EP0705330A1

EP0705330A1 - Method of producing extrudates with washing or cleaning properties

Info

Publication number: EP0705330A1
Application number: EP94920447A
Authority: EP
Inventors: Kathrin Schnepp; Wolfgang Seiter; Bernd Larson; Manfred Greger; Hubert Pawelczyk
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1993-06-21
Filing date: 1994-06-13
Publication date: 1996-04-10
Also published as: DE4320358A1; WO1995000629A1

Abstract

The invention concerns the production of extrudates with improved dispersing power by the extrusion of a solid mixture containing a plastifier and/or lubricant to produce a continuous extrusion which, on emerging from the die, is chopped by a cutting device to the required granule size. The extrudates produced have improved dispersing power if amorphous silicates are included in the solid mixture, the silicates being incorporated in the mixture (a) at least partly as solid components, water or aqueous solutions being used as plastifiers and/or lubricants, or (b) at least partly as plastifiers and/or lubricants in the form of an aqueous solution. Alternative (b) is that preferred for the method. The silicates also improve the granule stability of the extrudates.

Description

"Process for the production of wash- or clean-unoactive extrudates"

The invention relates to a method for producing washable or cleaning-active extrudates with high density.

From the international patent application WO-A-91/02047 a process for the production of extrudates is known, wherein a solid premix is extruded under pressure and the strand is cut to the predetermined granule size after exiting the hole shape by means of a cutting device. The solid and free-flowing premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers, which are preferably used in liquid, paste-like or gel-like preparation form. The premix can also contain powders and / or granules, the granules being obtained, inter alia, by granulation processes or also by conventional spray drying processes. After exiting the hole shape, the system no longer has any shear forces and the viscosity of the system is reduced in such a way that the extruded strand can be cut to predeterminable extrudate dimensions. For example, an extruder is known from international patent application WO-A-91/13678 which can be used to carry out this method.

It is generally known from the prior art that the joint processing of zeolite and amorphous silicates in conventional spray drying processes leads to undesired interactions. For example, European patent application EP-A-0 240 356 describes that this procedure results in agglomerates which are difficult to redisperse. The spray-dried products therefore have not only a poor washing performance but also a high level of hardness and their suction capacity is reduced.

The object of the invention was to provide a process for the production of extrudates which are active in washing or cleaning and which have improved redispersibility and which additionally allows zeolite and amorphous silicon to process likate. The extrudates should have improved redispersion behavior even when a premix is used which contains at least one spray-dried component.

The invention accordingly relates to a method for producing washable or cleaning-active extrudates with high density, wherein a solid premix, which contains a plasticizer and / or lubricant, is extruded under pressure, the strand after exiting the hole shape by means of a cutting device onto the predetermined granule dimension cut and amorphous silicates are used in the solid premix, either

(a) the amorphous silicates at least partially as a solid component and as a plasticizer and / or lubricant, water or aqueous solutions or

(b) the amorphous silicates are used at least partially in the form of an aqueous solution as plasticizers and / or lubricants.

To explain the actual extrusion process, reference is expressly made to the applications WO-A-91/02047, WO-A-93/02176 and to the older German patent application P 42 35 646.6. In a preferred embodiment of the invention, the premix is preferably continuously fed to a 2-screw extruder with a co-rotating or counter-rotating screw guide, the housing and the extruder granulating head of which can be heated to the predetermined extrusion temperature. Under the action of the shear of the extruder screws, the premix is compressed, plasticized, and extruded in the form of fine strands through the perforated die plate in the extruder head under pressure, which is preferably at least 25 bar, but can also be below this at extremely high throughputs depending on the apparatus used and finally the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating cutting knife. The hole diameter of 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, the absolute particle size large can be adapted to the intended purpose. In general, particle diameters of up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. In an important embodiment, the length / diameter ratio of the chipped primary granules is in the range from about 1: 1 to about 3: 1. Furthermore, it is preferred to feed the still plastic and moist primary granulate to a further shaping processing step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this stage. This shape can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. The extrudates are then preferably fed to a drying step, for example a fluidized bed dryer. The extruded granules, which contain peroxy bleaching agents, for example perborate monohydrate, can be dried at supply air temperatures between 80 and 150 ° C. without loss of active oxygen. Optionally, it is also possible to carry out the drying step directly after the extrusion of the crude extrudate and thus before a final shaping, if desired, in a rounding device.

The amorphous silicates used in accordance with the invention are preferably amorphous alkali silicates such as sodium silicates and potassium silicates, especially sodium silicates, with a molar ratio of metal oxide to silicon dioxide of 1: 1 to 1: 4.5, preferably of 1: 1.9 to 1: 4.0 and especially from 1: 2 to 1: 3.5. The content of the extrudates in amorphous alkali likates, in particular in sodium silicates, is generally up to 10% by weight and preferably between 2 and 8% by weight. The amorphous silicates are preferably introduced into the extrusion process at least in part in the form of an aqueous solution. In the process, these solutions serve as plasticizers and / or lubricants. The concentration of the aqueous solutions of amorphous silicates can vary over a wide range. In the course of the extrusion process, however, it is preferred to use aqueous solutions use which have an amorphous silicate content of between 10 and 45% by weight, in particular between 20 and 40% by weight. However, amorphous silicates can also be used in addition or even exclusively in solid form as an admixture component to at least one further solid. Here, for example, granular or powdery, in particular spray-dried, water glasses come into consideration. In addition, they can also be part of a granular component which contains various, preferably customary, ingredients of washing or cleaning agents. This granular component - if it contains silicates in amounts above 3% by weight - is essentially free of zeolite, ie it contains not more than 5% by weight, preferably not more than 3% by weight, of zeolite (based on anhydrous Active substance) and in particular contains no zeolite at all. If the amorphous silicates are introduced into the process as solid admixture components, water is a preferred plasticizer and / or lubricant. In a preferred embodiment of the invention, amorphous silicates are used in the form of an aqueous solution and additionally as a solid powdery or granular admixture component in the solid premix. In the context of this invention, “amorphous” silicates are also taken to mean those X-ray amorphous silicates as are described in the older German patent application P 4400024.3. These silicates are particularly suitable as powdery or granular admixture components. In a particularly preferred embodiment of the invention, however, amorphous silicates are only introduced into the extrusion process in the form of an aqueous solution as plasticizers and / or lubricants. The silicates not only improve the redispersion behavior of the extrudates, they also contribute to the stability of the extrudate.

The solids contained in the premix can be introduced into the process as powdered raw materials. However, it is preferred that at least one granular component, which was produced by granulation, extrusion or conventional spray drying, is used for the production of the premix. It can be particularly advantageous if the premix contains at least one spray-dried component, which zeolite, preferably in substantial amounts, ie in amounts above 10% by weight (calculated as anhydrous active Substance), based on the component contains. Because of the known negative interactions of zeolite and amorphous silicates in a spray drying process, components are preferred which do not contain amorphous silicates in amounts above 3% by weight, preferably in amounts up to 1% by weight and in particular no amorphous ones Contain silicates. The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder as a solid admixture. However, it is preferred that it is used in the spray-dried component mentioned which also contains other ingredients. In the production of this component, the zeolite is used in particular as a suspension which contains small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22,% by weight of bound water. The zeolite is preferably introduced into the process in the form of this finely divided powder or in the form of a granular component which can be granulated or spray-dried.

Further ingredients of the granular component (s) and in particular of the spray-dried component (s) mentioned are, for example, anionic sides, further builders such as phosphates, crystalline layer silicates, polycarboxylates and (co) polymeric polycarboxylates, alkali metal carbonates, in particular sodium carbonate, optical brighteners and / or other inorganic salts. A spray-dried component is preferred which contains polymeric polycarboxylates in amounts of 1 to 5% by weight and in particular in amounts of 2 to 4% by weight, based in each case on the spray-dried component.

In a further embodiment of the invention, at least one further plasticizer and / or lubricant is used in the solid premix in addition to the aqueous silicate solutions. Which plasticizing and / or lubricants can be considered here, is already known from international applications W0-A-91/02047 and W0-A-93/02176. In particular, liquid surfactants or liquid surfactant mixtures and / or aqueous polymeric polycarboxylate solutions are used as further plasticizers and / or lubricants in the context of this invention. However, it is particularly preferred that no polymeric polycarboxylates in the form of an aqueous solution are introduced into the process as plasticizers and / or lubricants if the premix has zeolite and / or amorphous silicates as solid admixing components.

The components used in the premix in addition to zeolite and amorphous silicates are for the most part the usual ingredients of detergents or cleaning agents. These include, in particular, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and zwitterionic surfactants, as well as other builder substances, alkaline salts, bleaching agents, graying inhibitors, foam inhibitors, optical brighteners and enzymes. It is particularly advantageous if premixes are prepared which contain 30 to 60% by weight, preferably 35 to 50% by weight, in each case based on anhydrous active substance, zeolite in detergent quality, 0.5 to 10% by weight and above ¬ preferably 1 to 5 wt .-% amorphous silicates and 5 to 40 wt .-%, preferably 10 to 30 wt .-% surfactants. Weight ratios of anionic surfactants to nonionic surfactants of 10: 1 to 1: 5 are preferred. Amounts of 5 to 15% by weight of anionic surfactants and 5 to 15% by weight of nonionic surfactants are particularly preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates as well as disulfonates, such as are obtained, for example, from Ci2-Ci8 * monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates) are also suitable, for example the α-sulfonated methyl esters of the hydrogenated ten coconut, palm kernel or tallow fatty acids and their salts. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or by the esterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. The salts of alkylsulfosuccinic acid can also be used.

Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. The alk (en) yl sulfates are the sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the Cιo-C2θ "0 ^χoa crude oils, and those sekun¬ Preferred alcohols of this chain length are further preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials Ci6-Ci8-Alk (en) yl sulfates are particularly preferred, but it can also be particularly advantageous and particularly advantageous for machine washing agents to use Ci6-Ci8-alk (en) yl sulfates in combination with lower-melting anionic surfactants and in particular with such anionic surfactants which have a lower Krafft point and at relatively low washing temperatures of for example, room temperature to 40 ° C show a low tendency to crystallize. In a preferred embodiment of the invention, the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C8-Cis-alkyl sulfates, in particular Cβ-alkyl sulfate, Ci2-alkyl sulfate or C 2 ~ Ciβ-alkyl sulfate mixtures with high proportions of Ci2 Alkyl sulfate in combination with Ci6-Ci8-fatty alkyl sulfates. It is particularly advantageous that these alkyl sulfates are again in the form of a spray-dried, spray-neutralized, granulated or granulated and, at the same time, dried. Compounds are used. Compounds are preferred which contain C 1 -C 2 -alkyl sulfate and alkali carbonate, in particular sodium carbonate, and optionally alkoxylated alcohols having 10 to 40 ethylene oxide groups (EO) as the carrier material for the alkyl sulfate.

In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably Cβ to C22 are used. Mixtures of saturated, predominantly C 6 -sulfonated fatty alcohols and unsaturated, predominantly C 18 -sulfonated fatty alcohols are particularly preferred, for example those which are derived from solid or liquid HD-Ocenol ( ^R ) fatty alcohol mixtures (commercial product of the applicant) deduce. Weight ratios of alkyl sulfates to alkenyl sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred.

The sulfuric acid monoesters of the straight-chain or branched C7 ~ C2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (E0) or Ci2-Ci8 -Fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of up to 4% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-C24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.

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

The nonionic surfactants used are preferably alkoxylated, advantageously liquid ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 40 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2 Position can be methyl-branched, or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 C atoms are preferred, e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values which can be an integer or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). Other preferred nonionic surfactants are, in particular, tallow fatty alcohols with 11 EO, 14 EO or 25 EO. It has been shown that these nonionic surfactants can also be granulated or spray-dried together with anionic surfactants and thus lead to improved application properties of the finished extrudates. According to the teaching of international application WO-A-93/02176, in addition to the alkoxylated alcohols mentioned, alkoxylated alcohols with up to 80 EO, preferably tallow fatty alcohol with 40 E0, or polyethylene glycols, preferably with a relative molecular weight between 200 and 600, can also be used in mi ¬ be used with other nonionic surfactants. In the context of this invention, however, it is preferred to introduce alkoxylated alcohols with 10 to 40 E0 in the form of a solid preparation into the premix, particularly preferably if the premix contains alk (en) yl sulfates.

In addition, alkyl glycosides of the general formula R0 (G) _x in which R is a primary non-ionic surfactant can also be used. Radkettigen or methyl branched, in particular in the 2-position 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 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 can be present in the premix in amounts of, for example, 1 to 5% by weight.

Another class of usable nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP-A-58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them. Other suitable surfactants which can replace alkyl glycosides or can be used in combination with them are polyhydroxy fatty acid amides of the formula (I),

R3

I.

R ² -C0-N- [Z] (I)

in which R ^{2 is} C0 for an aliphatic acyl radical with 6 to 22 carbon atoms, R3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid iden are known Substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798, as well as international patent application WO 92/06984.

In addition to the zeolite already mentioned, the builders may include phosphates, preferably in amounts not exceeding 15% by weight, and in particular crystalline, layered sodium silicates of the general formula (II) NaMS _x θ2χ + ι ^, yH2θ, where M is sodium or hydrogen means x is a number from 1.9 to 4 and 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 EP-A-0 164 514. Preferred crystalline layered silicates of the formula (II) are those in which M is sodium and x is 2 or 3. In particular, ^{'Na2Si2θ5-sodium} * yH2θ both .beta.- and δ preferred.

Layered silicates which are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405 are also suitable. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonite, are preferred here.

Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures 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 thereof, preferably in amounts of 2 to 10% by weight and in particular in amounts of 3 to 8% by weight. . Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 20 to 55% by weight. % aqueous solutions are preferred. Also particularly preferred are biodegradable terpolymers, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0280 223 . Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable ingredients of the premix are water-soluble inorganic, in particular alkaline, salts such as bicarbonates and carbonates. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. Alkali carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group having amino acids and / or their salts. In the context of this invention, it is entirely possible for the alkali metal carbonates to be partially or completely replaced by glycine or glycinate. Among the compounds which serve as bleaching agents and supply H2O2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the premix is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations. Examples of this are N-acyl or 0-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose sepentaacetate. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacety1-2,4-dioxo-hexahydro-1,3,5-triazine.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8-C24 fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred. Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Of particular interest here are enzyme mixtures, for example of protease and aylase 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 . (Per) oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in Hü11 substances 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.

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

It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) "" d, pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.

In addition, the agents can also contain components which have a positive effect on the ability to wash off fat and fat from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether, and the Polymers of phthalic acid and / or terephthalic acid or, respectively, known from the prior art. of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl ethyl 11, methyl hydroxypropyl ethyl 11, methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the extrudates, are preferred. used.

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanola ino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. It has been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight. %, also small amounts, for example 10 ~ 6 to 10 ^-3 wt .-%, preferably around 10 ~ 5 wt .-%, of a blue dye. A particularly preferred dye is Tinoluχ ( ^R ) (commercial product from Ciba-Geigy).

The finished washing or cleaning agents can be built up uniformly from extrudates which have the above-mentioned ingredients. In a further embodiment of the invention, however, the extrudates are prepared with further ingredients of washing or cleaning agents. This can be such that the washing or cleaning agents are obtained from a mixture of several different granules, of which the extrudates according to the invention form the main component. Bleach activators, for example N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine, enzyme granules containing enzymes, in particular protease and / or lipase and / or cellulase and / or amylase, with mixtures of 2 or 3 enzymes can be particularly beneficial, and perfume added afterwards. The extrudates can also be prepared with further finely divided dry powders before the enzymes and the other constituents are mixed. Examples of these are zeolite, silicas and salts of fatty acids, for example calcium stearate, bleach activator or mixtures of zeolite with one of the other powders mentioned. It has also been shown that the foam behavior for detergents can be influenced positively if the foam inhibitor, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized Silica or bistearylethylenediamide, at least partially not extruded, but is subsequently mixed with the extrudate. It is also possible that the surface of the extrudate according to the invention is first coated, for example, with zeolite or a mixture containing zeolite and then with a foam inhibitor. Such measures make it possible to further improve the flushing behavior of the extrudates. The bulk density of the extrudates produced according to the invention is preferably between 600 and 1200 g / 1, bulk densities between 700 and 1000 g / 1 and in particular between 750 and 950 g / 1 being particularly preferred. Examples

Example 1:

In a batch mixer equipped with a cutter head chopper, a mixture of 66.2 parts by weight of spray-dried product, 7 parts by weight of a granular component (consisting of 47% by weight of lauryl sulfate, 47% by weight) was mixed % Sodium carbonate, 1% by weight water and 5% by weight sodium sulfate), 4 parts by weight of a granular foam inhibitor based on silicone oil (15% by weight), 7.1 parts by weight sodium citrate, 9 , 15 parts by weight of a mixture of Ci2-Ci8 fatty alcohol with 5 ethylene oxide groups (EO) and Ci2-Ci4-fatty alcohol with 3 EO in the ratio 4: 1 and 6.6 parts by weight of a 30 parts by weight % aqueous water glass solution (Na2θ: Siθ2 1: 2.0) and extruded according to the teaching of international application WO-A-91/02047. The spray-dried product ("tower powder", abbreviated TP) contained 10.3 parts by weight of Cg-Cis-alkylbenzenesulfonate, 2.9 parts by weight of Ci2-Ci8 * sodium fatty acid soap, 1.5 parts by weight of tallow fatty alcohol 5 E0, 56.4 parts by weight of zeolite (calculated as anhydrous active substance), 3.4 parts by weight of sodium carbonate, 2.3 parts by weight of polyvinylpyrrolidone, 1 part by weight of other salts from solutions and raw materials, 16, 8 parts by weight of water and 5.4 parts by weight of Sokalan CPδ ( ^R ) (commercial product from BASF, copolymers based on the sodium salts of acrylic acid and maleic acid), which is 3.6 parts by weight , based on the premix. The finished extrudate was dried, but not worked up any further. The bulk density was 750 g / 1.

Example 2:

Example 1 was repeated with a premix, now containing 7 parts by weight of the 30% by weight waterglass solution and 3.6 parts by weight of Sokalan CPδ ( ^R ), which in turn was introduced into the premix via the spray drying product . The bulk density was 780 g / 1.

Comparative example VI:

Example 1 was repeated, but now 2.2 parts by weight became amorphous

Water glass (1: 2.0) and 2 parts by weight of Sokalan CP δ ( ^R ) over the spray Product and 5.3 parts by weight of a 30 wt .-% aqueous Sokalan CPδ ( ^R ) solution as a plasticizer and / or lubricant in the premix. The proportion of Sokalan CP δ ( ^R ) in the premix was therefore again 3.6 parts by weight. The bulk density was 730 g / 1.

Comparative example V2:

Comparative example 1 was repeated, but the spray drying product contained no copolymer of acrylic and maleic acid. Instead, 7 parts by weight of the 30% by weight aqueous Sokalan CP 5 ( ^R ) solution were introduced into the premix. The bulk density was 825 g / 1.

Comparative example V3:

Comparative Example 1 was repeated. However, now only 5.1 parts by weight of the aqueous Sokalan CPδ ( ^R ) solution and 2 parts by weight of amorphous water glass (1: 2.0) were used, the water glass being incorporated as a powder in the premix. This premix was not capable of extrusion (disturbances until the conveying elements failed in the extruder; sticking in the knife area).

Determination of residues on dark textiles in the washing machine (R test)

30 l of water were initially introduced into a tub washing machine (Arcelik type or comparable type), 80 g of the extrudates were added and the mixture was dissolved by stirring. The laundry, consisting of various dark-colored, easy-care delicate items made of wool, cotton, polyamide and polyacrylonitrile, was then inserted and the machine was heated to a temperature of 30 ° C. After this temperature had been reached, the laundry was washed for 10 minutes by actuating the agitator, the washing liquor was then drained off, rinsed three times with 30 l of water each time and the laundry was spun for 15 seconds. The laundry was dried with an infrared heater and graded by 5 trained people according to the following scheme (averaging): grade 1: perfect, no discernible residues Grade 2: tolerable, isolated, not yet disturbing residues Grade 3: recognizable residues from grade 4 which are already disturbing in the event of a critical assessment: clearly recognizable and disturbing residues in increasing number and quantity

Determination of the Residue Behavior in the Handwash Test (HW in) 32 g of extrudate were pre-dissolved in a bowl in 4 liters of water (16 ° d) at a temperature of 30 ° C. for 15 seconds. Then a Nicki sweater was submerged three times, pressed and turned by 90 °. After a minute, the sweater was removed from the wash liquor 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%.

Determination of the release behavior (release time in seconds)

500 ml of de-mineralized water (20 ° C.) were poured into a 1-1 vessel, the propeller stirrer was switched on at a speed of 900 revolutions per minute and the conductivity measuring cell was immersed. 5 g of the agent (granules, extrudate) were then added. The change in conductivity was recorded by a recorder. The measurement was carried out until there was no longer any increase in conductivity. The time to reach the constant conductivity is the dissolving time of the agent (granulate, extrudate) (100 •%). The dissolving time at 90% resolution was calculated.

Table: Results on residue and dissolution behavior

TP extrudate extrudate dissolving time R-test R-test HW in% 90% in s (grade) (grade)

Example 1 3.0 2.1 19.2 135 Example 2 2.6 2.1 21.5 149

VI 5.5 3.1 28.6 172 V2 10.0 2.0 40.0 234

Claims

claims

1. Process for the production of washable or cleaning-active extrudates with high density, a solid premix, which contains a plasticizer and / or lubricant, being extruded under pressure and the strand after exiting the hole shape by means of a cutting device to the predetermined granule dimension be cut, characterized in that amorphous silicates are used in the solid premix, the amorphous silicates either

(a) at least partially as a solid admixture component and as a plasticizer and / or lubricant, water or aqueous solutions or

(b) at least partially in the form of an aqueous solution as plasticizer and / or lubricant.

2. The method according to claim 1, characterized in that at least one granular component is used in the pre-mix.

3. The method according to claim 1 or 2, characterized in that at least one spray-dried component which contains zeolite is used in the premix.

4. The method according to claim 3, characterized in that the spray-dried component, which contains zeolite, contains amorphous silicates in quantities not above 3% by weight.

δ. Process according to Claim 3 or 4, characterized in that the spray-dried component contains polymeric polycarboxylates, preferably in amounts of 1 to δ% by weight and in particular 2 to 4% by weight.

6. The method according to any one of claims 1 to δ, characterized in that amorphous silicates are used in the form of an aqueous solution and additionally as a solid powdery or granular admixture in the solid premix.

7. The method according to claim 6, characterized in that the amorphous silicates introduced as solid powdery or granular admixing components in the process are part of granular components which contain the silicates in amounts above 3% by weight and other ingredients of washing - Contain or cleaning agents, but are essentially free of zeolite.

8. The method according to claim 6, characterized in that the amorphous silicates introduced as solid powdery or granular admixing component in the process are water glasses, in particular spray-dried water glasses.

9. The method according to any one of claims 1 to 3 or 5, characterized gekenn¬ characterized in that the amorphous silicates are used exclusively in the form of an aqueous solution as a plasticizer and / or lubricant.

10. The method according to any one of claims 1 to δ, characterized in that the amorphous silicates are introduced into the process exclusively as a solid admixture component, preferably in the form of granular to powdered water glasses, water being used in particular as a plasticizer and / or lubricant .

11. The method according to any one of claims 1 to 10, characterized in that as amorphous silicates alkali metal silicates, preferably sodium silicates, with a weight ratio of metal oxide to silicon dioxide of 1: 1 to 1: 4, δ, preferably from 1: 1.9 to 1 : 4.0 and in particular from 1: 2 to 1: 3.5.

12. The method according to any one of claims 1 to 11, characterized in that at least one further plasticizer and / or lubricant is used in the solid premix.

13. The method according to claim 12, characterized in that liquid surfactants or liquid surfactant mixtures and / or aqueous polymeric polycarboxylate solutions are used as further plasticizers and / or lubricants.

14. The method according to any one of claims 1 to 8 or 10 to 12, characterized in that amorphous silicates are used as solid admixture component and polymeric polycarboxylates, but the poly polycarboxylates are not in the form of an aqueous solution as plasticizers and / or lubricants can be introduced into the process.

15. The method according to any one of claims 1 to 14, characterized in that in the premix 30 to 60 wt .-%, preferably 35 to 50 wt .-% zeolite, each based on the anhydrous active substance, 0.5 to 10 wt. %, preferably 1 to 5% by weight of amorphous silicates and δ to 40% by weight, preferably 10 to 30% by weight of surfactants, in particular δ to lδ% by weight of anionic surfactants and δ to lδ% by weight of nonionic surfactants be used.

16. The method according to any one of claims 1 to lδ, characterized in that mixtures of short-chain and long-chain alkyl sulfates, preferably Cβ-Ciβ-alkyl sulfates, in particular Cβ-alkyl sulfate, C12-AI-alkyl sulfate and Ci2-Ci8-alkyl sulfate mixtures with high proportions of C12 alkyl sulfate in combination with Ciö-Cis alkyl sulfates are used.

17. The method according to claim 16, characterized in that the short chain alkyl sulfates are used in the form of a spray-dried, spray-neutralized, granulated or granulated and simultaneously dried compounds.

18. The method according to claim 16 or 17, characterized in that the alkyl sulfate-containing compounds used as a carrier material for the alkyl sulfate alkali carbonate, especially sodium carbonate and optionally alkoxylated alcohols containing 10 to 40 ethylene oxide groups (E0).

19. The method according to any one of claims 1 to 18, characterized in that the extrudates produced are processed with further ingredients of washing or cleaning agents.