EP0793708A1

EP0793708A1 - Washing or cleaning agents containing water-soluble builders

Info

Publication number: EP0793708A1
Application number: EP95941007A
Authority: EP
Inventors: Volker Bauer; Hermann-Josef Welling; Kathrin Schnepp; Monika Böcker; Katrin Erbs; Wolfgang Seiter; Jörg Poethkow; Horst Upadek; Beatrix Kottwitz
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1994-12-02
Filing date: 1995-11-23
Publication date: 1997-09-10
Anticipated expiration: 2015-11-23
Also published as: EP0793708B1; DE59504841D1; ES2128793T3; ATE175717T1; WO1996017045A1; DE4442977A1

Abstract

The aim of the invention is the production, in particular by extrusion, of washing or cleaning agents with bulk densities higher than 600 g/l containing anionic and, optionally, non-ionic surfactants plus water-soluble builders such as sodium carbonate and amorphous sodium silicate to an extent such that zeolites become unnecessary or are necessary only in smaller quantities, but without causing problems in the production of the agents, particularly as regards the extrusion procedure. This aim is achieved by reducing the average zeolite content to less than 19 % by wt. (calculated on the basis of the anhydrous substance) and adding sodium carbonate and amorphous sodium silicate to give a total content of 10 to 40 % by wt. (also calculated based on the anhydrous substances), the ratio by weight of sodium carbonate to sodium silicate lying within the range 5:1 to 1:10 and at least part of the sodium carbonate being added in granular form. Preferably added are granular carbonate-containing materials which also contain amorphous silicates.

Description

"Detergent or cleaning agent with water-soluble builder substances"

The invention relates to detergents or cleaning agents which contain water-soluble inorganic builder substances, and to a process for the production of extruded detergents or cleaning agents which contain water-soluble inorganic builder substances.

Modern, compacted detergents or cleaning agents generally have the disadvantage that, owing to their compact structure, they show poorer dissolving behavior in aqueous liquors than, for example, lighter, spray-dried detergents or cleaning agents of the prior art. Detergents or cleaning agents generally tend to have a lower dissolving rate in water, the higher their degree of compaction. Zeolites, which are usually contained in washing or cleaning agents as builder substances, also contribute to the deterioration in dissolving behavior due to their water insolubility.

From the European patent EP-B-0486 592 a method for the production of extrudates with high density is known, whereby a solid and free-flowing premix is extruded under pressure. The solid and free-flowing premix contains a plasticizer and / or lubricant, which causes the premix to soften plastically under the pressure or the entry of specific work and thus to be extrudable. After exiting the hole shape, the system is no longer subjected to shear forces and the viscosity of the system increases in such a way that the extruded strand can be cut to predeterminable extrudate dimensions. From international patent application WO-A-94/09111 it is now known that the premix to be extruded must contain both constituents which have an intrinsically viscous behavior and constituents which have dilatant properties. If there were only structurally viscous constituents in the premix, it would soften due to the strong shear gradient, in fact become almost fluid, so that the strand would no longer be able to be cut after it emerged from the hole shape. Components with a dilatant action are therefore also used, which have increasing plasticity with increasing shear rate and thereby the cutting ability of the extruded strand to ensure. Most of the ingredients in detergents or cleaning agents show structurally viscous behavior. Dilated behavior tends to be the exception. However, a common component of conventional washing or cleaning agents has dilated properties; they are the aluminosilicates used as builder substances and phosphate substitutes such as zeolite. However, zeolite is water-insoluble and therefore contributes to the fact that the rate of dissolution of extruded washing or cleaning agents in water is lower than that of conventional, lighter agents of the prior art. Extruded washing or cleaning agents are known from international patent application W0-A-94/09111, which contain 19% by weight of zeolite (based on anhydrous active substance), 12.5% by weight of sodium carbonate and 2.2% by weight contain amorphous sodium silicate; However, it was not known that, from a process engineering point of view, zeolite can be partially or even completely replaced by water-soluble inorganic builder substances if these are added in a certain form.

The object of the invention was to provide washing or cleaning agents with bulk densities above 600 g / l, which contain water-soluble builder substances to the extent that zeolite can be partially or completely dispensed with from an application point of view. Another object was also to provide extruded detergents or cleaning agents with bulk densities above 600 g / l and a process for their production which contain the water-soluble builder substances to the extent that zeolite is used not only for technical reasons, but also for applications can also be partially or completely omitted from a procedural point of view.

Accordingly, the invention relates in a first embodiment to a washing or cleaning agent, in particular an extruded washing or cleaning agent with a bulk density above 600 g / l, which contains anionic and optionally nonionic surfactants and, as water-soluble inorganic builder substances, sodium carbonate and amorphous sodium silicate, the content of zeolite (based on anhydrous active substance) is less than 19% by weight and the content of the sum of sodium carbonate and amorphous sodium silicate (in each case based on anhydrous active substance) is 10 to 40% by weight, with the Stipulations that the weight ratio of sodium carbonate to amorphous sodium silicate is in the range from 5: 1 to 1:10 and the sodium carbonate used has at least partially been in the form of granules.

It is preferred that the carbonate-containing granules additionally contain amorphous silicate, in particular sodium silicate, with a molar ratio a2θ: Siθ2 of 1: 1 to 1: 4.5. Particularly preferred sodium silicates are those with a molar weight ratio Na2θ: Siθ2 of 1: 2 to 1: 3.5, disilicate and silicates with a molar ratio Na2θ: Siθ2 to 1: 2.8 being particularly advantageous. Such carbonate and silicate-containing granules can be produced by conventional methods such as spray drying, granulation and compacting, for example roller compacting. Some carbonate and silicate-containing granules which can be used according to the invention are commercially available, for example, under the names Nabion lδ ( ^R ) (commercial product from Rhönen-Poulenc), Gransil (R) (commercial product from Colin Stewart) or Dizzil ( ^R ) G (commercial product from Akzo & Nobel) available. Carbonate-silicate granules of this type are preferred which have a carbonate to silicate weight ratio of 3: 1 to 1: 9 and in particular 2.5: 1 to 1: 5.

The synthetic zeolite used is preferably finely crystalline and contains bound water. Suitable are, for example, zeolite A, but also zeolite X and zeolite P and mixtures of A, X and / or P. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small amounts of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 1 -C 4 -fatty alcohols with 2 to 5 Ethylene oxide groups, Ci2-Ci4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. It is also possible to use zeolite suspensions and zeolite powder. Suitable zeolite powders have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. In a preferred embodiment of the invention, the washing or cleaning agents contain 10 to 16% by weight of zeolite (based on anhydrous active substance) and 10 to 30% by weight of a carbonate and silicate-containing compound (based on anhydrous active substance).

In a further preferred embodiment of the invention, however, the washing or cleaning agents contain 0 to 5% by weight of zeolite (based on anhydrous active substance) and 15 to 40% by weight of a carbonate- and silicate-containing compound (based on anhydrous active substance) . In the case of extruded agents, it is possible for the zeolite not only to be coextruded, but for the zeolite to be introduced into the washing or cleaning agent partially or completely subsequently, that is to say after the extrusion step. Detergents or cleaning agents which contain granules or extrudates which are free of zeolite in the interior of the grain are particularly preferred.

Crystalline phyllosilicates and / or conventional phosphates can also be used as substitutes for the zeolite. However, it is preferred that the detergents or cleaning agents contain only small amounts, in particular up to 10% by weight, of phosphates.

Crystalline layered silicates are, in particular, crystalline, layered sodium silicates of the general formula (I) NaMS _x θ _χ + ι * yH2θ, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4, are suitable. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula (I) are those in which M is sodium and x is 2 or 3. In particular, both β- and ft-sodium disilicate Na2Sι ^' 2θ5- H2θ are preferred. However, these crystalline layered silicates are preferably contained in the agents according to the invention only in amounts of not more than 10% by weight, in particular less than 8% by weight, advantageously not more than 5% by weight.

In addition to the inorganic builder substances, organic builder substances can also be used. Usable organic scaffolding 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), are punched, provided that such use is not objectionable for ecological reasons is, 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.

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, according to DE-A-4300772, as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as DE-C-4221381 as monomers, salts of acrylic acid and 2 -Alkylallyl- sulfonic acid and sugar derivatives included. Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and P 44 17 734.8 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Other suitable builder systems are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110. The known polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred builder substances.

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

In a preferred embodiment of the invention, the washing or cleaning agents have, as organic cobuilders, polymeric polycarboxylates and / or salts of polycarboxylic acids, preferably in amounts of from 2 to 20% by weight and in particular from 5 to 15% by weight.

Surprisingly, it has been found that zeolite can be replaced not only partially or completely by the carbonate-containing granules, for technical reasons, but also that the washing properties of the washing or cleaning agents according to the invention and / or extruded washing or cleaning agents can be improved. Thus, the detergents according to the invention not only have the same good primary washing performance as the analogous conventional zeolite-containing detergents without the carbonate-containing granules and in particular without the compounds containing carbonate and silicate, but with preferred embodiments even significantly improved primary washing performances are achieved. The same applies to the graying inhibition.

Other ingredients of the washing or cleaning agents according to the invention are, in particular, surfactants, above all anionic surfactants and, if appropriate, nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.

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 used for example with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are composed of Ci2-Ci8-Al. for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Further suitable anionic surfactants are the α-sulfofatty acids obtainable by ester cleavage of the α-sulfofatty acid alkyl esters or their di-salts. The mono-salts of the α-sulfofatty acid alkyl esters are obtained already in their industrial production as an aqueous mixture with limited amounts of di-salts. The salt content of such surfactants is usually below 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.

Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. The alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid semiesters of the Ci2-Cιg fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cιo-C2θ " Ox ° ^a T ⁽ alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds on the Based on oleochemical raw materials, C15-C18-alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be of particular advantage, and particularly advantageous for machine-wash detergents, Ci5-Ci8 ~ alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular those anionic surfactants which have a lower Have Krafft point and show a low tendency to crystallize at relatively low washing temperatures of, for example, room temperature to 40 ° C. In a preferred embodiment of the dung Erfin therefore the means of short-chain and long-chain fatty alkyl sulfates mixtures, preferably mixtures of Ci2-Ci4-fatty alkyl sulfates or Ci2-C _j 8-fatty alkyl sulfates with Ci5-CI8 fatty alkyl sulfates and, in particular Ci2-Ci6 fatty alkyl sulfates with Cis- -Ciβ fatty alkyl sulfates. 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 C15 to C22 are used. Mixtures of saturated sulfonated fatty alcohols predominantly consisting of C15 and unsaturated, predominantly consisting of Cjg existing sulfated fatty alcohols are preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol ( ^R ) type (commercial product of the applicant), the weight ratios of alkyl sulfates to alkenyl sulfates being from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 preferred.

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

The sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cu alcohols with an average of 3.5 mol of ethylene oxide (E0) or with 1 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.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs ~ to Q- Fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

In addition to the anionic surfactants, the agents can also contain soaps, preferably in amounts of 0.2 to 5% by weight. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 2 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.

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

Preferred anionic surfactants are alkylbenzenesulfonates and alk (en) yl sulfates, in particular alkyl sulfates in the specified C chain range. In conventional extrudates, the alkyl sulfates led to a reduction in the rate of dissolution in comparison to the alkyl benzenesulfonates. Surprisingly, it has now been found that the extrudates according to the invention have such an increased dissolving rate compared to the conventional extrudates that even with significantly increased alkyl sulfate contents, in particular by replacing alkylbenzenesulfonate with alkyl sulfate, the dissolving rates of the extrudates are equally good to better than with the conventional extrudates which did not contain the carbonate-containing granules. In one embodiment of the invention, therefore, detergents or cleaning agents, in particular extruded detergents or cleaning agents, are preferred, which contain 10 to 30% by weight of anionic surfactants, preferably at least 3% by weight of surfactant and surfactants on the anionic surfactants as a whole - contain at least 15% by weight, in particular 20 to 100% by weight, of sulfate surfactants. Agents which contained 30 to 90% by weight, based on the anionic surfactants present, of sulfate surfactants, in particular alkyl sulfates, have proven to be particularly advantageous. In one embodiment of the invention, agents are provided which have an extruded component which contains the carbonate-containing granules and at least one further surfactant-containing component which contains the major part of the alkyl sulfate introduced into the agent as a whole.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol in which the alcohol radical has a methyl or linear branching, preferably in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 E0 or 4 E0, Cg-Cn alcohol with 7 E0, Ci3-Ci5 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, Ci2-Ci8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of C12-Ci4 alcohol with 3 E0 and Ci2-Ci8 alcohol with 5 E0. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 E0 can also be used. Examples of this are tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols, 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 ethyl ester, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

In addition, alkyl glycosides of the general formula R0 (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C., can also be used as further nonionic surfactants -Atoms means 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.

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 are polyhydroxy fatty acid of the formula (II),

R3

I 2_CO-N- [Z] (II)

in which R ^{2 is} C0 for an aliphatic acyl radical with 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched poly- hydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanol and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO-A-92/06984. The polyhydroxyfatty acid derivatives are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.

In addition, the agents can also contain components which have a positive influence on the oil and fat washability 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 cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene glycol terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof .

The agents can also contain constituents which further improve the solubility of the heavy granules. Such components and the introduction of such components are described for example in the international patent application WO-A-93/02176 and in the German patent application DE 4203031. The components preferably used include, in particular, fatty alcohols with 20 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 E0 and tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 EO and polyethylene glycols with a relative molecular weight between 200 and 2000.

Of the compounds which serve as bleaching agents and supply H2O2 in water, the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids providing H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used. Percarbonate is also preferred as an ingredient. However, percarbonate is preferably not coextruded but, if necessary, mixed in subsequently.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or 0-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Further known bleach activators are acetylated mixtures of sorbitol and mannitol, as are described, for example, in European patent application EP-A-0525239. The bleach activator content of the bleach-containing agents is 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 (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,5,5-triazine (DADHT) and acetylated sorbitol mannitol Mixtures (S0RMAN).

It can be advantageous to add conventional foam inhibitors to the compositions. 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 signed silica, and also paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / 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 or lipolytically acting enzymes, aylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Strepto yces griseus and Humica insolens, are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or protease, lipase and cellulase, in particular, however, mixtures containing proteases and / or lipases or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytic enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

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

The agents can also contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which salt with soluble calcium and a calcium content of preferably about 1.2% by weight, based on the enzyme, is stabilized. 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) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.

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. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, 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 diethanolamino 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. The finished washing or cleaning agents can be constructed uniformly from granules or extrudates which contain the above-mentioned ingredients. In a further embodiment of the invention, however, the granules or extrudates are processed 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 main constituent of the invention. 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 advantageous, and perfume mixed in afterwards. The extrudates can also be processed with further finely divided dry powders before the enzymes and the other constituents are added. Examples of these are zeolite, silicas and salts of fatty acids, for example calcium stearate, bleach activators or mixtures of zeolite with one of the other powders mentioned. Mixtures of zeolite and silicas, which are available on the market, for example, as Aerosil ( ^R ), are particularly preferred. The weight ratios of zeolite to silica are advantageously above 1, in particular in a range from 200: 1 to 2: 1. It has also been shown that the foaming behavior for detergents can be positively influenced 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 bistearylethylene diid, 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 covered, for example, with zeolite or a zeolite-containing mixture and then with a foam inhibitor. Such measures enable a further improvement in the induction behavior of the extrudates.

In a preferred embodiment of the invention, the agent, in particular the extrudate accordingly, has subsequent treatment on the surface of finely divided ingredients of detergents or cleaning agents in amounts of up to 5% by weight, based on the agent, in particular that treated extrudate, and in particular 0.1 to 2% by weight of finely divided zeolite. The same applies to non-extruded washing or cleaning agents.

The bulk density of the granules or extrudates produced according to the invention and of the finished washing or cleaning agents is preferably between 700 and 1200 g / 1, bulk densities between 700 and 1000 g / 1 and in particular between 750 and 950 g / 1 being particularly preferred.

The agents according to the invention can be produced by any of the known spray drying, granulating, compacting and / or mixing processes.

However, in a further embodiment of the invention, the invention relates in particular to a process for the production of extruded washing or cleaning agents with a bulk density above 600 g / l, which contain anionic and optionally nonionic surfactants and sodium carbonate and amorphous sodium silicate as water-soluble builder substances . Here, according to the teaching of European patent EP-B-0 486 592, a solid and free-flowing premix is extruded in the form of strands at pressures of up to 200 bar, the strand is cut to the predetermined granule dimension by means of a cutting device after exiting the hole shape, and the like Plastic raw, optionally moist crude extrudate optionally fed to a further shaping processing step and then dried. According to the invention, sodium carbonate and amorphous sodium silicate (in each case based on anhydrous active substance) are used in a total amount of between 10 to 40% by weight, sodium carbonate and amorphous sodium silicate in a weight ratio of 5: 1 to 1:10 and the sodium carbonate at least partially in the form of a Granules are used, with the proviso that the quantities refer to the optionally dried extrudate. It is preferred that a carbonate-silicate compound is used as the carbonate-containing granulate, which can be produced, for example, by spray drying or granulation and, if appropriate, subsequent compacting, such as roller compaction. However, it is not necessary that the total amount of carbonate or carbonate and silicate can be introduced into the process via such a granulate or compound.

To explain the actual extrusion process, reference is expressly made to the European patent EP-B-0486 592 and to the international patent applications WO-A-93/02176 and WO-A-94/09111. In a preferred embodiment of the invention, the premix is preferably fed continuously to a twin-screw extruder with a co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and closed under pressure, which is preferably at least 25 bar, but can also be below this at extremely high throughputs depending on the apparatus used ¬ Lich the extrudate preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives. The hole diameter of the perforated nozzle plate and the length of the strand cut are matched to the selected granule dimension. In this embodiment, granules of an essentially uniformly predeterminable particle size can be produced, the absolute particle sizes in particular being able to be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules 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 chopped-off 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 crude extrudate 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. 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 fed to a drying step, for example a fluidized bed dryer. there 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.

In a preferred process variant, zeolite (based on anhydrous active substance) is used in amounts of 10 to 30% by weight, preferably less than 19% by weight, the amounts given relating to the optionally dried extrudate, and sodium carbonate and Na¬ trium silicate, in particular in the form of granules or compound, are introduced into the process in such quantities that the weight ratio - based in each case on anhydrous active substances - of zeolite to the sum of carbonate and silicate is 2: 1 to 1: 2 and preferably 1.5: 1 to Is 1: 1.5.

In a further preferred process variant, zeolite (based on anhydrous active substance) is used only in amounts of 0 to 5% by weight. It is possible, and in some cases may also be preferred, that zeolite is only partially or not co-extruded, but is subsequently added to the crude extrudate. Overall, it is preferred to add dry powder as a powdering agent to the crude extrudate in amounts of up to 5% by weight, zeolite (anhydrous active substance) preferably being used in amounts of 0.1 to 2% by weight. The powdering agents can be added before, during or after the drying which may have been carried out, but the addition is preferably carried out after completion of the shaping processing step which is carried out and which is carried out, for example, in a commercially available rounder.

Examples

Example 1: Partial exchange of zeolite in the extrudate grain

According to the teaching of European patent EP-B-0486 592, the following agents M1, M2 and M3 and the comparative agent VI according to the invention were obtained by extrusion and subsequent admixing of the bleach activator granules, the enzyme granules and the foam inhibitor granules Starch base manufactured. The extrusion mixtures of agents Ml to M3 could be extruded without any process problems. The crude extrudates were each powdered before mixing with a mixture of zeolite and silica in a weight ratio of 4: 1. The compositions of the finished compositions in parts by weight were as shown in Table 1. The bulk density of the finished compositions was between 720 and 780 g / 1. The agents according to the invention had a significantly better primary washing power than the comparative agent VI over all the soiling tested at 60 ° C. and a water hardness of 16 ° d.

The Nabion lδ ( ^R ) used in the agents according to the invention is a commercial product from Rhönen-Poulenc and consisted of 55% by weight sodium carbonate, 29% by weight sodium disilicate and 16% by weight water.

The residue behavior of the agents was tested as follows. In a bowl, 32 of the respective means 1 water (16 ° d) were pre-dissolved in ei¬ ner temperature of 30 ^β C for 15 seconds with the hand g in Fig.4. 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 determined in each case are given in% of the quantity weighed in Table 2. It is striking that - although only a small proportion of zeolite was replaced by a soda-containing compound - not only Ml has a clearly better residue behavior than VI, but also that M2 and M3, which had higher alkyl sulfate contents than VI, also have one show improved residue behavior. Table 1: Compositions of agents Ml to M3 and VI (in parts by weight)

VI Ml M2 M3

Cg-C-3-alkylbenzenesulfonate 13.6 13.6 9.4 9.2

C-.2-Ci8 alkyl sulfate 3.9 3.9 8.0 7.9 Ci2-Ci8 alcohol with 5 EO 3.6 3.6 3.6 2.4

Ci2-Ci8 fatty acid soap 0.7 0.7 0.8 0.5

Polyethylene glycol with a 1.5 1.5 1.5 2.4 molecular weight of 400

Zeolite (anhydrous active substance) 22.3 17.6 17.6 17.0

Sodium carbonate 6.3 1.6

Nabion lδ ( ^R ) (anhydrous active 12.0 12.0 14.1

Substance)

Acrylic acid-maleic acid copolymer 3.5 3.5 3.5 2.3

(Sodium salt)

amorphous sodium disilicate 1.5 1.5 1.5 1.0

Perborate onohydrate 17.4 17.4 17.4 17.7

Phosphonate 0.5 0.5 0.5 0.5

Zeolite / silica 1.5 1.5 1.5 1.5

Tetraacetylethylenediamine 7.0 7.0 7.0 7.0

Protease granules 1.6 1.6 1.6 1.6

Starch-based foam inhibitor 3.6 3.6 3.6 3.6

Water and salts from solutions 11.2 10.3 10.3 8.5

Table 2: Residue behavior in%

VI 24.3

Ml 13.9

M2 18.9

M3 19.6 Example 2: Full exchange of zeolite in the extrudate grain

Comparative agent VI and agents M4 to MIO according to the invention were prepared as described in Example 1, agents M4 to MIO according to the invention differing from VI in that they instead of zeolite, sodium carbonate and acrylic acid-maleic acid Polymers had the builder combinations given in Table 3. The extrusion mixtures of agents M4 to MIO could be extruded without any process problems, although the mixtures to be extruded did not contain any zeolite.

The primary washing power of agents M4 to MIO according to the invention was significantly better in terms of fat / pigment stains, protein-containing stains and high-fat stains than that of Comparative Example VI (Table 4). Only on bleachable stains (red wine and tea) were the performance of the agents M4 to MIO compared to VI the same to only slightly improved. Likewise, the graying of the fabrics that had been washed with M4 to MIO was significantly less than when VI was used. Surprisingly, some fabrics after 25 washes with the agents M4 to MIO according to the invention even had better rejection values than before the washes (Table 5). In addition, the ash contents of individual textile samples were also determined after 25 washes (Table 6). The ash values for the fabrics washed with the agents according to the invention were not significantly worse for all fabrics than for the fabrics washed with VI.

The application test was carried out under practical conditions in household washing machines. For this purpose, the machines were loaded with 3.0 kg of clean laundry and 0.5 kg of test fabric, the test fabric being impregnated with conventional test soils for testing the primary washing ability and consisting of white fabric for testing the graying inhibition and the ash determination. Strips of standardized cotton fabric (laundry research institute Krefeld, WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling fabric (FT) were used as the white test fabric. Washing conditions for primary washing ability and graying inhibition: tap water of 23 ° d (equivalent to 230 mg CaO / l), amount of detergent used per detergent and machine 80 g, washing temperature 90 ° C, liquor ratio (kg laundry: liters of washing liquor in the main wash cycle) 1: 5,7,3 rinsing with tap water, spinning and drying. Soiling: Dust-wool fat on cotton (SW-B) Dust-skin fat on cotton (SH-B) Dust-skin fat on refined cotton (SH-BV) Dust-skin fat on mixed fabrics made of polyester and refined cotton (SH-PBV) Milk soot on cotton (MR-B) Milk cocoa on cotton (MK-B)

Primary washing power: 5-fold determination

Graying inhibition and ash determination: 25 washes

Table 3: Compositions of the builder combinations in the compositions M4 to MIO (in parts by weight)

M4 M5 M6 M7 M8 M9 MIO

Nabion lδ ( ^R ) (anhydrous active 25 25 20 20 20 20 20

Substance) Acrylic acid-maleic acid copolymer 5 - 10 7.5 5 2.5

(Sodium salt) sodium citrate dihydrate (water - - 5 - 2.5 5 7.5 10 free active substance) Table 4: Primary washing power (reflectance in%)

VI M4 M6 M7 M8 M9

SW-B 67.7 73.8 73.3 72.5 71.9 71.0

SH-B 60.3 64.5 63.7 62.4 63.7 61.2

SH-BV 71.1 74.2 74.7 74.4 75.2 74.7

SH-PBV 64.9 69.4 71.0 68.5 68.9 68.0

0 66.0 70.5 70.7 69.5 69.9 68.7

MR-B 74.9 78.4 78.4 78.2 78.2 78.0

MK-B 77.4 80.4 79.9 79.4 80.3 79.0

0 76.2 79.4 79.2 78.8 79.3 78.5

Table 5: Graying inhibition (reflectance in%)

WFK BN B FT 0

Initially worth 86.0 82.0 83.9 82.9 83.7

VI 73.6 74.5 69.4 70.8 72.1

M4 82.6 85.6 85.4 83.6 84.3

M5 83.9 86.7 85.9 83.9 85.1

M6 81.8 85.4 84.6 82.9 83.7

M7 81.5 84.5 84.0 82.8 83.2

M8 81.3 83.5 83.6 82.1 82.6

M9 81.1 84.1 84.2 82.2 82.9

MILLION 80.5 84.3 83.6 81.8 82.6 Table 6: Ash values

Average wt% ash

WFK BN FT B 0

Initial value 0.70 0.10 0.62 0.67 0.52

VI 5.94 3.01 2.65 3.49 3.77

M7 5.29 3.31 3.45 3.31 3.84

M9 5.99 3.57 3.04 2.96 3.89

MIO 5.78 3.27 3.07 2.72 3.71

Claims

claims

1. washing or cleaning agent, in particular extruded washing or cleaning agent with a bulk density above 600 g / 1, containing anionic and optionally nonionic surfactants and as water-soluble inorganic builder substances sodium carbonate and amorphous sodium silicate, characterized in that the content of zeolite (based on anhydrous active substance) is on average less than 19% by weight and the content of the sum of sodium carbonate and amorphous sodium silicate (in each case based on anhydrous active substance) is 10 to 40% by weight, with the provisos that the weight ¬ ratio of sodium carbonate to amorphous sodium silicate is in the range from 5: 1 to 1:10 and the sodium carbonate used has been at least partially in the form of granules.

2. Detergent or cleaning agent according to claim 1, characterized in that the carbonate-containing granules additionally contain amorphous silicate.

3. washing or cleaning agent according to claim 1 or 2, characterized gekenn¬ characterized in that it contains 10 to 16 wt .-% zeolite (based on anhydrous active substance) and 10 to 30 wt .-% of a carbonate- and silicate-containing compound ( based on the anhydrous active substances).

4. washing or cleaning agent according to claim 1 or 2, characterized gekenn¬ characterized in that it 0 to 5 wt .-% zeolite (based on anhydrous active substance) and 15 to 40 wt .-% of a carbonate and silicate-containing compound ( based on the anhydrous active substances).

5. washing or cleaning agent according to one of claims 1 to 4, characterized in that it contains 10 to 30 wt .-% anionic surfactants, preferably at least 3 wt .-% sulfate surfactants and - based on the anionic surfactants - at least 15 % By weight, in particular 20 to 100% by weight, of sulfate surfactants.

6. washing or cleaning agent according to one of claims 1 to 5, characterized in that it is a carbonate-silicate granules with a Weight ratio carbonate to silicate from 3: 1 to 1: 9, preferably from 2.5: 1 to 1: 5 contains.

7. Detergent or cleaning agent according to one of claims 1 to 6, characterized in that it is organic cobuilder polymeric polycarboxy late and / or salts of polycarboxylic acids, preferably in amounts of 2 to 20 wt .-% and in particular from 5 to 15 Wt .-% contains.

8. washing or cleaning agent according to one of claims 1 to 7, characterized in that the agent by subsequent treatment on the surface of finely divided ingredients of washing or cleaning agents, preferably in amounts of up to 5% by weight, based on the treated agent, in particular the treated extrudate, and in particular 0.1 to 2 wt .-% of finely divided zeolite.

9. Process for the production of an extruded washing or cleaning agent with a bulk density above 600 g / l, containing anionic and optionally nonionic surfactants and as water-soluble inorganic builder substances sodium carbonate and amorphous sodium silicate, a solid and free-flowing premix at printing up to 200 bar extruded, the extrudate after the exit from the hole shape is cut to the predetermined granulate size by means of a cutting device, and the still plastic, possibly moist crude extrudate is fed to a further shaping processing step and then dried, characterized in that sodium carbonate and Amorphous sodium silicate (in each case based on anhydrous active substance) is used in a total amount of between 10 to 40% by weight, sodium carbonate and amorphous sodium silicate in a weight ratio of 5: 1 to 1:10 and the sodium carbonate at least partially can be used in the form of granules, with the proviso that the quantities refer to the optionally dried extrudate.

10. The method according to claim 9, characterized in that a carbonate-silicate compound is used as the carbonate-containing granulate, which was produced by spray drying or granulation and, if appropriate, subsequent compacting.

11. The method according to claim 9 or 10, characterized in that zeolite (based on anhydrous active substance) in amounts of 10 to 30 wt .-%, preferably less than 19 wt .-%, the quantitative information on the optionally dried Obtain extrudate, and sodium carbonate and sodium silicate are used in particular as granules or compound in amounts such that the weight ratio - based in each case on anhydrous active substances - of zeolite to the sum of carbonate and silicate is 2: 1 to 1: 2 and preferably 1 , 5: 1 to 1: 1.5.

12. The method according to claim 9 or 10, characterized in that zeolite (based on anhydrous active substance) is used in amounts of 0 to 5 wt .-%.

13. The method according to any one of claims 9 to 12, characterized in that dry powder is added to the crude extrudate as a powdering agent in amounts of up to 5% by weight, zeolite (anhydrous active substance) preferably in amounts of 0.1 to 2% by weight. is used.