EP0793708B1 - Process for the preparation of extruded washing or cleaning agents containing water-soluble builders - Google Patents

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

The invention relates to detergents or cleaning agents which are water-soluble contain inorganic builder substances, in particular a process for the preparation of extruded washing or cleaning agents, which contain water-soluble inorganic builder substances.

Modern, compressed washing or cleaning agents generally have the Disadvantage that they have a poorer because of their compact structure Show dissolving behavior in aqueous liquor than, for example, lighter, spray-dried washing or cleaning agents of the prior art. Washing or cleaning agents generally tend to do so lower dissolving speed in water, the higher their degree of compaction is. Zeolites used in detergents or cleaning agents as builders are usually included due to their water insolubility in addition to the deteriorated dissolving behavior.

From the European patent EP-B-0486 592 is a manufacturing process known from high density extrudates, being 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 under the pressure or the entry specific work plastically softened and thus extrudable. After the exit from the hole shape no longer affects the system with shear forces and the viscosity of the system increases in such a way that the extruded strand cut to predetermined extrudate dimensions can be. From international patent application WO-A-94/09111 is now known that in the premix to be extruded both components, which have a structurally viscous behavior, as well as components, which have dilatant properties must be included. Just lay Components with a pseudoplastic action in the premix, it would soften in this way due to the strong shear gradient, almost liquid be that the strand after leaving the hole shape no longer would be able to be cut. It therefore also has dilating components used, which with increasing shear rate an increasing plasticity have and thereby the cutting ability of the extruded strand to ensure. Most of the ingredients in washing or cleaning agents show structurally viscous behavior. A dilatante behavior poses rather the exception. A common part of conventional laundry or detergent has dilatant properties; they are alumosilicates used as builder and phosphate substitute such as Zeolite. However, zeolite is insoluble in water and therefore helps that the dissolving speed of extruded washing or cleaning agents in water is less than that of conventional, lighter means of State of the art. From international patent application WO-A-94/09111 extruded washing or cleaning agents are known, which 19th % By weight of zeolite (based on anhydrous active substance) and 12.5% by weight Contain sodium carbonate and 2.2 wt .-% amorphous sodium silicate; it was however, it is not known that zeolite is partially process-related or even entirely through water-soluble inorganic builder substances can be replaced if they are added in a certain form.

Spray-dried detergents are known from US Pat. No. 4,075,117 Substitutes for phosphates do not contain carbonates and silicates as builder components but zeolites. The agents described there have a comparable agent containing phosphates or superior cleaning performance. However, according to the teaching of No. 4,075,117 is not used in any particular form.

From the unpublished German patent application DE 44 05 511 A1 Detergent with amorphous silicate builder substances known, besides Detergent ingredients such as surfactants contain carboxylates, the Containing amorphous alkali silicates and alkali carbonates in the form of a compound, which has neither a homogeneous surface nor a uniform grain spectrum. The carbonate-silicate compounds are subsequently added to the process claimed there mixed with a basic detergent of the usual composition.

The object of the invention was to include washing or cleaning agents Provide bulk densities above 600 g / l, which are water soluble Builders contain to the extent that on zeolite from application technology View can be partially or completely omitted. Also existed another job in extruded washing or cleaning agents with bulk densities above 600 g / l and a process for their preparation to provide which the water-soluble builder substances in the Dimensions included that on zeolite not only for technical reasons but partially or completely waived from a procedural point of view can be.

The subject of the invention is a method of making extruded Detergents or cleaning agents with a bulk density above 600 g / l, which anionic and optionally nonionic surfactants as well as water-soluble Builder substances sodium carbonate and amorphous sodium silicate contain. According to the teaching of the European patent EP-B-0 486 592 a solid and free-flowing premix at pressures up to 200 bar strand-pressed, the strand after exiting from the hole shape by means of a cutting device cut to the predetermined granule dimension as well as the still plastic, possibly moist crude extrudate optionally fed to a further shaping processing step and then dried. According to the invention, sodium carbonate and amorphous sodium silicate (based in each case on anhydrous active substance) in the sum between 10 to 40 wt .-% used, sodium carbonate and amorphous sodium silicate in a weight ratio of 5: 1 to 1:10 and that Sodium carbonate at least partially used in the form of granules with the proviso that the quantities refer to the obtain dried extrudate; in addition, the extrudate is optionally with other ingredients of washing and Prepared cleaning agents and zeolite in quantities less than 19% by weight (based on anhydrous active substance). It is preferred that the carbonate Granulate a carbonate-silicate compound is used, which for example by spray drying or granulation and, if appropriate subsequent compaction, such as roller compaction, are produced can. However, it is not necessary that the total amount of carbonate or on carbonate and silicate via such a granulate or compound in the procedure be introduced.

According to the invention, it is preferred that the carbonate-containing granules used additionally contain amorphous silicate, in particular sodium silicate, with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5. Particularly preferred sodium silicates are those with a molar Na ₂ O: SiO ₂ weight ratio of 1: 2 to 1: 3.5, disilicates and silicates with a Na ₂ O: SiO ₂ molar ratio of 1: 2.8 being particularly advantageous are. Such carbonate and silicate-containing granules can be produced by conventional methods such as spray drying, granulation and compacting, for example roller compaction. Some granules containing carbonate and silicate which can be used according to the invention are commercially available, for example, under the names Nabion 15 ^(R) (commercial product from Rhône-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 weight ratio of carbonate to silicate of 3: 1 to 1: 9 and in particular of 2.5: 1 to 1: 5.

The synthetic zeolite used is preferably finely crystalline and contains bound water. Zeolite A, for example, but also zeolite X and zeolite P and mixtures of A, X and / or P are suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ 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 laundry detergents produced according to the invention contain or cleaning agent 10 to 16 wt .-% zeolite (based on anhydrous Active substance) and 10 to 30 wt .-% of a carbonate and silicate-containing Compounds (based on anhydrous active substance).

In a further preferred embodiment of the invention, those produced according to the invention contain Washing or cleaning agents, however, 0 to 5 wt .-% zeolite (based on anhydrous active substance) and 15 to 40 wt .-% of a carbonate and silicate-containing Compounds (based on anhydrous active substance). With extruded It is possible that the zeolite not only co-extrudes is, but that the zeolite partially or completely retrospectively, ie after introduced into the washing or cleaning agent during the extrusion step becomes. Washing or cleaning agents which are produced according to the invention are particularly preferred here contain a granulate or extrudate that is free inside the grain of zeolite.

Crystalline layered silicates can also be used as substitutes for the zeolite and / or conventional phosphates are used. However, it is preferred that phosphates only in small amounts, in particular up to a maximum 10% by weight are contained in the washing or cleaning agents produced according to the invention.

-Natriumdisilikate Na₂Si₂O₅·yH₂O bevorzugt. Diese kristallinen Schichtsilikate sind jedoch in den erfindungsgemäß hergestellten Mitteln vorzugsweise lediglich in Mengen von nicht mehr als 10 Gew.-%, insbesondere von weniger als 8 Gew.-%, vorteilhafterweise von maximal 5 Gew.-% enthalten.Crystalline layered silicates are, in particular, crystalline, layered sodium silicates of the general formula (I) NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 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 sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both are

Sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O is preferred. However, these crystalline layered silicates are preferably only contained in the agents produced according to the invention 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 ones can also be used Builder substances are used. Usable organic builders are, for example, those preferably used in the form of their sodium salts Polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use for ecological reasons is not objectionable, and mixtures of these. Preferred Salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of this.

Suitable polymeric polycarboxylates are, for example, the sodium salts 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 acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain. Their relative molecular mass, 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 can be used either as a powder or as an aqueous solution, 20 up to 55% by weight aqueous solutions are preferred. Particularly preferred are also biodegradable terpolymers, for example those that according to DE-A-43 00 772 as monomer salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. Other preferred copolymers are those that are described in German patent applications DE-A-43 03 320 and P 44 17 734.8 are described and as monomers preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Other suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble Salts such as those used in the international patent application WO-A-93/08251 are described or their production, for example, in of international patent application WO-A-93/16110.

Also known are the other preferred builder substances To name polyaspartic acids or their salts and derivatives.

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

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

Surprisingly, it was found that zeolite is not only made from process engineering Partly or entirely due to the carbonate-containing granules can be replaced, but also the washing properties the extruded according to the invention Detergents or cleaning agents can be improved. So point the detergents produced according to the invention not only have an equally good primary washing performance like the conventional detergents containing zeolite without the carbonate-containing granules and in particular without the carbonate and silicate-containing compounds, but with preferred embodiments significantly improved primary washing performance is even achieved. The same applies to the graying inhibition.

As further ingredients of the washing or cleaning agents produced according to the invention come in particular surfactants, especially anionic surfactants, and optionally nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.

Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Alkanesulfonates made from C ₁₂ -C ₁₈ alkanes are also suitable. 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 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 in their industrial production as an aqueous mixture with limited amounts of di-salts. The disalt 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 represent mono-, di- and triesters and their mixtures as they do in the production 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 Glycerin can be obtained.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₆ -C ₁₈ alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C ₁₆ -C ₁₈ alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones 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 prepared according to the invention therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C ₁₂ -C ₁₄ fatty alkyl sulfates or C ₁₂ -C ₁₈ fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates and in particular C ₁₂ - C ₁₆ fatty alkyl sulfates with C ₁₆ -C ₁₈ 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 C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfonated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those derived from solid or liquid HD-Ocenol (R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.

Also 2,3-alkyl sulfates, which, for example, according to the US patents 3,234,258 or 5,075,041 are manufactured and sold as commercial products Shell Oil Company can be obtained under the name DAN (R) suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (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 are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₂₄ fatty acid soaps and 0 to 50% by weight of oleic acid soap.

The anionic surfactants and soaps can be 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 are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium salts.

Preferred anionic surfactants are alkylbenzenesulfonates and alk (en) ylsulfates, especially alkyl sulfates in the specified C chain range. In conventional Extrudates led the alkyl sulfates to the alkyl benzene sulfonates to a reduction in the release speed. Surprisingly it has now been found that the extrudates produced according to the invention such an increased dissolving speed compared to conventional extrudates exhibit that even with significantly increased alkyl sulfate contents, in particular by replacing alkyl benzene sulfonate with alkyl sulfate, the dissolving speeds of the extrudates are equally good to better than in the conventional extrudates, which the carbonate-containing granules do not contained.

In one embodiment of the invention, washing or cleaning agents produced according to the invention are therefore particularly preferred extruded washing or cleaning agents according to the invention, which 10 to 30 wt .-% anionic surfactants, preferably at least 3 wt .-% sulfatic surfactants and - based on the anionic Total surfactants - at least 15% by weight, especially 20 to 100% by weight contain sulfate surfactants. Agents manufactured according to the invention have 30 to 90 % By weight, based on the anionic surfactants present, of sulfate surfactants, contained especially on alkyl sulfates, as particularly advantageous proven. In one embodiment of the invention, means are provided which is an extruded component that contains the carbonate Contains granules and at least one other surfactant-containing component having the major part of the total brought into the means Contains alkyl sulfate.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred non-ionic surfactants that either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated Fatty alcohols used 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 ester, as for example in the Japanese patent application JP 58/217598 are described or which are preferably according to the in the international patent application WO-A-90/13533 getting produced.

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

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable. The amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II),

in the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.

The polyhydroxy fatty acid amides are known substances that usually 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 can be obtained. Regarding the processes for their manufacture see U.S. Patent Nos. 1,985,424, 2,016,962 and US-A-2,703,798 and International Patent Application WO-A-92/06984 referred. The polyhydroxy fatty acid amides are preferably derived from reducing agents Sugars with 5 or 6 carbon atoms, especially from that Glucose.

In addition, the agents produced according to the invention can also contain components which and grease washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent prepared according to the invention that this oil and contains fat-dissolving component, is washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers from ethylene glycol terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these.

The agents produced according to the invention can also contain constituents which have solubility of the heavy granules further improve. Such components and The introduction of such components is, for example, in the international Patent application WO-A-93/02176 and in the German patent application DE 42 03 031. The preferred ingredients include in particular fatty alcohols with 20 to 80 moles Ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 E0 as well Polyethylene glycols with a molecular weight between 200 and 2000.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents produced according to the invention is preferably 5 to 25% by weight and in particular 10 to 20% by weight, wherein perborate monohydrate is advantageously used. Percarbonate is also preferred as an ingredient. However, percarbonate is preferably not co-extruded, but optionally 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 produced according to the invention. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239. The bleach activator content of the bleach-containing agents produced according to the invention 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'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).

It may be advantageous to add conventional foam inhibitors to the agents produced according to the invention. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those 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.

Enzymes come from the class of proteases, lipases or lipolytic acting enzymes, amylases, cellulases or mixtures thereof in question. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola Insolens obtained enzymatic agents. Preferably be Subtilisin-type proteases, and in particular proteases derived from Bacillus lentus are used. There are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or protease, lipase and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic acting enzymes of particular interest. Examples of such lipolytic acting enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The amount the enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

The stabilizers come in particular for per-compounds and enzymes Salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid into consideration.

The agents produced according to the invention 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 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 (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

Graying inhibitors have the task of removing the fiber Keep dirt suspended in the fleet and prevent 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 Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch or aldehyde starches. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures and polyvinylpyrrolidone, for example in amounts from 0.1 to 5 % By weight, based on the agents produced according to the invention, are used.

The agents produced according to the invention can be derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present be, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

The finished washing or cleaning agents can consist of 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 detergents or cleaning agents are obtained from a mixture of several different granules, of which the main constituent is that produced according to 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 beneficial, and perfume added afterwards. The extrudates produced according to the invention can also be prepared with further finely divided dry powders before the enzymes and the other constituents are added. Examples include 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 bistearylethylenediamide, at least partially does not extrude , but is subsequently mixed with the extrudate. It is also possible that the surface of the extrudate produced according to the invention is first covered, for example, with zeolite or a mixture containing zeolite and then with a foam inhibitor. Such measures enable a further improvement in the induction behavior of the extrudates produced according to the invention.

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

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

To explain the actual extrusion process is explicit to the European patent EP-B-0486 592 and to the international ones Patent applications WO-A-93/02176 and WO-A-94/09111 referenced. In a preferred one Embodiment of the invention is preferably the premix continuously a 2-screw extruder with co-rotating or fed counter-rotating screw guide, its housing and Extruder pelletizing head heated to the predetermined extrusion temperature could be. Under the shear action of the extruder screws, this is Premix under pressure, which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used can also lie below, condensed, plasticized, in the form of finer Extrudates through the perforated die plate in the extruder head and finally the extrudate preferably by means of a rotating knife reduced to approximately spherical to cylindrical granules. Of the Hole diameter of the perforated nozzle plate and the strand cut length are thereby matched to the selected granule size. In this embodiment the production of granules succeeds essentially uniformly Predeterminable particle size, with the absolute Particle sizes can be adapted to the intended application. in the particle diameters of up to at most 0.8 cm are generally preferred. Important embodiments see the production of uniform Granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from about 0.8 to 3 mm. The length / diameter ratio the chopped off primary granules in an important embodiment in the range from about 1: 1 to about 3: 1. Furthermore, it is preferred that the plastic and moist Feed raw 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 are obtained can. This shape can be done in standard rounding machines. Care should be taken to ensure that only small amounts of Fine grain fraction arise. The extrudates are then subjected to a drying step, for example, fed to a fluidized bed dryer. Here the extruded granules, which are peroxy bleaches, for example Perborate monohydrate, included, at supply air temperatures between 80 and 150 ° C can be dried without loss of active oxygen.

In the process according to the invention, zeolite (based on anhydrous active substance) in amounts of less than 19 wt .-% used, the amounts given on the optionally obtain dried extrudate, and sodium carbonate and sodium silicate in particular as granules or compound in the quantities in it Processes are introduced that the weight ratio - based in each case on anhydrous active substances - zeolite to the sum of carbonate and silicate 2: 1 to 1: 2 and preferably 1.5: 1 to 1: 1.5.

In a further preferred process variant, zeolite (based on anhydrous active substance) used only in amounts of 0 to 5 wt .-%. It is possible and in some cases may also be preferred that Zeolite co-extruded only partially or not at all, but subsequently is added to the crude extrudate. Overall, it is preferred to use the crude extrudate Add dry powder as a powder in amounts of up to 5% by weight where zeolite (anhydrous active substance) preferably in quantities from 0.1 to 2% by weight is used. The addition of powdering agents can doing this before, during or after the drying that may have been carried out take place, but preferably the addition after completion of the optionally carried out shaping processing step, for example is carried out in a commercial rounding machine.

Examples Example 1: Partial exchange of zeolite in the extrudate grain

According to the teaching of European patent EP-B-0486 592, the following were Means M1, M2 and M3 produced according to the invention and the comparison means V1 by extrusion and subsequent admixing of the bleach activator granules, of the enzyme granules and the foam inhibitor granules based on starch manufactured. The extrusion mixtures of agents M1 to M3 left extrude without procedural problems. The crude extrudates were each before mixing with a mixture of zeolite and silica powdered in a weight ratio of 4: 1. The compositions of the finished compositions in parts by weight were listed in Table 1. The Bulk density of the finished agents was between 720 and 780 g / l. The invention produced means had over all soiling tested at 60 ° C and a water hardness of 16 ° d a significantly better primary washing ability as the comparison means V1.

The Nabion 15 ^(R) used in the agents produced 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 g of the respective agent were pre-dissolved in 4 1 of water (16 ° d) at a temperature of 30 ° C for 15 seconds by hand. Then a Nicki sweater was submerged three times, pressed and turned by 90 °. After a minute, the sweater was removed from the soapy water and wrung out. The wash liquor was decanted off, the residues were transferred to a sieve and dried at 40 ° C. The residues 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 M1 has a significantly better residue behavior than V1, but also M2 and M3, which had higher alkyl sulfate contents than V1, also show an improved residue behavior. Compositions of agents M1 to M3 and V1 (in parts by weight) V1 M1 M2 M3 C ₉ -C ₁₃ alkylbenzenesulfonate 13.6 13.6 9.4 9.2 C ₁₂ -C ₁₈ alkyl sulfate 3.9 3.9 8.0 7.9 C ₁₂ -C ₁₈ alcohol with 5 EO 3.6 3.6 3.6 2.4 C ₁₂ -C ₁₈ fatty acid soap 0.7 0.7 0.8 0.5 Polyethylene glycol with a molecular weight of 400 1.5 1.5 1.5 2.4 Zeolite (anhydrous active substance) 22.3 17.6 17.6 17.0 sodium 6.3 ---- ---- 1.6 Nabion 15 ^(R) (anhydrous active substance) ---- 12.0 12.0 14.1 Acrylic acid-maleic acid copolymer (sodium salt) 3.5 3.5 3.5 2.3 amorphous sodium disilicate 1.5 1.5 1.5 1.0 Perborate monohydrate 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 Residue behavior in% V1 24.3 M1 13.9 M2 18.9 M3 19.6

Example 2: Full exchange of zeolite in the extrudate grain

As described in Example 1, the comparison agent V1 and the Agents M4 to M10 produced according to the invention are produced, the agents according to the invention manufactured means M4 to M10 distinguished from V1 in that they instead of the zeolite, the sodium carbonate and the acrylic acid-maleic acid polymer had the builder combinations given in Table 3. The extrusion mixtures of agents M4 to M10 could be processed without process technology Extrude problems even though the blends to be extruded did not contain any zeolite.

The primary washability of the agents M4 to M10 produced according to the invention was on Fat / pigment stains, protein-containing stains and high-fat stains Soiling significantly better than that of the comparative example V1 (Table 4). Only on bleachable stains (red wine and tea) were the performances of the agents M4 to M10 according to the invention compared to V1 right up to only slightly improved. So was the graying of the fabrics, that had been washed with agents M4 to M10, much less than when using V1. Surprisingly, some tissues were detected 25 washes with the agents M4 to M10 produced according to the invention even better remission values on than before the washes (Table 5). In addition, after 25 washes also determined the ash content of individual textile samples (table 6). The ash values for those washed with the agents produced according to the invention Tissues were not significantly worse than that for all tissues fabric washed with V1.

The application test was carried out under practical conditions in household washing machines. For this purpose, the machines with 3.0 kg clean laundry and 0.5 kg of test fabric loaded, the test fabric impregnated with conventional test soiling to test the primary washing ability was and to test the graying inhibition and the ash determination consisted of white fabric. Streaks were used as white test fabric made from standardized cotton fabric (Krefeld laundry research institute, WFK), nettle (BN), knitwear (cotton jersey; B) and terry fabric (FT) used.

Anschmutzungen:

Staub-Wollfett auf Baumwolle (SW-B)
Staub-Hautfett auf Baumwolle (SH-B)
Staub-Hautfett auf veredelter Baumwolle (SH-BV)
Staub-Hautfett auf Mischgewebe aus Polyester und veredelter Baumwolle (SH-PBV)
Milch-Ruß auf Baumwolle (MR-B)
Milch-Kakao auf Baumwolle (MK-B)

Primärwaschvermögen:

5fach-Bestimmung

Vergrauungsinhibierung und Aschebestimmung:

25 Wäschen Zusammensetzungen der Builderkombinationen in den Mitteln M4 bis M10 (in Gew.-Teilen) M4 M5 M6 M7 M8 M9 M10 Nabion 15^(R) (wasserfreie Aktiv-substanz) 25 25 20 20 20 20 20 Acrylsäure-Maleinsäure-Copolymer (Natriumsalz) 5 -- 10 7,5 5 2,5 -- Natriumcitrat-Dihydrat (wasserfreie Aktivsubstanz) -- 5 -- 2,5 5 7,5 10 Primärwaschvermögen (Remission in %) V1 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 ⊘ 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 ⊘ 76,2 79,4 79,2 78,8 79,3 78,5 Vergrauungsinhibierung (Remission in %) WFK BN B FT ⊘ Anfangswert 86,0 82,0 83,9 82,9 83,7 V1 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 M10 80,5 84,3 83,6 81,8 82,6 Asche-Werte Mittel Gew.-% Asche WFK BN FT B ⊘ Anfangswert 0,70 0,10 0,62 0,67 0,52 V1 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 M10 5,78 3,27 3,07 2,72 3,71

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 washing: liters of washing solution in the main wash cycle) 1: 5.7, Rinsing 3 times with tap water, spinning off and drying.

Soiling:

Dust-wool grease on cotton (SW-B)
Dust skin fat on cotton (SH-B)
Dust skin grease on refined cotton (SH-BV)
Dust-skin grease on blended fabrics made of polyester and finished 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 Compositions of the builder combinations in the compositions M4 to M10 (in parts by weight) M4 M5 M6 M7 M8 M9 M10 Nabion 15 ^(R) (anhydrous active substance) 25th 25th 20th 20th 20th 20th 20th Acrylic acid-maleic acid copolymer (sodium salt) 5 - 10th 7.5 5 2.5 - Sodium citrate dihydrate (anhydrous active substance) - 5 - 2.5 5 7.5 10th Primary washing power (remission in%) V1 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 ⊘ 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 ⊘ 76.2 79.4 79.2 78.8 79.3 78.5 Graying inhibition (remission in%) WFK BN B FT ⊘ Initial value 86.0 82.0 83.9 82.9 83.7 V1 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 M10 80.5 84.3 83.6 81.8 82.6 Ash values medium Wt% ash WFK BN FT B ⊘ Initial value 0.70 0.10 0.62 0.67 0.52 V1 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 M10 5.78 3.27 3.07 2.72 3.71

Claims (5)

1. A process for the production of an extruded detergent with a bulk density of more than 600 g/l containing anionic and optionally nonionic surfactants and, as water-soluble inorganic builders, sodium carbonate and amorphous sodium silicate, in which a solid free-flowing compound is extruded under pressures of up to 200 bar to form a strand, the strand thus formed after leaving the extrusion die is cut by means of a cutting unit into granules of a predetermined size and the still soft and optionally moist crude extrudate is subjected to another forming step and then dried, characterized in that sodium carbonate and amorphous sodium silicate (expressed as water-free active substances) are used in a total quantity of 10 to 40% by weight and in a ratio by weight of 5:1 to 1:10, the sodium carbonate being used at least partly in the form of granules, with the proviso that the quantities shown are based on the optionally dried extrudate, in that the extrudate is optionally compounded with other ingredients of detergents and in that zeolite is used in quantities of less than 19% by weight (expressed as water-free active substance).
2. A process as claimed in claim 1, characterized in that a carbonate/silicate compound obtained by spray drying or granulation, optionally followed by compacting, is used as the carbonate-containing granules.
3. A process as claimed in claim 1 or 2, characterized in that zeolite (expressed as water-free active substance) is used in quantities of 10 to 16% by weight and in that 10 to 30% by weight of a carbonate- and silicate-containing compound (expressed as water-free active substance) are used.
4. A process as claimed in claim 1 or 2, characterized in that zeolite (expressed as water-free active substance) is used in quantities of 0 to 5% by weight.
5. A process as claimed in any of claims 1 to 4, characterized in that dry powder is added to the crude extrudate as powdering agent in quantities of up to 5% by weight, zeolite (water-free active substance) preferably being used in quantities of 0.1 to 2% by weight.