surfactant in the amounts that thereby provide 0.5 wt.% to 30 wt.%, in particular 6 wt.% to 25 wt.%, based in each case on the total agent, of surfactants.

The extruded components can be produced by any of the known methods. However, a method according to the teaching of European patent EP-B-0486 592 or the teaching of international patent application WO-A-94/09111 is preferred. The size of the almost spherical extrudates thus produced is preferably between 0.8 mm and 2 mm.

The non-extruded granular and surfactant-containing component contains anionic surfactants or a combination of anionic and nonionic surfactants, preferably in amounts of 30 to 95% by weight, based on the non-extruded granular component. It is preferred that the non-extruded granular component contains anionic surfactants, but is largely free of nonionic surfactants. Alkylbenzene sulfonates and / or straight-chain and / or branched alkyl sulfates are advantageously used as anionic surfactants.

The non-extruded granular and surfactant-containing components are preferably contained in the amounts in such a way that they contain 2% by weight to 30% by weight, in particular 5% by weight to 25% by weight. , each based on the total agent, of surfactants.

In a further preferred embodiment of the invention, surfactant-containing extruded components and surfactant-containing non-extruded granular components are used, the weight ratio of surfactant-containing extruded component to non-extruded surfactant-containing granular component being 6: 1 to 2: 1 and in particular 5: 1 to 3 : 1 is

The non-extruded granular component or the further non-extruded granular components, in particular the surfactant-containing components, can have been produced by any of the processes known today, for example by means of spray drying, superheated steam drying, spray neutralization or granulation. Here are anionic surfactants containing granular components preferred, which are obtained by spray re-abstraction according to German patent application DE 44 25 968 or by granulation and optionally simultaneous drying in a fluidized bed according to the teaching of international patent applications WO-A-93/04162 and WO-A-94/18303. For reasons of homogeneity, the grain size distribution of the non-extruded surfactant-containing granules should not be fundamentally different from the grain size distributions of the other components, so that the grain size spectrum is not broadened too much. In particular, according to the teaching of WO-A-93/04162, granules of almost any particle size and particle size distribution can be produced in the fluidized bed. Particularly preferred are therefore non-extruded surfactant-containing granules which are almost spherical and have a particle size distribution which is roughly the same as the particle size distribution of another granular component, for example an enzyme granulate, a foam inhibitor granulate, a bleach activator granulate and in particular an extruded granulate corresponds.

Enzymes which may be present in agents according to the invention are those from the class of proteases, lipases, cutinases, amylases, pullulanases, cellulases, oxidases, peroxidases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active Enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of lipolytic enzymes. The enzymes are preferably adsorbed onto carrier substances and / or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1% by weight to 5% by weight, preferably 0.1% by weight to about 2% by weight.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors include for example, soaps are natural or synthetic origin, ₂₄ a high proportion of CI8 C - have fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular foam and / or paraflfin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance and thus form a further granular component of the agents according to the invention. Mixtures of paraffins and bistearylethylenediamide and mixtures of paraffins and silicones on inorganic carriers are particularly preferred. Granules which contain mixtures of paraffins and silicones in a weight ratio of 1: 1 to 3: 1 are particularly preferred.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose penta- acetate. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239. Particularly preferred bleach activators are N, N, N ', N ^, tetraacetylethylenediamine (TAED), l, 5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN). The content of bleach activators in the bleach-containing agents is in the usual range. In particular, the bleach activators are introduced in granular form, that is to say as a further granular component, in the compositions according to the invention in amounts such that the compositions contain 1 to 10% by weight and preferably 3 to 8% by weight, based in each case on the total composition Bleach activator included.

Further ingredients of the agents according to the invention are preferably inorganic and organic builder substances, bleaching agents, substances which have a positive influence on the oil and fat washability, graying inhibitors, optionally substances which improve the solubility and the dissolving rate of the individual granular components and / or of the entire agent, fabric softening agents, optical brighteners, colorants and fragrances as well as alkaline and / or neutral salts in the form of their sodium and / or potassium salts.

Suitable inorganic builder substance is, for example, fine crystalline, synthetic and bound water-containing zeolite in detergent quality. Zeolite A and / or P and, if appropriate, zeolite X and mixtures of A and X and / or P are particularly suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₂ -C 6 fatty alcohols with 2 to 5 ethylene oxide groups pen, -C ₂ -C ₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotride canoles. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. Zeolites can be contained both in the extruded components and in the non-extruded granular components. Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula

'yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ Os yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171. Crystalline layered sodium silicates can be contained both in the extruded and in the non-extruded granular components. However, they are preferably introduced into the composition in non-extruded granular form.

Amorphous silicates, so-called X-ray amorphous silicates, which in X-ray diffraction experiments do not give sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle, can have secondary washing power own and are used as builder substances. It can even lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size 10 nm to a few hundred nm, values up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Silicates and silicate compounds according to German patent application DE 44 00 024 or silicates and silicate compounds are particularly preferred, for example those which are commercially available under the names Nabion 15® or Britesil® (Akzo-PQ). Spray-dried sodium carbonate-sodium silicate compounds are also particularly preferred, which may additionally contain surfactants, in particular anionic surfactants such as alkylbenzenesulfonates or alkylsulfates, including 2,3-alkyl sulfates. Amorphous silicates and silicate comp Pounds like the silicate-carbonate compounds mentioned can also be contained in the extruded as well as in the non-extruded granular components.

In addition to the alkali metal carbonates or instead of the alkane carbonates, in particular the sodium carbonates, bicarbonates, in particular sodium bicarbonates, may also be present in the compositions. Sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5 is primarily used as amorphous silicate, and preferably from 1: 2 to 1: 3.0 as amorphous silicate with secondary washing ability. The content of sodium carbonate and / or sodium bicarbonate in the agents is preferably up to 20% by weight, advantageously between 5% by weight and 15% by weight. The content of sodium silicate in the compositions is generally up to 30% by weight and preferably between 2% by weight and 25% by weight.

Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000. Terpolymers and quadropolymers are also particularly preferred. For example, those which according to German patent application DE-A-43 00 772 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to German patent DE-C-42 21 381 as monomer salts of acrylic acid and 2- Contain alkylallylsulfonic acid as well as sugar derivatives.

Further suitable builder systems are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110 .

The known polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred builder substances.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

The organic builder substances can be used both in the extruded and in the non-extruded granular components, the use in the extruded component being preferred.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate and sodium percarbonate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10% by weight to 20% by weight, with perborate monohydrate and / or percarbonate advantageously is set. The bleaching agents can be contained both in the extruded and in the non-extruded components of the agent. It is preferred to introduce perborates into the composition via extruded components, while percarbonates are preferably used in the form of almost spherical, non-extruded granules.

In addition, the agents can also contain components which have a positive effect on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid with diols known from the prior art, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalate or anionically and / or nonionically modified derivatives thereof. These substances can be contained both in the extruded and in the non-extruded granular components, their content in the non-extruded granular components being preferred.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch and aldehyde starches. Polyvinyl pyrrolidone can also be used. However, preference is given to cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition. These substances can also be contained both in the extruded and in the non-extruded granular components.

The agents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds which, instead of the morpholino group, contain a diethanolamino group - pe, a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- ( 2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

The above-mentioned further ingredients of the agents according to the invention may also be contained in the agents as fine-grained components. Fine-grained components are understood to mean those which have a particle size of less than 0.2 mm. For reasons of homogeneity and to avoid separations, such fine-grained fractions are however preferably only present in the compositions in amounts not above 10% by weight and in particular not above 5% by weight.

Some fine-grained components can also be used to powder off existing granules, thereby, for example, reducing stickiness of the granules and increasing the bulk densities of the individual granules and also of the entire composition. Suitable surface modifiers of this type are known, for example, from international patent application WO-A-994/01526. In addition to other suitable ones, finely divided zeolites, silicas, which can also be hydrophobicized, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but especially precipitated silica acids, mixtures of zeolite and silica or mixtures of zeolite and calcium stearate are preferred.

The bulk density of the granular detergents or cleaning agents is above 600 g / 1, preferably at least 725 g / 1 and in particular in the range from 745 g / 1 to 950 g / 1. Due to the high proportions of spherical granules, the phenomenon occurs that the density of the granular agent after scooping with a currently commercially available scoop from a commercially available packing, the so-called scooping density, is higher than the initially determined bulk density. The scoop density of the agents preferably lies at values above 790 g / 1, in particular in the range from 800 g / 1 to 820 g / 1. In order to achieve such high densities of the entire composition, it is necessary that the individual and in particular the granular components already have high bulk densities.

Processes in which several subcomponents, at least one of which is extruded, can be mixed with non-extruded granular components, for example spray-dried and / or granulated components, are particularly suitable for producing the agents according to the invention. It is also possible here for spray-dried or granulated components to be subsequently treated, for example with nonionic surfactants, in particular ethoxy-containing fatty alcohols, in the preparation for the ready-to-sell agent by the customary processes. It is also possible and, depending on the recipe, can be advantageous if further individual constituents of the agent, for example carbonates, citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, for example layered crystalline ones Disilicates are added, the proportion of fine-grain fractions on average, that is to say particles with a particle size below 0.2 mm, not above 15% by weight, in particular not above 5% by weight, in each case based on the total composition , Should cherish. Examples

Detergents of the composition given in Table 1 were produced:

Table 1: Composition [% by weight]

1) granules of 85% by weight of the sodium salts of coconut and tallow fatty alcohol sulfate in a weight ratio of 1: 1, 12% by weight of sodium sulfate, the remainder unsulfated and water; produced by granulation and simultaneous drying in the fluidized bed.

The agents listed in Table 1 above (VI, V2, Ml, M2 and M3) each contained an extrudate (VEI, VE2, ME1, ME2 or ME3) prepared according to the teaching of the European patent EP-B-0486592 mentioned from the components ( a) to (f), (1) and (m) in the stated proportions, in each case based on the finished product. Component (k) was used for subsequent powdering of the extruded granules. The granular components (g) to (j) were subsequently mixed in. The tower powders TP1 and TP2 (components a and b) were produced by spray-drying aqueous slurries and consisted of the ingredients listed in Table 2 below in the respective amounts (based on tower powder):

Table 2: Composition [% by weight] of the tower powders

The agents M1, M2 and M3 according to the invention contained no structure breaker and no non-surfactant organic pastifying agent (component e) in the extrudates (ME1, ME2 or ME3).

Table 3 shows the bulk densities of the extruded components VEI, VE2, ME1, ME2 and ME3 as well as the agents VI, V2, MI, M2 and M3 made from them. It can be seen that only in the absence of the non-surfactant plasticizer or structural breaker (component e) can extrudates with high particle stability and high bulk density be produced, which lead to finished compositions with an equally high bulk density. The dissolving behavior of the agents M1, M2 and M3 according to the invention and the comparison agents VI and V2 was good without significant difference.

Table 3: Bulk weights [gΛ]

Claims

claims

1. Extruded preliminary product, suitable for the production of granular detergents and cleaners with a bulk density above 600 g / l, the surfactant content of which is 0 to less than 35% by weight, characterized in that it is free of structure breakers and non-surfactant organic plasticizer and has a bulk density of at least 760 g / 1.

2. An intermediate according to claim 1, characterized in that it has a bulk density in the range from 770 g / 1 to 870 g / 1, in particular in the range from 790 g / 1 to 850 g / 1.

3. An intermediate product according to claim 1 or 2, characterized in that the inorganic neutral salt contained therein, at least in part, preferably in amounts of from 10% by weight to 100% by weight, in particular from 30% by weight to 65% by weight .-%, each based on the neutral salt content in the extruded product, are added to the premix by separate admixing.

4. Pre-product according to claim 3, characterized in that it is manufactured by extrusion of a premix containing powdered tower.

5. Granular washing or cleaning agent with a bulk density above 600 g / 1, containing an extruded component and anionic and / or nonionic surfactants in amounts of at least 15% by weight, at least two different granular components, of which at least one is extruded and at least one is not extruded, the extruded component (s) being present in amounts of 30 to 85% by weight, based on the total composition, in the composition and at least one non- Extruded granular and surfactant-containing component is contained in the amounts on average that this component provides at least 1% by weight, based on the entire composition, of surfactants, characterized in that the content of the extruded component (s) is Surfactants 0 to less than 35 wt .-%, based to the respective extruded component, and at least one extruded component is free from structural breakers and non-surfactant organic plasticizer and has a bulk density of at least 760 g / l.

6. Composition according to claim 5, characterized in that its bulk density is at least 725 g / 1, in particular in the range from 745 g / 1 to 950 g / 1.

7. Composition according to claim 5 or 6, characterized in that non-extruded granular and surfactant-containing components are contained in the amounts in the composition, that thereby 2 wt .-% to 30 wt .-%, preferably 5 wt .-% % to 25 wt .-%, each based on the total agent, of surfactants are provided.

8. Composition according to one of claims 5 to 7, characterized in that the compositions contain extruded components containing tenides in amounts such that 0.5% by weight to 30% by weight, in particular 6% by weight to 25% by weight, based on the total agent, of surfactants are provided.

9. Composition according to one of claims 5 to 8, characterized in that the extruded components, preferably surfactant-containing extruded components, are contained in the total composition to 50% by weight to 80% by weight.

10. Composition according to one of claims 5 to 9, characterized in that the weight ratio of surfactant-containing extruded component to non-extruded surfactant-containing granular component is 6: 1 to 2: 1, in particular 5: 1 to 3: 1.