EP0815196B1 - Process for manufacturing a powder washing or cleaning agent - Google Patents

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

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

Granular washing or cleaning agents with high bulk densities and high Surfactant levels are known and are used, for example, in European countries Patent applications EP 340 013, EP 352 892 and EP 460 925 are described. The one in these Agents described are obtained by granulation.

In the international patent application WO 91/02047 a method for the production described compacted granules used in detergents or cleaning agents can be. A homogeneous premix is added with the addition of a plasticizer. and / or lubricant extruded at high pressures between 25 and 200 bar. This application teaches that surfactants are used as plasticizers and / or lubricants can. It is possible that the plasticizers and / or lubricants are limited Contain quantities of auxiliary liquids. These auxiliary fluids also include higher boiling, optionally polyethoxylated alcohols, at room temperature or moderately elevated temperature flowable polyalkoxylates and the like.

The ones produced in the above-mentioned international patent application Washing or cleaning agents contain anionic and nonionic surfactants as well optionally soap and other common ingredients such as builder substances and optionally alkalizing agents. Alkylbenzenesulfonates and Called alkyl sulfates. However, alkylbenzenesulfonates have the disadvantage that they are made from petrochemicals Basic materials can be obtained. Alkyl sulfates, especially the Fatty alkyl sulfates are based on renewable fat chemical raw materials, however on the other hand, is known to be in 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 detergents or cleaning agents with a high bulk density, which one to improve the dissolution behavior and to facilitate the Incorporation of the nonionic surfactants in intimate mixing with a structure breaker a weight ratio of liquid nonionic surfactant: structure breaker of 10: 1 to 1: 2 starts. Polyethylene glycol or polypropylene glycol can be used as structure breakers. their Sulfates and / or disulfates, sulfosuccinates and / or disulfosuccinates or mixtures out of these are used.

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. To improve the dissolving and washing 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 ₈ -C ₂₂ alcohol sulfates, ethoxylated alcohol sulfates , α-sulfofatty acid esters and mixtures of these is 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.

In Japanese patent application Heisei 6-108099 tablet-shaped Detergent compositions described, the 5 to 50 wt .-% surfactant and 10 to 70% by weight of potassium carbonate and 0.5 to 5% by weight of powdered fragrance preparation contain. Such tablets dissolve, especially if the middle ones Particle diameter of the potassium carbonate are below 150 μm and about 40% by weight Potassium carbonate is used very well.

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 determine the solubility of the solid washing or Increase detergent. The increase in surfactant content as seen in modern Detergents is made, especially when using nonionic Surfactants such as ethoxylated fatty alcohols often leads to this. that the fixed Glue detergent particles together, which makes them free-flowing and easy to rinse deteriorate. To improve these properties, the particles usually coated or powdered. However, this measure can turn to lead to a deterioration in solubility. In addition, some surfactants in the Dissolve in water or dilute their solutions to form a gel phase. This Gel formation leads to a significant deterioration in both the washability and of solubility.

Another problem is that solid detergents containing a surfactant system which good solubility and good rinsing behavior in the usual Domestic 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 use detergents high levels of active detergent. Especially when washing or It is intended to produce cleaning agents with lower foaming power possible to add foam inhibitors, but this increases the cost, or lower the surfactant content of the products, but this leads to a significant loss of Washing performance leads

The present invention was based on the object of a method for producing solid detergents or cleaning agents with a high bulk density to develop the good solubility and good washing-in behavior in conventional household washing machines show, with an at least equally good detergency compared to that of the prior art Technology known washing or cleaning agents is obtained, and that the solid Detergents or cleaning agents as extrudates or tablets with an increased non-ionic surfactant content can be produced without these sticking.

worin

R¹

für eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 5 bis 21 C-Atomen steht,

R²

für Wasserstoff oder eine geradkettige oder verzweigtkettige Alkylgruppe mit 1 bis 6 C-Atomen steht,

R³, R⁴ und R⁵

gleich oder verschieden sein können und für Wasserstoff oder Ø

worin R⁶ eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 5 bis 21 C-Atomen sein kann, mit der Maßgabe, daß R³, R⁴ und R⁵ nicht gleichzeitig Wasserstoff sind, steht,

AO

für eine C₂-C₄-Alkylenoxydeinheit steht,

m, n, o und p

gleich oder verschieden sein können und für eine Zahl von 1 bis 60, vorzugsweise 1 bis 30, insbesondere 3 bis 12, stehen.

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, comprising anionic surfactants, nonionic surfactants, builder substances and optionally alkalizing agents, is prepared and pressed, more than 50% by weight of those used Nonionic surfactants are fatty acid alkyl ester alkoxylates with the formulas I, II or III, R ¹ -CO ₂ - (AO) _m -R ² R ² -CO ₂ - (AO) _m -R ¹

wherein

R ¹

represents a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 carbon atoms,

R ²

represents hydrogen or a straight-chain or branched-chain alkyl group having 1 to 6 C atoms,

R ³ , R ⁴ and R ⁵

can be the same or different and for hydrogen or Ø

in which R ^{6 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

represents a C ₂ -C ₄ alkylene oxide unit,

m, n, o and p

may 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 method according to the invention, in particular Extrudates and tablets can be obtained.

For the production of extrudates, a method is preferred in which a premix is first is made from detergent ingredients. This solid, preferably free-flowing Premix, is with the addition of a plasticizer and / or lubricant over hole forms with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar extruded. The strand is immediately after leaving the Hole shape by means of a cutting device to the predetermined granule dimension tailored. The application of the high working pressure causes the plasticization of the Premix in the formation of granules and provides the cutting ability of the freshly extruded Strands sure. The premix consists at least partly of solid, preferably fine-particle usual ingredients of washing and cleaning agents, which optionally liquid components are mixed. The solid ingredients can Tower powder obtained by spray drying, but also agglomerates, each selected mixture components as pure substances, which are in the finely divided state with one another be mixed, as well as mixtures of these. Following that optionally the liquid ingredients are added and then the invention selected plasticizers and / or lubricants mixed. As a plasticizer and / or Lubricants are aqueous solutions of polymeric polycarboxylates as well highly concentrated anionic surfactant pastes and nonionic surfactants preferred. For detailed Description of the process and the appropriate ingredients of the premix and the appropriate plasticizer and / or lubricant is based on the disclosure the international patent application WO 91/02047.

In a possible embodiment of this method, the liquid nonionic surfactants also as a liquid component or as a plasticizer and / or lubricant be added to the solid premix or they are part of a solid Mixing component of the premix, this solid mixing component consisting of may consist of a carrier bead which is mixed with the nonionic surfactant or an aqueous dispersion of the non-ionic surfactant was applied. The addition of the liquid component in liquid Form can be made at any point in the process, for example during manufacture of the premix, but also when processing the plasticized premix, however, before passing through the perforated shape (perforated nozzle plate). As a homogenizer can preferably kneaders of any configuration, for example 2-screw kneaders to get voted. The intensive mixing process can already lead to a desired increase in temperature. In doing so moderately elevated temperatures of, for example, 60 to 70 ° C usually not exceeded. In a preferred embodiment, the premix is preferred continuously fed to a 2-screw kneader (extruder), its housing and whose extruder pelletizing head is tempered to the predetermined extrusion temperature, for example, are heated to 40 to 60 ° C. Under the shear of the extruder screws the premix at pressures of 25 to 200 bar, preferably above 30 bar and especially compressed at pressures from 50 to 180 bar, plasticized, in shape fine strands through the perforated nozzle plate in the extruder head and finally that Extrudate by means of a rotating knives preferably in spherical to cylindrical granules reduced. The hole diameter in the hole nozzle plate and the strand cut length are matched to the selected granule dimension. In this embodiment, the production of granules in a substantially uniformly predeterminable particle size, with the absolute Particle sizes can be adapted to the intended application. in the particle diameters of up to at most 0.8 cm are generally preferred. Important Embodiments see 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 of 0.8 to 3 mm. The length / diameter ratio of the In an important embodiment, the chopped off primary granulate lies in Range from 1: 1 to about 3: 1. It is further preferred that the still plastic, moist To supply primary granulate to a further shaping processing step; there edges present on the raw granulate are rounded off, so that ultimately spherical or at least approximately spherical granules can be obtained. If Desired or required, small amounts of dry powder, for example zeolite powder, such as zeolite NaA powder, can also be used. This Shaping can be done in standard rounding machines, for example in rounding machines with rotating bottom disc. The granules are then preferably one Drying step, for example a fluidized bed dryer, supplied.

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. Optionally, it is also possible to carry out the drying step directly after the extrusion of the primary granulate 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 back zeolite NaA powder, but also precipitated or pyrogenic silica, as obtainable, for example, as Aerosil ^® or Sipernat ^® (products of Degussa) in trade, and mixtures with zeolite. Preference is also given here 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 prepared in such a way that the Builder substances, preferably amorphous, partially crystalline and / or crystalline layered Sodium silicates and possibly all other ingredients in a mixer mixed together and the mixture using conventional tablet presses For example, eccentric presses, hydraulic presses or rotary presses Pressing pressures in the range from 1 to 300 bar, advantageously in the range from about 5 to 200 bar and in particular between 10 and 150 bar pressed. This is preferably done Compression without the addition of water. In a preferred embodiment However, the premixes intended for compression can be obtained by mixing the individual ingredients, which at least partially in pre-assembled form as granular compound are produced. These include, for example roller-compacted crystalline layered or amorphous sodium disilicates, the optionally with liquid to waxy components, for example have been impregnated with nonionic surfactants. In particular, this makes it water-free Pre-assembly enables, which is particularly advantageous. You get like that Unbreakable without problems and yet sufficiently fast under conditions of use soluble tablets with good breaking strength. The pressing conditions are in each case usually on setting the desired solubility of the tablet at the same time to optimize sufficient strength or hardness of the tablet. It applies in itself known way that higher pressures reduce the solubility of the tablet cause. Preferred tablets have a breaking strength of at least 55 N and in particular from at least 60 N. There are also tablets with tensile strengths above 150 N possible.

Practically all sensible, manageable design forms come in as the spatial form Consider as long as they meet the requirement that contact with the Tableting equipment is relatively small during the manufacturing process. Are preferred here cylindrical configurations with an oval or circular cross section Art specified below. A tablet produced in this way preferably has a weight from 10 to 120 g, in particular from 20 to 100 g, the diameter of the Tablets is usually less than 100 mm. Have preferred detergent tablets a maximum diameter of 80 mm and in particular from 30 to 80 mm. It is however also possible and in particular also with regard to improved solubilities preferred, several, ie at least 2 tablets with the same or different Use 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 so that a as little abrasion as possible on the vertical walls of the tabletting apparatus (higher Diameter / low height) with sufficient stability and not too large Surface (small diameter / high height) is guaranteed. Preferred diameter / height ratios the cylindrical compacts are about 0.5: 1 to 10: 1, especially at 1: 1 to 8: 1.

The fatty acid alkyl ester alkoxylates of the formulas (I) and (II) used in the compressed solid detergents according to the invention can be prepared by conventional methods, 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 process is described in detail in WO-A-90/13533 and WO-A-91/15441. The products which result are distinguished by a low OH number, the reaction is carried out in one stage and light-colored products are obtained. Those fatty acid alkyl ester alkoxylates of the formula (1) 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 or produced synthetically.

The partial glyceride alkoxylates according to formula (III) can, for example, by Alkoxylation of triglycerides in the presence of polyols, here in particular in 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 ₁₂ -C ₁₈ fatty acids with 1 to 30 EO and in particular with 3 to 12 being particularly preferred. Ethoxylated fatty acid alkyl esters can be introduced into the process in liquid, pasty or solid, compounded form. Thus it is 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.

Are the solid detergents produced according to the invention for removing lipophilic Soiling is used, fatty acid alkyl ester alkoxylates are preferred with a low degree of ethoxylation in the range according to the invention; should Removing hydrophilic soiling is the use of Fatty acid alkyl ester ethoxylates with higher ones in the range according to the invention Degree of ethoxylation expedient.

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

As further nonionic surfactants it is also possible to use alkylglycosides of the general formula RO (G) _X , in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization 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.

in der R⁷CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁸ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.Other suitable surfactants are polyhydroxy fatty acid amides of the formula IV,

in which R ⁷ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ⁸ 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 stands.

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 an average of 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, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO. 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 include 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.

In the finished product, the nonionic surfactants can be used in an amount of 1 to 25% by weight, preferably 2 to 20 wt .-% be included. In a preferred embodiment, contains the finished agent compounds with the formulas I, II or III in an amount of 2 to 20 % By weight. In a further preferred embodiment, nonionic surfactants used, of which at least 50% by weight of fatty acid alkyl ester alkoxylates with the Formula I and the remainder alkoxylated alcohols and / or alkyl polyglycosides and / or polyhydroxy fatty acid amides of the general formula IV, the weight ratio of 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 can.

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. Suitable structure breakers are particularly ethoxylated C ₈ -C ₁₈ 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 of polyethylene 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 detergents or cleaning agents produced by the process according to the invention show an improved dissolving speed and an improved induction behavior Temperatures between 15 and 60 ° C and especially between 20 and 45 ° C. In particular, detergents produced by the process according to the invention preferred which contain 15 to 55 wt .-%, in particular 20 to 55 wt .-%, surfactants.

In addition to the surfactants described above, anionic surfactants can also be present. The anionic surfactants can be selected from the group of C ₆ -C ₁₈ alkyl sulfates, C ₉ -C ₁₃ alkyl benzene sulfonates, C ₆ -C ₁₈ alkane sulfonates, C ₆ -C ₁₈ alkyl polyglycol ether sulfates, α-olefin sulfonates, C ₆ -C ₁₈ -Alkylpolyglykolethersulfonate, glycerol ether, Glycerol ether, Hydroxymischethersulfate, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, C ₆ -C ₁₈ -Fettsäureamidethersulfate, C _6-18 alkyl carboxylates, fatty acid isethionates, NC ₆ -C ₁₈ acyl Sarconisate, NC ₆ -C ₁₈ acyl -Taurides and -Methyltaurides, C ₆ -C ₁₈ alkyl oligoglucoside sulfates, C ₆ -C ₁₈ alkyl phosphates, fatty acid soaps and mixtures thereof.

Other possible anionic components are the so-called disalts, which are caused by Implementation of saturated or unsaturated, mainly on natural raw materials based fatty acids by reaction with sulfur trioxide and subsequent Conversion into the alkali metal salts are obtained, the reaction being more saturated Fatty acids leads to disalts which are sulfonated in the α-position, while the reaction is unsaturated Fatty acid disalts results, which are predominantly internal to the formerly double-bound C atoms are sulfonated. These connections work well in Work in powder detergent. Preferred disalts are derived from fatty acids or fatty acid mixtures, in particular of natural origin, which have a C chain length have 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 as well as soluble salts of organic bases, such as mono-, di- or triethanolamine.

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

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 C ₆ -C ₁₈ alkyl sulfates and / or C ₉ -C ₁₃ alkyl benzene sulfonates and / or monoglyceride sulfates is used.

The solid detergent produced according to the invention can be conventional builders contain. The builders can 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, be included.

For example, fine-crystalline, synthetic and bound water can be used as builders containing zeolite and alkali silicates are used. As the zeolite, zeolite is of the A type or preferred of the P type. Mixtures of zeolite A or P and are also suitable X, the proportion of the zeolite NaX in such mixtures expediently below 30% lies. Suitable zeolites have practically no particles larger than 30 µm and preferably consist of at least 80% of particles smaller than 10 microns. Suitable zeolites have an average particle size of less than 10 microns (Measurement method: Frauenhofer diffraction; mean volume distribution), preferred 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 content of funds finely divided, in particular crystalline, hydrated zeolite 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, especially the amorphous sodium silicates, with a Na2O: SiO2 molar ratio of 1: 2 to 1: 3.3. Amorphous alkali metal silicates are available, for example under the name Portil ^® (Henkel) in trade. 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. Crystalline sheet silicates of the formula NaMSi _x O _2x + 1y · H ₂ O, in which M represents sodium, x is a number from 1.9 to 4 and, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates y is a number from 0 to 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 Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in the 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, based in each case 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 compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate: crystalline alkali silicate is 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 can also be used as additional builders be included. These polymeric carboxylates or carboxylic acids can in detergents according to the invention are present in an amount of 2 to 15% by weight. Coming 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, such as polyacrylates, polyhydroxyacrylates, Polymethacrylates, polymaleates and in particular copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those made from 50 to 70% acrylic acid and 50 to 10% maleic acid. The relative molecular weight of the homopolymers is in the generally between 1000 and 100000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid. A special one preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of these Class are copolymers of acrylic acid or methacrylic acid with vinyl ether, such as vinyl methyl ether, Vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Instead of the copolymers mentioned can also Terpolymers or mixtures of copolymers and terpolymers can be used. These organic builders can be used in an amount of 2 to 20% by weight, preferably 5 up to 15% by weight, based on the agent. Polymers with more than 2 various monomer units, especially those that are biodegradable, are preferred. Such polymers can be obtained, for example, from the company Stockhausen (Federal Republic of Germany) can be purchased. Also polymers according to the patent applications DE-A-43 03 320 and P 44 17 734.6, which are monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate contain, are preferably used.

Further usable organic builders are, for example, those preferred in Form of their sodium salts used polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, Nitrilotriacetic acid (NTA), unless such use for ecological reasons objectionable, and mixtures of 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.

The detergents produced according to the invention preferably contain peroxy bleaching agents and in particular peroxy bleaching agents in combination with bleach activators. Among the compounds which serve as bleaching agents and which are H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -containing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid. The detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleaching agent, sodium perborate monohydrate or tetrahydrate preferably being used.

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 which form organic peracids with H ₂ O ₂ . Examples of these are N- or O-acyl compounds, for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanuric acid hydrides, and also carboxylic acid hydrides , Carboxylic acid esters, especially sodium isonanoyloxybenzenesulfonate, 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 tetraacetylethylene diamine (TAED) granulated with carboxymethyl cellulose with average grain sizes from 0.01 to 0.8 mm, 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. Extruded TAED which contains 70 70% by weight of TAED, 15 to 25% by weight of C _12-18 fatty alcohol sulfate and 2 to 6% by weight of soda can also be used. The content of bleach activators in the detergents containing bleach is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.

Other suitable ingredients of the agents according to the invention are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; in particular alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 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.

The other detergent ingredients, the proportion of which depends on the composition of the Detergent is 0.1 to 5% by weight, include foam inhibitors, optical brighteners, Enzymes, fabric softening agents, colors and fragrances. Neutral salts can also be used be contained in an amount up to 20 wt .-%, their proportion is preferably ≤ 10 wt .-%.

The agent can also contain additional graying inhibitors in an amount of 0.1 to 5 % By weight, based on the composition. As additional graying inhibitors are Suitable water-soluble colloids mostly organic, for example soluble Starch preparations and e.g. B. degraded starch, aldehyde starches, etc. carboxymethyl cellulose (Na salt), methyl cellulose, methyl hydroxyethyl cellulose and their mixtures as well Polyvinyl pyrrolidone are preferably used.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus and Humicola insolens obtained enzymatic agents. Preferably are proteases of the subtilisin type and in particular proteases derived from Bacillus lentus are used. Enzyme mixtures are, for example, from Protease and amylase or protease and lipase or protease and cellulase or from Cellulase and lipase or from protease, amylase and lipase or protease, lipase and Cellulase, but especially cellulase-containing mixtures 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, to protect them against premature decomposition. The percentage of enzymes Enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2% by weight.

Suitable 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. With advantage Mixtures of various foam inhibitors can also be used, e.g. such made of silicone oil, paraffin oil or wax. The foam inhibitors are preferably attached to one granular, water-soluble or dispersible carrier substance bound.

The solid detergents produced according to the invention can, for example, derivatives of the optical brighteners Contain diaminostilbenedisulfonic acid or its alkali metal salts, which are good in the Let the dispersion work in. The maximum amount of brightener in the agents according to the invention is 0.5% by weight, amounts of 0.02 are preferred up to 0.25% by weight.

The salts come from as stabilizers, in particular for per-compounds and enzymes Polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP) in Consideration.

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

In a preferred embodiment of the invention, low-foaming Detergents or dishwashing detergents, especially for machine use, manufactured.

In a further preferred embodiment of the invention, foaming Detergents or cleaning agents, especially for manual use.

Examples Manufacturing

There were agents with different fatty acid alkyl ester alkoxylates and anionic surfactants manufactured. The comparison formulations contain fatty alcohol derivatives. The basic recipe is reproduced in Table 1, Table 2 contains the various fatty acid alkyl ester alkoxylates and anionic surfactants and 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. component Quantity (% by weight) Anionic surfactant 12.0 Fatty acid alkyl ester alkyloxylate or fatty alcohol derivative 13.0 Na soap 0.8 Polyethylene glycol (molecular weight 400) 2.0 Zeolite A (anhydrous active substance) 28.0 Citrate 3.0 amorphous sodium disilicate 2.0 Sodium perborate monohydrate 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 Recipe no. Nonionic surfactant Anionic surfactant Fatty alcohol derivative Fatty acid alkyl ester alkoxylate 1 C _12/18 fatty acid _{methyl ester} x 5 EO C _12/18 fatty _alcohol sulfate 2nd C _12/18 fatty acid _{methyl ester} x 4.5 EO " 3rd C _12/18 fatty acid _{methyl ester} x 6 EO " 4th C _12/18 fatty acid _{methyl ester} x 12 EO " 5 C _12/18 fatty acid n-butyl ester x 12 EO " 6 C _16/18 fatty acid methyl ester x 5 EO " 7 C _12/18 fatty acid _{monoglyceride} x 9 EO " 8th Soybean fatty acid triglyceride x 25 EO (double bonds in soybean fatty acid are epoxidized) " V1 (compare) Na-C _12/18 fatty alcohol X 5 EO - " 9 - C _12/18 fatty acid _{ethyl ester} x 12 EO C _11/13 alkylbenzenesulfonate 10th - C _12/18 fatty acid n-butyl ester x 12 EO " V2 (compare) Na-C _12/18 fatty alcohol X 5 EO - "

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

Gel behavior

1 keine Gelbildung

2 Viskositätserhöhung ohne Gelbildung, die sich von selbst zurückbildet

3 Gelbildung, die sich nach kurzem Umrühren mit dem Glasstab auflöst

4 leichte Gelbildung, das Gel setzt sich am Glasrand ab und verflüssigt sich unter Fingerdruck

5 leichte Gelbildung, das Gel setzt sich am Glasrand ab und läßt sich unter Fingerdruck nicht verflüssigen

6 starke Gelbildung, Gel läßt sich am Glasstab aus dem Wasser ziehen

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, 32 g of the agent in 4 l of water (16 ° d) at a temperature of 30 ° C for 15 seconds by hand. Then a nicki sweater was made three times submerged, pressed and rotated by 90 °. After a minute the sweater was off the wash liquor removed and wrung out. The wash liquor was decanted, the Residues transferred to a sieve and dried at 40 ° C. The residues are in % By weight.

A: 1,6 > K > 1,25 mm

B: 1,25 > K > 1,0 mm

C: 1,0 > K > 0,8 mm

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 in Table 3 play. It was found that the solubility depends on the size of the grain, on the one hand depends in particular on the gel behavior of the agents.

Foaming behavior

0 kein Schaum

1 Schaum im Bullauge der Waschmaschine gerade sichtbar

3 Bullauge der Waschmaschine bis zur Hälfte mit Schaum bedeckt

5 Bullauge der Waschmaschine nahezu vollständig mit Schaum bedeckt

6 Überschäumen, d.h. Austreten des Schaums aus der Waschmaschine

Rezeptur- Nr. Gelverhalten Löslichkeit A B C 1 1,5 15 10 6 2 1,5 11 5 5 3 1,5 10 6 4 4 2 9 3 4 5 1 6 2 2 6 2,5 7 3 2 7 2,5 20 12 7 8 1 11 5 2 V1 6 32 24 14 9 2 10 5 5 10 1 7 2 1 V2 6 25 14 7 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 foam escaping from the washing machine

Recipe no. Gel behavior solubility A B C. 1 1.5 15 10th 6 2nd 1.5 11 5 5 3rd 1.5 10th 6 4th 4th 2nd 9 3rd 4th 5 1 6 2nd 2nd 6 2.5 7 3rd 2nd 7 2.5 20th 12th 7 8th 1 11 5 2nd V1 6 32 24th 14 9 2nd 10th 5 5 10th 1 7 2nd 1 V2 6 25th 14 7

Induction behavior

To determine the flushing behavior of the extrudates, 80 g of the extrudates were placed in the Dishwashing troughs of the standard Elektrolux Öko 3 washing machines, Privilege source 1100 and Miele Novotronic W717 and after a rest period of 1 minute a pressure of 0.5 bar 12.7 l, 11.7 l or 13.1 l of water. The amount of the remaining residue was then balanced. The one in Table 4 The value given is the average value from these 3 measurements.

Washability in the wash-in chamber:

A: Initial value

B: After 4 weeks storage at room temperature

C: After 4 weeks of 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 compressed granules (extrudates) have been decisively improved. Analogous results were also obtained for tablets. Recipe no Washability . A B C. 1 3rd 0.5 1 2nd 4th 2nd 2nd 3rd 5 3rd 2nd 4th 7 7 5 5 3rd 2nd 1 6 4th 3rd 1 7 3rd 0.5 0.5 8th 5 4th 2nd V1 23 23 24th 9 5 3rd 2nd 10th 4th 3rd 2nd V2 19th 15 16

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 ° C (heating up time 60 minutes, 15 minutes at 90 ° C), liquor ratio (kg of laundry: liters of wash water in the main wash cycle) 1: 4, rinse five times with tap water, draining and drying.

The test fabrics were soiled with grease / pigment. The washing effect is determined by measuring the remission. (Measurement of whiteness: Zeiss reflectometer, 465 nm, suppression of the brightener effect). The trials were each repeated six times. The specified remission values are the Average values across all measurements. The washed test fabric was placed on the Residual fat content examined. The determined values are in the following table reproduced. This table shows that with the invention Detergent the largest amount of fat on the test fabric could be removed.

A: Nach Herstellung

B: Nach 16 Wochen Lagerung in der Klimazelle bei 80 % rel. Luftfeuchtigkeit und 30°C Rezeptur- Nr. Waschkraft Schaumverhalten A B A B 1 62 63 0 0 2 60 62 0 0 3 62 60 0,1 0 4 61 60 0,2 0,2 5 62 62 0,1 0,1 6 60 61 0 0 V1 61 61 4,5 4,5 9 61 60 0,2 0,2 10 62 61 0,1 0,1 V2 61 61 4,5 4,5

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 ° C Recipe no. Washing power Foaming behavior A B A B 1 62 63 0 0 2nd 60 62 0 0 3rd 62 60 0.1 0 4th 61 60 0.2 0.2 5 62 62 0.1 0.1 6 60 61 0 0 V1 61 61 4.5 4.5 9 61 60 0.2 0.2 10th 62 61 0.1 0.1 V2 61 61 4.5 4.5

From the above test results it is clear that in the inventive Recipes that maintain washing power.

As is known, the foaming behavior can be achieved, for example, by using others Surfactants or the surfactants in other weight ratios can be set specifically. In this way, more foaming agents could be obtained especially suitable for manual use.

Claims (11)

1. A process for the production of moulded detergents of high bulk density in which a compound of detergent ingredients containing anionic surfactants, nonionic surfactants, builders and optionally alkalizing agents is prepared and moulded, characterized in that more than 50% by weight of the nonionic surfactants used are fatty acid alkyl ester alkoxylates corresponding to formula I, II or III: R¹-CO₂-(AO)_m-R² R²-CO₂-(AO)_m-R¹

   

   in which

   R¹ is a linear or branched, saturated or unsaturated alkyl group containing 5 to 21 carbon atoms,

   R² represents hydrogen or a linear or branched, saturated or unsaturated alkyl group containing 1 to 6 carbon atoms,

   R³, R⁴ and R⁵ may the same or different and represent hydrogen or

   

   where R⁶ may be a linear or branched, saturated or unsaturated alkyl group containing 5 to 21 carbon atoms,

   with the proviso that R³, R⁴ and R⁵ are not all hydrogen,

   AO is a C_2-4 alkylene oxide unit,

   m,n,o and p may be the same or different and represent a number of 1 to 60.
2. A process as claimed in claim 1, characterized in that m, n, o and p stand for a number between 1 and 30 and, more particularly, for a number between 3 and 12.
3. A process as claimed in claim 1 or 2, characterized in that the compound is extruded under high pressures of 25 to 200 bar into strand form through multiple-bore dies with bore diameters corresponding to the predetermined granule size, extrusion being carried out in the presence of a plasticizer and/or lubricant, and immediately after leaving the extrusion die the strand is cut by a cutting unit into granules of the predetermined size.
4. A process as claimed in claim 1 or 2, characterized in that the compound is tabletted.
5. A process as claimed in any of claims 1 to 4, characterized in that C_12-18 fatty acid methyl esters containing 1 to 30 EO and, more particularly, 3 to 12 EO are used.
6. A process as claimed in any of claims 1 to 5, characterized in that a solid compound containing anionic surfactants and ethoxylated fatty acid methyl esters and/or a builder-containing solid compound, more particularly a silicate-containing compound, impregnated with ethoxylated fatty acid alkyl esters is used.
7. A process as claimed in any of claims 1 to 6, characterized in that at least 50% by weight of the nonionic surfactants used are used as fatty acid alkyl ester alkoxylates of formula (I) and alkoxylated alcohols and/or alkyl polyglycosides and/or polyhydroxyfatty acid amides are used as further nonionic surfactants, the ratio by weight 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. A process as claimed in any of claims 1 to 7, characterized in that anionic surfactants in solid or liquid to paste-like form are used.
9. A process as claimed in any of claims 1 to 8, characterized in that the detergents are adjusted to a bulk density of 600 to 1,000 g/l.
10. A process as claimed in any of claims 1 to 9, characterized in that a low-foaming laundry or dishwashing detergent, more particularly for use in machines, is produced.
11. A process as claimed in any of claims 1 to 9, characterized in that a foaming laundry or dishwashing detergent, more particularly for manual use, is produced.