EP0815196A1

EP0815196A1 - Process for manufacturing a powder washing or cleaning agent

Info

Publication number: EP0815196A1
Application number: EP96906756A
Authority: EP
Inventors: Ansgar Behler; Monika Böcker; Thomas Förster; Manfred Greger; Peter Krings; Amerigo Pastura; Renate Pfennig-Dahmen; Peter Sandkühler
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1995-03-17
Filing date: 1996-03-08
Publication date: 1998-01-07
Anticipated expiration: 2016-03-08
Also published as: DE19509752A1; ATE183230T1; EP0815196B1; DE59602716D1; WO1996029389A1; ES2136391T3

Abstract

The invention concerns the production of compressed washing or cleaning agents of high apparent density: a pre-mixture of washing agent components containing anionic surfactants, non-ionic surfactants, builders, and (optionally) alkalisation agents is produced and compressed; more than 50 wt.% of the non-ionic surfactants are fatty acid alkylester alkoxylates of formula (I): R<1>-CO2-(AO)m-R<2>, (II): R<2>-CO2-(AO)m-R<1> or (III), in which: R<1> stands for a branched or straight-chain, saturated or unsaturated alkyl group with 5-21 carbon atoms; R<2> stands for hydrogen or a straight-chain or branched alkyl group with 1-6 carbon atoms; R<3>, R<4> and R<5> can be identical or different and can stand for hydrogen or the group (a) shown, in which R<6> can be a branched or straight-chain, saturated or unsaturated alkyl group with 5-21 carbon atoms; (a condition is that R<3>, R<4> and R<5> may not all be hydrogen); AO stands for a C2-C4 alkylene oxide unit; m, n, o and p can be identical or different and stand for a number between 1 and 60, preferably 1 and 30, in particular 3 and 12. The process yields washing and cleaning agents of high pouring density and good solubility, without any deterioration in washing power.

Description

Process for the preparation of a powdered washing or cleaning agent

The invention relates to a method for producing solid washing or cleaning agents.

Granular washing or cleaning agents with high bulk densities and high surfactant contents are known and are described, for example, in European patent applications EP 340 013, EP 352 892 and EP 460 925. The agents described in these publications are obtained by granulation processes.

International patent application WO 91/02047 describes a process for the production of compacted granules which can be used in washing or cleaning agents. A homogeneous premix is extruded in the form of a strand with the addition of a plasticizer and / or lubricant at high pressures between 25 and 200 bar. This application teaches that surfactants can be used as plasticizers and / or lubricants. It is possible that the plasticizers and / or lubricants contain limited amounts of auxiliary liquids. These auxiliary liquids also include higher-boiling, optionally polyethoxylated alcohols, polyalkoxylates which flow at room temperature or moderately elevated temperatures and the like.

The washing or cleaning agents produced in the international patent application mentioned above contain anionic and nonionic surfactants as well as optionally soap and other conventional ingredients such as builder substances and optionally alkalizing agents. Alkylbenzenesulfonates and alkylsulfates are mentioned as anionic surfactants. However, alkylbenzenesulfonates have the disadvantage that they are obtained from petrochemical raw materials. Although alkyl sulfates, especially fatty alkyl sulfates, are based on renewable oleochemical raw materials, it is known, on the other hand, that higher amounts, and especially in combination with nonionic surfactants, can lead to unacceptable dissolving and flushing behavior.

In the international patent application WO 93/02176, a method for the production of solid washing or cleaning agents with a high bulk density is proposed, in which one improves the dissolving behavior and to facilitate the Incorporation of the nonionic surfactants uses them in intimate mixing with a structure breaker in a weight ratio of liquid nonionic surfactant: structure breaker of 10: 1 to 1: 2. Polyethylene glycol or polypropylene glycol, their sulfates and / or disulfates, sulfosuccinates and / or disulfosuccinates or mixtures of these can be used as structure breakers.

The international patent application WO 94/13771 describes granular washing or cleaning agents with a bulk density of 700 g / l and above, which contain a high surfactant content and anionic surfactants with good degradation behavior. In order to improve the dissolving and washing-in behavior, it is proposed that the granular detergents and cleaning agents contain 20 to 55% by weight of anionic and nonionic surfactants and optionally including soap, the content of the agents being C 3 -C 4-alcohol sulfates, ethoxylated Alcohol sulfates, α-sulfofatty acid esters and mixtures thereof are above 8% by weight and the weight ratio of these anionic sulfates and / or sulfofatty acid esters to nonionic surfactants should be 10: 1 to 1: 1.25.

Japanese patent application Heisei 6-116599, for example, describes granular detergents with a bulk density of 0.5 to 1.2 g / cm 3. To improve their solubility, the detergents contain fatty acid alkyl ester alkoxylates as nonionic surfactants.

As can be seen from the prior art described above, numerous attempts have been made to increase the solubility of the solid washing or cleaning agents. The increase in the surfactant content as is done in modern detergents, especially when using nonionic surfactants such as ethoxylated fatty alcohols often leads to the solid detergent particles sticking, as a result of which the flowability and the washability are impaired. To improve these properties, the particles are usually coated or powdered. However, this measure can in turn lead to a deterioration in solubility. In addition, some surfactants form a gel phase when dissolved in water or when their solutions are diluted. This gel formation leads to a marked deterioration in both the flushability and the solubility.

Another problem is that solid detergents which contain a surfactant system which give the detergent good solubility and good rinsing behavior in the usual way Household washing machines gives, often show a deteriorated washing power, so that larger amounts of detergents and cleaning agents must be used.

Another goal in the manufacture of detergents or cleaners is to provide detergents with high levels of detergent. In particular, if detergents or cleaning agents with a lower foaming capacity are to be produced, it is possible to add foam inhibitors, but this increases the costs or reduces the surfactant content of the products, but this leads to a considerable loss in washing performance.

The present invention was based on the object of developing a process for the production of solid detergents or cleaning agents with a high bulk density, which show good solubility and good washing-in behavior in conventional household washing machines, with an at least equally good washing power compared to those from the prior art Detergents or cleaning agents known in the art are obtained, and that the solid washing or cleaning agents can be produced as extrudates or tablets with an increased nonionic surfactant content without them sticking.

The present invention relates to a process for the production of pressed detergents or cleaning agents with a high bulk density, in which a premix of detergent constituents containing anionic surfactants, nonionic surfactants, builder substances and, if appropriate, alkalizing agents is produced and compressed, more than 50% by weight of those used Nonionic surfactants are fatty acid alkyl ester alkoxylates with the formulas I, II or III,

R1 CO ₂ - (AO) _m -R2 (I),

R ² -COHAO) _m -R ¹ (II),

CH2 CH CH ₂ ι ι ι ÖD

O O O

wherein

R ^{1 represents} a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms, R ^{2 represents} hydrogen or a straight-chain or branched-chain alkyl group with 1 to

6 carbon atoms,

R3, R ⁴ and R5 may be the same or different and represent hydrogen or O.

O

II 6 6

- C - R, in which R can be a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms, with the proviso that R ³ , R ⁴ and R ^{5 are} not simultaneously hydrogen,

AO stands for a C2-C4 alkylene oxide unit, m, n, o and p can be the same or different and stand for a number from 1 to 60, preferably 1 to 30, in particular 3 to 12.

When carrying out the process according to the invention, extrudates and tablets in particular can be obtained.

For the production of extrudates, a method is preferred in which a premix of detergent components is first prepared. This solid, preferably free-flowing premix is strand-shaped with the addition of a plasticizer and / or lubricant via hole shapes with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar. The strand is cut to the predetermined pellet dimension immediately after exiting the hole shape by means of a cutting device. The application of the high working pressure causes the premix to be plasticized during the formation of the granulate and ensures the cutting ability of the freshly extruded strands. The premix consists at least in part of solid, preferably finely divided, conventional ingredients of detergents and cleaning agents, to which liquid constituents may have been added. The solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these. Subsequently, the liquid ingredients are optionally added and then the plasticizer and / or lubricant selected according to the invention is mixed in. Preferred plasticizers and / or lubricants are aqueous solutions of polymeric polycarboxylates, as well as highly concentrated anionic surfactant pastes and nonionic surfactants. For a detailed description of the process and the suitable ingredients of the Mix and the suitable plasticizer and or lubricant is made to the disclosure of international patent application WO 91/02047.

In a possible embodiment of this process, the liquid nonionic surfactants can also be added to the solid premix as a liquid constituent or as a plasticizer and / or lubricant, or they are part of a solid mixture component of the premix, which solid mixture component can consist of a carrier bead, which has been treated with the nonionic surfactant or an aqueous dispersion of the nonionic surfactant. The liquid component can be added in liquid form at any point in the process, for example in the preparation of the premix, but also in the processing of the plasticized premix, but before it passes through the perforated mold (perforated nozzle plate). Kneaders of any configuration, for example 2-screw kneaders, can preferably be selected as the homogenizing device. The intensive mixing process can in itself lead to a desired temperature increase. Moderately elevated temperatures of, for example, 60 to 70 ° C. are generally not exceeded. In a preferred embodiment, the premix is preferably fed continuously to a 2-screw kneader (extruder), the housing and the extruder granulation head of which are heated to the predetermined extrusion temperature, for example heated to 40 to 60 ^° C. Under the shear action of the extruder screws, the premix is compressed at pressures from 25 to 200 bar, preferably above 30 bar and in particular at pressures from 50 to 180 bar, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally by means of the extrudate a rotating knives preferably reduced in spherical to cylindrical granules. The hole diameter in the perforated nozzle plate and the strand cut length are matched to the selected granule dimension. In this embodiment, the production of granules of an essentially uniformly predeterminable particle size succeeds, wherein in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules with diameters in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from 0.8 to 3 mm. In an important embodiment, the length / diameter ratio of the chopped-off primary granules is in the range from 1: 1 to about 3: 1. It is also preferred to feed the still plastic, moist primary granules to a further shaping processing step; the edges on the raw granules are rounded off so that ultimately spherical or at least approximately spherical granules can be obtained. If desired or necessary, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shaping can be carried out in standard rounding machines, for example in rounders with a rotating base plate. The granules are then preferably fed to a drying step, for example a fluidized bed dryer.

It has been found that extruded granules which contain peroxy compounds as bleaching agents, for example perborate monohydrate, can be dried at supply air temperatures between 80 and 150 ° C. without loss of active oxygen. The free water content of the dried granules is preferably up to about 3% by weight, in particular between 0.1 to 1% by weight. Alternatively, it is also possible to carry out the drying step directly after the extrusion of the primary granules and thus before a final shaping, if desired, in a rounding device. In order to achieve an increased bulk density, it is advantageous if necessary to cover the dried granules again with finely divided dry powders. Examples of such dry powders are again zeolite-NaA powder, but also precipitated or pyrogenic silica, as are commercially available, for example, as Aerosil® or Sipemat (products from Degussa), and mixtures with zeolite. Preference is also given to highly concentrated, at least 90% by weight fatty alcohol sulfate powders which essentially, that is to say at least 90% by weight, consist of particles with a particle size of less than 100 μm.

Tablets can, for example, be produced in such a way that the builder substances, preferably amorphous, partially crystalline and / or crystalline layered sodium silicates and optionally all other constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses, hydraulic presses or rotary presses with pressures in the range of 1 to 300 bar, advantageously in the range from about 5 to 200 bar and in particular between 10 and 150 bar. Preferably, the pressing takes place without the addition of water. In a preferred embodiment, however, the premixes provided for the vaporizing can be prepared by mixing the individual ingredients, which are at least partially present in a pre-assembled form as a granular compound. These include, for example, roll-compacted, crystalline, layered or amorphous sodium disilicates, which may have been impregnated with liquid to wax-like components, for example nonionic surfactants. In particular, this allows free pre-assembly, which is particularly advantageous. In this way, break-resistant tablets with good breaking strength, which dissolve sufficiently quickly under application conditions, are obtained without any problems. The pressing conditions in the respective case are usually to be optimized for the setting of the desired solubility of the tablet with sufficient strength or hardness of the tablet. It applies in a manner known per se that higher compression pressures reduce the solubility of the tablet. Preferred tablets have a breaking strength of at least 55 N and in particular at least 60 N. Tablets with breaking strengths above 150 N are also possible.

Practically all sensible, manageable design forms come into consideration as the spatial form, as long as they meet the requirement that the contact with the tabletting apparatus during the manufacturing process is relatively low. Cylindrical configurations with an oval or circular cross-section of the type specified below are preferred. A tablet produced in this way preferably has a weight of 10 to 120 g, in particular 20 to 100 g, the diameter of the tablets usually being less than 100 mm. Preferred detergent tablets have a maximum diameter of 80 mm and in particular from 30 to 80 mm. However, it is also possible and in particular also preferred with regard to improved solubilities to use several, that is to say at least 2, tablets with the same or different composition. These tablets preferably have a weight of 10 to 40 g, with diameters of 20 to 50 mm being preferred. The diameter / height ratio of the tablets should be optimized in such a way that the least possible abrasion on the vertical walls of the tabletting apparatus (high diameter / low height) is ensured with sufficient stability and a surface that is not too large (small diameter / high height) . Preferred diameter / height ratios of the cylindrical compacts are about 0.5: 1 to 10: 1, in particular 1: 1 to 8: 1.

The fatty acid alkyl ester alkoxylates of the formulas (I) and (II) used in the powdered detergents according to the invention can be prepared by conventional methods, such as, for example, by esterification of fatty acids with alkoxylated lower alkyl alcohols or lower hydroxyalkyl alcohols. The fatty acid alkyl ester alkoxylates of the formulas (I) and (II) can also be prepared by heterogeneously catalyzed direct alkoxylation of fatty acid alkyl esters with alkylene oxide, in particular ethylene oxide. This synthesis method is described in detail in WO 90/13533 and WO 91/15441. The resulting products are characterized by a low OH number, the The reaction is carried out in one step and light-colored products are obtained. Those fatty acid alkyl ester alkoxylates of the formula (I) which are formed by ethoxylation of fatty acid alkyl esters, ie in which AO in the formula (I) for an ethylene oxide unit and R ³ for a short-chain alkyl group having 1 to 6 carbon atoms, in particular for a methyl, Ethyl, propyl or butyl group or their isomers. The fatty acid alkyl esters used as starting materials can be obtained from natural oils and fats, as well as produced synthetically.

The partial glyceride alkoxylates according to formula (III) can be obtained, for example, by alkoxylation of triglycerides in the presence of polyols, here in particular in the presence of glycerol.

Preferably more than 50% by weight of the nonionic surfactants used are used in the form of the ethoxylated fatty acid alkyl esters of the formula (I), methyl C.rCiβ fatty acid esters with 1 to 30 EO and in particular 3 to 12 being particularly preferred. Ethoxylated fatty acid alkyl esters can be introduced into the process in liquid, pasty or solid, compounded form. It is therefore preferred to use a solid compound containing anionic surfactants and ethoxylated fatty acid alkyl esters, and / or a builder-containing solid compound, in particular a silicate-containing compound, which is impregnated with ethoxylated fatty acid alkyl esters.

If the powder detergents according to the invention are to be used to remove lipophilic soiling, preference is given to choosing fatty acid alkyl ester alkoxylates with a low degree of ethoxylation in the range according to the invention; if hydrophilic soiling is to be removed, the use of fatty acid alkyl ester ethoxylates with a higher degree of ethoxylation in the range according to the invention is expedient.

The compounds of the formulas I, II or III can be used alone or in combination with other nonionic surfactants.

As further nonionic surfactants it is also possible to use alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The oligomerization degree x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. The alkyl glycosides are characterized by the fact that they are easily degradable and therefore ecologically harmless.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula IV,

R ⁸

7 '

R -CO-N- [Z] (IV)

7 ⁸ in the R CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 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.

Alkoxylated, advantageously ethoxylated, alcohols can also be used as further nonionic surfactants. The ethoxylated alcohols are derived from primary alcohols with preferably 9 to 18 carbon atoms and have on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. The alcohol radical can be linear or methyl-branched in the 2-position, or contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, e.g. B. from coconut, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, Cg-C- * - (- alcohol with 7 EO, C- | 3-C 35 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C- | 2-C <| 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Ci2-C- _| 4 alcohol with 3 EO and C ^< i2-Ci8 " ^Alkono ' ^m ' ^{t 5} - = 0 * Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to the ethoxylated fatty alcohols mentioned above, those with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO In a preferred embodiment of the present invention, the use of ethoxylated alcohols is dispensed with. The non-ionic surfactants can be present in the finished agent in an amount of 1 to 25% by weight, preferably 2 to 20% by weight. In a preferred embodiment, the finished composition contains compounds of the formulas I, II or III in an amount of 2 to 20% by weight. In a further preferred embodiment, nonionic surfactants are used, of which at least 50% by weight of fatty acid alkyl ester alkoxylates having the formula I and the remainder being alcohols and / or alkyl polyglycosides and / or polyhydroxy fatty acid amides of the general formula IV, the weight ratio of the fatty acid alkyl ester alkoxylates to the alkoxylated alcohols and / or alkyl polyglycosides and / or polyhydroxy fatty acid amides 1: 1 to 9: 1, preferably 1: 1 to 3: 1.

Structure breakers can be used as further components, but they are not necessary in the extrudates according to the invention in order to improve the processability of extrudates. Particularly suitable structure breakers are ethoxylated Cs-C ^ - fatty alcohols with 20 to 45 EO, preferably tallow fatty alcohols with 30 and 40 EO, polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccinates from Poly¬ ethylene glycol or polypropylene glycol or mixtures of these. The nonionic surfactants and the structure breakers can be used in a ratio of nonionic surfactant to structure breaker of 1: 1 to 15: 1.

The washing or cleaning agent prepared by the process of this invention show an improved dissolution rate and an improved dispensing behavior at temperatures between 15 and 60 ^β C and especially between 20 and 45 ° C. In particular, detergents produced by the process according to the invention which contain 15 to 55% by weight, in particular 20 to 55% by weight, of surfactants are preferred.

In addition to the surfactants described above, anionic surfactants can also be present. The anionic surfactants can be selected from the group of the CQ-Ci _β- alkyl sulfates, Cg-Co-alkylbenzenesulfonates, Cβ-C-Jβ-alkanesulfonates, CQ-C- \ Q-alkyl polyglycol ether sulfates, α-olefin sulfonates, Cg-Ci 8-alkyl polyglycol ether sulfonates , Glycerol ether sulfonates, glycerol ether sulfates, hydroxy mixed ether sulfates,

Monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, Ce-Ciβ-fatty acid amide ether sulfates, Cß-i _β- alkyl carboxylates, fatty acid isethionates, N-Ce-C-jβ-acyl sarconisates, N-Ce-Ci _β- acyl taurides and methyl taurides, Ce -Ciβ-alkyl oligoglucoside sulfates, CQ-C <Q- alkyl phosphates, fatty acid soaps and mixtures thereof. Other possible anionic constituents are the so-called disalts, which are obtained by reacting saturated or unsaturated fatty acids based predominantly on natural raw materials by reacting with sulfur trioxide and then converting them to the alkali metal salts, the reaction of saturated fatty acids leading to disalts which are in the α-position are sulfonated, while the conversion of unsaturated fatty acids results in salts which are predominantly sulfonated internally on the formerly double-bonded carbon atoms. These compounds can be easily incorporated into powder detergents. Preferred disalts are derived from fatty acids or fatty acid mixtures, in particular of natural origin, which have a C chain length between 8 and 18 and preferably between 12 and 18.

The anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.

The content of anionic surfactants or anionic surfactant mixtures in the detergents produced according to the invention is preferably 5 to 35, in particular 8 to 30,% by weight. The anionic surfactants can be used in solid form, for example in spray-dried or granulated form, or in liquid to pasty form. Thus, it is preferred to introduce at least some of the anionic surfactants used as plasticizers and / or lubricants into the process in the form of an aqueous surfactant paste.

The nonionic and anionic surfactants can be used in any mixture. In a preferred embodiment, a combination of the compounds of the formulas I and II and optionally further nonionic surfactants and C6-C- | 8-alkyl sulfates and / or Cg-C ^ -alkylbenzenesulfonates and / or monoglyceride sulfates is used.

The powder detergent produced according to the invention can contain conventional builders. The builders can be present in the agent according to the invention in an amount of 10 to 60% by weight, preferably in an amount of 15 to 50% by weight, based on the agent.

For example, finely crystalline, synthetic and bound water-containing zeolite and alkali silicates can be used as builders. A-type or P-type zeolite is preferred as the zeolite. Mixtures of zeolite A or P and X are also suitable, the proportion of the zeolite NaX in such mixtures advantageously being below 30% lies. Suitable zeolites have practically no particles larger than 30 μm and preferably consist at least 80% of particles smaller than 10 μm.

Suitable zeolites have an average particle size of less than 10 μm

(Measurement method: Frauenhofer diffraction; mean volume distribution), preferably between 1.5 and 4.5 μm, in particular between 2.0 and 4.0 μm. you

Calcium binding capacity, which according to the information in German patent application 24 12

837 is determined, is in the range of 100 to 200 mg CaO / g. The fine-particle, in particular crystalline, hydrated zeolite content of the agents is preferably 30 to

65 wt .-% and in particular 32 to 45 wt .-%, based on anhydrous active substance.

The zeolite generally has a water content of 17 to 25% by weight, preferably 18 to 22% by weight, in particular 20 to 22% by weight.

If alkali silicates are used as builders, these are usually added as a solid and not in the form of a solution. They can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na2O: SiO2 molar ratio of 1: 2 to 1: 3.3. Such amorphous alkali silicates are commercially available, for example, under the name Portil (Henkel). Further preferred amorphous silicates are those which can be produced, for example, according to German patent applications 44 00 024, 44 15 362, 44 06 591, 44 06 592 and 44 08 359. Commercially available carbonate-silicate compounds can also be used. As crystalline silicates, which may be present alone or in a mixture with amorphous silicates, crystalline sheet silicates of the formula NaMSiχθ2x + iy H2θ are preferably used, in which M represents sodium, x is a number from 1, 9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 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 Na2Si2θ5 yH2θ are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO91 / 08171. The content of alkali silicates in the compositions is preferably 1 to 15% by weight and in particular 2 to 8% by weight, based on the anhydrous active substance. The weight ratio of zeolite: amorphous silicate, in each case based on anhydrous active substance, is preferably 4: 1 to 10: 1. The crystalline layered silicates are preferably used in amounts of 1 to 15% by weight and in particular 2 to 7% by weight, the weight ratio of zeolite to crystalline layered silicate, in each case based on anhydrous active substance, being at least 5: 1. In agents that contain both amorphous and crystalline alkali silicates the weight ratio of amorphous alkali silicate: crystalline alkali silicate preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1. Such silicates can also serve as carriers for nonionic surfactants.

Polymeric carboxylates or polymeric carboxylic acids may also be present as further builders. These polymeric carboxylates or carboxylic acids can be present in the detergent according to the invention in an amount of 2 to 15% by weight. Polymeric carboxylates or polymeric carboxylic acids with a relative molecular weight of at least 350 in the form of their water-soluble salts, in particular in the form of the sodium and or potassium salts, are considered, such as polyacrylates, polyhydroxyacrylates, polymethacrylates, polymaleates and in particular copolymers of acrylic acid Maleic acid or maleic anhydride, preferably those composed of 50 to 70% acrylic acid and 50 to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers. Vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Instead of the copolymers mentioned, it is also possible to use te polymers or mixtures of copolymers and te polymers. These organic builders can be contained in an amount of 2 to 20% by weight, preferably 5 to 15% by weight, based on the composition. Polymers with more than 2 different monomer units, in particular those that are biodegradable, are also preferably used. Such polymers can be purchased, for example, from Stockhausen (Federal Republic of Germany). Polymers according to patent applications DE-A-43 03 320 and P 44 17 734.6, which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers, are preferably used.

Other useful organic builders are, for example, the polycaΦonic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these this. 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. The detergents produced according to the invention preferably contain peroxy bleaching agents and in particular peroxy bleaching agents in combination with bleach activators. Of the compounds which provide H2O2 in water and which serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-containing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or dipperoxydodecanedioic acid. The detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleaching agent, preferably sodium perborate monohydrate or tetrahydrate being used.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be introduced into the preparations that form organic peracids with H2O2. Examples of these are N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanuric acidides, and also carboxylic acid hydrides , Carboxylic acid esters, especially sodium isononoyloxybenzenesulfonate, and acylated sugar derivatives, especially pentaacetyl glucose. The bleach activator can be coated with coating substances in a known manner or, if necessary with the aid of auxiliaries, granulated or extruded pelletized and, if desired, contain further additives, for example dye. Such granules preferably contain over 70% by weight, in particular from 90% by weight to 99% by weight, of bleach activator. A bleach activator is preferably used which forms peracetic acid under the washing conditions. Among these is tetraacetylethylenediamine (TAED) with average grain sizes of 0.01 to 0.8 mm, granulated with the help of carboxymethyl cellulose, as can be produced by the process described in European Patent EP 037 026, and / or granulated 1, 5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), as can be prepared by the process described in German Patent DD 255 884, is particularly preferred. It can also be extruded TAED are used which> 70 wt .-% TAED, 15 to 25 wt .-% ^c i2-18 ^{"Fettalkonolsu ^_':} ^{at 2 to 6 and} G contains ^β w .-% Soda The content of. Bleichaktivato ^¬ ren in the bleach-containing detergents is in the usual range, preferably between 1 and 10 wt .-% and in particular between 3 and 8 wt .-%. Other suitable ingredients of the agents according to the invention are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof; in particular alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Nβ2θ: S.O2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously 5 and 15% by weight. The sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.

Other detergent components, the proportion of which, depending on the composition of the detergent, is 0.1 to 5% by weight, include foam inhibitors, optical brighteners, enzymes, fabric softening agents, colorants and fragrances. Neutral salts can also be present in an amount of up to 20% by weight, the proportion of which is preferably <10% by weight.

The agent can also contain additional graying inhibitors in an amount of 0.1 to 5% by weight, based on the agent. As additional graying inhibitors, water-soluble colloids, mostly of an organic nature, are suitable, for example soluble starch preparations and z. B. degraded starch, aldehyde starches, etc. Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and polyvinylpyrrolidone are preferably used.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtiiis, Bacillus licheniformis and 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 of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

Suitable foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally signed silica and paraffins, Waxes, microcrystalline waxes and their mixtures with signed silica. Mixtures of different foam inhibitors can also be used with advantage, for example those made from silicone oil, paraffin oil or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

The powder detergents can contain, for example, derivatives of diaminostilbenedisulfonic acid or the alkali metal salts thereof as optical brighteners, which can be readily incorporated into the dispersion. The maximum content of brighteners in the agents according to the invention is 0.5% by weight, preferably from 0.02 to 0.25% by weight.

The salts of polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), are suitable as stabilizers, in particular for per-compounds and enzymes.

The washing or cleaning agents can be produced uniformly from extrudates which have the above-mentioned ingredients. However, the agents can also be obtained from a mixture of several different granules, of which the extrudates according to the invention form the main constituent. For example, the bleach activator, the enzymes, and colorants and fragrances can be subsequently added to the extrudates. It is preferred to use the bleach activator and the enzymes each in compacted granular form, for example as extrudates produced separately, which are obtained by means of a kneader of the configuration described above or via a pellet press.

In a preferred embodiment of the invention, low-foaming detergents or dishwashing detergents are produced, in particular for machine use.

In a further preferred embodiment of the invention, foaming washing or cleaning agents, in particular for manual use, are produced. Examples

Manufacturing

Agents with different fatty acid alkyl ester alkoxylates and anionic surfactants were produced. The comparison formulations contain fatty alcohol derivatives. The basic formulation is shown in Table 1, Table 2 contains the various fatty acid alkyl ester alkoxylates and anionic surfactants as well as the fatty alcohol derivatives used in the comparison formulations.

The compositions with the compositions given in Table 1 were extruded in accordance with the teaching of international patent application WO91 / 02047. The enzyme and the bleach activator in granular form were subsequently added to the extrudate.

Table 1

Component quantity (% by weight)

Anionic surfactant 12.0

Fatty acid alkyl ester alkyloxylate or 13.0 fatty alcohol derivative

Na soap 0.8

Polyethylene glycol (relative molecular weight 2.0 mass 400)

Zeolite A (anhydrous active substance) 28.0

Citrate 3.0 amorphous sodium disilicate 2.0

Sodium perchlorate 20.0

Bleach activator (TAED) 6.0

Protease 1.24

Lipase 1.00

Perfume 0.45

Silicone defoamer 0.6

Water and salts from raw materials ad 100 Table 2

The gel behavior, the solubility and the flushing behavior of the recipes mentioned in Tables 1 and 2 were determined.

Gel behavior

To determine the gel behavior, 25 g of the agent were quickly placed in a 400 ml beaker with 200 ml of water without stirring. Gelation was observed. The amount of gel formed was rated with grades from 0 to 6, the grades being assigned as follows:

1 no gel formation

2 Increase in viscosity without gel formation, which regresses automatically

3 Gel formation, which dissolves after briefly stirring with the glass rod

4 slight gel formation, the gel settles on the edge of the glass and liquefies under finger pressure

5 slight gel formation, the gel settles on the edge of the glass and cannot be liquefied under finger pressure

6 strong gel formation, gel can be pulled out of the water using the glass rod

Determination of the dissolving behavior

In a bowl were (d 16 °) pre-dissolved at a temperature of 30 ^β C for 15 seconds with the hand 32 g of agent in 4 I of water. Then a Nicki sweater was submerged three times, pressed and turned by 90 °. After a minute, the sweater was removed from the soapy water and wrung out. The wash liquor was decanted off, the residues were transferred to a sieve and dried at 40 ° C. The residues are given in% by weight.

The solubility was determined at different grain sizes K:

A: 1.6> K> 1.25 mm

B: 1.25> K> 1.0 mm

C: 1.0>K> 0.8 mm The test results of the gel behavior and the solubility are shown in Table 3. It was found that the solubility depends on the one hand on the grain size, but in particular on the gel behavior of the agents.

Foaming behavior

The foam test was carried out at a temperature of 60 ° C and a water hardness of 16 + 2 ° d. The agent was dosed in a concentration of 45.9 g / l water. The amount of foam formed was rated with grades from 0 to 6, the grades being assigned as follows:

0 no foam

1 foam in the porthole of the washing machine is just visible

3 Half of the washing machine's porthole is covered with foam

5 porthole of the washing machine almost completely covered with foam

6 foaming, ie the foam emerges from the washing machine

Table 3

Induction behavior

To determine the induction behavior of the extrudates, 80 g of the extrudates were placed in the induction channels of the commercial washing machines Elektrolux eco 3, source Privileg 1100 and Miele Novotronic W717 and after a rest period of 1 minute at a pressure of 0.5 bar 12.7 I, 11 , 7 I or 13.1 I water fed. The amount of the remaining residue was weighed out in each case. The value given in Table 4 is the average of these 3 measurements.

Can be rinsed into the induction chamber A Initial value B After 4 weeks storage at room temperature C After 4 weeks storage in the climatic cell at 80% rel. Humidity and 30 ° C

The agents according to the invention all had excellent washability. By using the fatty acid alkyl ester alkoxylates, both the solubility and the flushability of pressed granules (extrudates) have been decisively improved. Analogous results were also obtained for tablets.

Table 4

Washing power

The washing performance was checked under practical conditions in household washing machines. For this purpose, the machines were loaded with 3.0 kg of normally soiled household linen (bed linen, table linen, underwear) and 0.5 kg of test fabric. Strips of standardized cotton fabric (Krefeld laundry research institute), nettle, knitwear (cotton tricot) and terry cloth were used as the test fabric.

Washing conditions: tap water of 23 ° d (equivalent to 230 mg CaO / l), main wash cycle 8.0 g / l at 30 ^β C (heating-up time 60 minutes, 15 minutes at 90 ° C), liquor ratio (kg of laundry: liter of washing solution in Main wash) 1: 4, rinse five times with tap water, spin off and dry. The test fabrics were soiled with grease / pigment. The washing effect is determined by measuring the reflectance. (Measurement of the whiteness: Zeiss reflectometer, 465 nm, suppression of the brightener effect). The experiments were repeated six times each. The specified remission values are the average values over all measurements. The washed test fabric was examined for the residual fat content. The values determined are shown in the following table. This table shows that the greatest amount of fat on the test fabric could be removed with the detergent according to the invention.

The detergency and the foaming behavior of Examples 1 to 6, 9 and 10 were compared with Comparative Examples V1 and V2. The foam behavior was also tested for these examples. The results are shown in Table 5.

A: After manufacturing

B: After 16 weeks of storage in the climatic cell at 80% rel. Humidity and 30 ^β C

Table 5

It is clear from the above test results that the washing power is retained in the formulations according to the invention.

As is known, the foaming behavior can be specifically adjusted, for example, by using other surfactants or the surfactants in other weight ratios. In this way, more foaming agents could be obtained, which were particularly suitable for manual use.

Claims

claims

1. A process for the preparation of pressed detergents or cleaning agents with a high bulk density, in which a premix of detergent constituents containing anionic surfactants, nonionic surfactants, builder substances and, if appropriate, alkalizing agents is prepared and pressed, characterized in that more than 50% by weight of the nonionic surfactants used Fatty acid alkyl ester alkoxylates with the formulas I, II or III,

Rl-CO ₂ - (AO) _m -R2 (I),

R ² -CO ₂ - (AO) _m -R ¹ (II),

CH2 CH CH ₂

I I I (III)

O O O

(AO) _n (AO) ₀ (AO) _p R ³ R ⁴ R ⁵

wherein

R ^{1 is} a branched or straight chain, saturated or unsaturated

Alkyl group having 5 to 21 carbon atoms, R ^{2 is} hydrogen or a straight-chain or branched-chain, saturated or unsaturated alkyl group having 1 to 6 carbon atoms, R ³ , R ⁴ and R5 can be the same or different and can be hydrogen or O

II - C - R®, in which R6 can be a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms, with the proviso that R ³ ,

R ⁴ and R ^{5 are} not simultaneously hydrogen,

AO stands for a C2-C4 alkylene oxide unit, m, n, o and p can be the same or different and stand for a number from 1 to 60.

2. The method according to claim 1, characterized in that m, n, o and p stand for a number between 1 to 30 and in particular between 3 to 12.

3. The method according to claim 1 or 2, characterized in that the pre-mixture with the addition of a plasticizer and or lubricant via hole shapes with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar veφreßt and the strand directly after the exit the hole shape is cut to the predetermined granule dimension by means of a cutting device.

4. The method according to claim 1 or 2, characterized in that the premix is veφreßt to tablets.

5. The method according to any one of claims 1 to 4, characterized in that C ₁₂ - Ciβ fatty acid methyl esters with 1 to 30 EO and in particular with 3 to 12 EO are used.

6. The method according to any one of claims 1 to 5, characterized in that a solid compound containing anionic surfactants and ethoxylated fatty acid methyl ester and / or a builder-containing solid compound, in particular a silicate-containing compound which is impregnated with ethoxylated fatty acid alkyl esters, is used.

7. The method according to any one of claims 1 to 6, characterized in that at least 50 wt .-% of the nonionic surfactants used as fatty acid alkyl ester alkoxylates of the formula (I) and as further nonionic surfactants alkoxylated alcohols and / or alkyl polyglycosides and / or polyhydroxy fatty acid amides used, the weight ratio of the fatty acid alkyl ester alkoxylates to the alkoxylated alcohols and / or alkyl polyglycosides and / or polyhydroxy fatty acid amides being 1: 1 to 9: 1.

8. The method according to any one of claims 1 to 7, characterized in that anionic surfactants are used in solid or liquid to pasty form.

9. The method according to any one of claims 1 to 8, characterized in that one sets a bulk density of the detergent or cleaning agent between 600 and 1000 g / l.

10. The method according to any one of claims 1 to 9, characterized in that a low-foaming detergent or dishwashing detergent, in particular for machine use, is produced.

11. The method according to any one of claims 1 to 9, characterized in that a foaming washing or cleaning agent, in particular for manual use, is produced.