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EP0746601B1 - Granular washing or cleaning agent - Google Patents

Granular washing or cleaning agent Download PDF

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Publication number
EP0746601B1
EP0746601B1 EP95910492A EP95910492A EP0746601B1 EP 0746601 B1 EP0746601 B1 EP 0746601B1 EP 95910492 A EP95910492 A EP 95910492A EP 95910492 A EP95910492 A EP 95910492A EP 0746601 B1 EP0746601 B1 EP 0746601B1
Authority
EP
European Patent Office
Prior art keywords
weight
extrudate
detergent
surfactants
extrudates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95910492A
Other languages
German (de)
French (fr)
Other versions
EP0746601A1 (en
Inventor
Eduard Smulders
Jochen Jacobs
Manfred Greger
Monika Böcker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
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Publication of EP0746601A1 publication Critical patent/EP0746601A1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds

Definitions

  • the invention relates to a granular detergent or cleaning agent which a high proportion of extruded components and an improved Has dissolving behavior.
  • the object of the invention was both to dissolve the extrudate Detergents or cleaning agents in the washing or cleaning liquor as well as the induction behavior of extrudate-containing detergents to improve.
  • the agents according to the invention can also contain further granular ones, in particular contain extruded components that are added to the mixture of these two partial extrudates are added.
  • extruded components that are added to the mixture of these two partial extrudates are added.
  • a partial extrudate I which contains surfactants from 25 to 40 wt .-% and a content of builder substances from the Group of zeolites (based on anhydrous active substance) and others Silicates, such as the amorphous silicates and the crystalline layered silicates, from 20 to 60% by weight.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those used in the production by esterification of a monoglycerol with 1 to 3 mols of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mols of glycerol be preserved.
  • anionic surfactants of the sulfate type are like the salts the sulfuric acid monoester from primary alcohols natural and synthetic Origin preferred.
  • alk (en) yl sulfates the alkali metal salts and in particular the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and preferred those secondary alcohols of this chain length.
  • 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 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.
  • the compositions 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.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • 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. Due to their high foaming behavior, they are only used in relatively small amounts in detergents.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, also known as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols represent. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or use their salts.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid or behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps.
  • the anionic surfactants and the soaps can be in the form of their alkali salts such as the sodium, potassium or ammonium salts and as soluble organic salts Bases, such as mono-, di- or triethanolamine, are present.
  • Bases such as mono-, di- or triethanolamine, are present.
  • the anionic surfactants and soaps in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • the content of the partial extrudates I in anionic surfactants is preferably 10 to 35 wt .-%, in particular 15 to 30 wt .-% fatty alk (en) yl sulfates and / or alkylbenzenesulfonate.
  • 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 can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • 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 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).
  • the partial extrudates I preferably contain 2 to 15% by weight of alkoxylated C 8 -C 18 alcohols and in particular 5 to 10% by weight of ethoxylated C 12 -C 18 alcohols.
  • 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-A-58/217598 are described or which are preferably according to the in the international patent application W0-A-90/13533 become.
  • surfactants described in JP 06/116599, which prevent gelation can also improve the Dissolving speed can be used.
  • More structure breakers that instead of these surfactants or can also be used are the Description can be found in the international patent application WO-A-93/02176.
  • 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; x is preferably 1.2 to 1.4.
  • the content of partial extrudates I in alkyl glycosides is generally about 0 to 5% by weight and preferably 0.5 to 3% by weight.
  • 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 and the alkoxylated fatty acid alkyl esters, in particular not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), 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 which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the finely crystalline, synthetic and bound water-containing zeolite used as builder substance is preferably zeolite NaA in detergent quality.
  • zeolite X or zeolite P and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite 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 or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • Layer substitutes are suitable substitutes or partial substitutes for the zeolite natural and synthetic origin.
  • Such layered silicates are, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405.
  • Their usability is not one special composition or structural formula limited. Are preferred here, however, smectites, especially bentonites.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number Number is from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula (II) are those in which M is sodium and x is 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • Amorphous silicates in particular sodium silicates with an Na 2 O: SiO 2 ratio of 1: 2.0 to 1: 3.0, preferably up to 1: 2.5, and / or carbonate-silicate compounds such as are also suitable they are commercially available as substitutes for the zeolite.
  • amorphous also means “X-ray amorphous” Roger that.
  • X-ray amorphous This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections as they do for crystalline ones Substances are typical, but at most one or more maxima scattered x-rays that are several units wide of the diffraction angle. However, it may very well be too special good builder properties lead when the silicate particles in electron diffraction experiments provide washed-out or even sharp diffraction maxima. This is to be interpreted as meaning that the products are microcrystalline Have ranges of size 10 to a few hundred nm.
  • the zeolite content of the partial extrudates I is preferably 25 to 50 wt .-% and in particular 25 to 45 wt .-%, with the Use of zeolite and crystalline layered silicates (II) a weight ratio 4: 1 to 1: 2, advantageously from 3: 1 to 1: 1, in particular is preferred.
  • weight ratios of 3: 1 to 1 : 3 and in particular from 2: 1 to 1: 2 are preferred.
  • organic builder substances can also be used.
  • Useful organic builder substances are preferred, for example polycarboxylic acids used in the form of their salts, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these.
  • Preferred salts are the sodium salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Their content in the partial extrudates I can generally 0 to 15 wt .-%.
  • 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.
  • polymeric polycarboxylates also preferred terpolymers described in the older German patent DE-C-42 21 381 and the older German patent application DE-A-43 00 722 to be discribed.
  • the content of polymeric polycarboxylates and inclusive the terpolymers is preferably 2 to 7% by weight.
  • Suitable ingredients of the partial extrudates I are - as already mentioned in part - water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the partial extrudates I is preferably up to 20% by weight, advantageously between 2 and 15% by weight.
  • the content of amorphous sodium silicate in the agents is generally up to 10% by weight and preferably between 1 and 5% by weight if the silicate is not used as a builder, because then the content can also significantly exceed 10% by weight .
  • the partial extrudates I can contain other known additives commonly used in detergents, for example Graying inhibitors, salts of polyphosphonic acids, enzymes, enzyme stabilizers, small amounts of neutral filling salts and, if necessary Dyes and fragrances, opacifiers or pearlescent and optical Brightener included.
  • the enzymes are advantageous not as components of partial extrudates I or II, but as a component another preferred granular component that also extrudes can be used.
  • the agents can also contain components that the oil and Influencing fat washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed.
  • 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 of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates.
  • Graying inhibitors have the task of detaching from 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.
  • soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethyl cellulose are preferred.
  • Carboxymethyl cellulose (sodium salt), Methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinyl pyrrolidone are preferred, for example in amounts of 0.1 to 5 % By weight, based on the partial extrudates I, used.
  • the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and Diethylenetriaminepentakis (methylenephosphonate) in amounts of 0.1 to 1.5 % By weight used.
  • the agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid 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 partial extrudate II preferably contains 0.1 to 15% by weight and in particular 2 to 12 wt .-%, each based on the partial extrudate II, surfactants such as given above, anionic surfactants and in particular alk (en) yl sulfates and / or alkylbenzenesulfates are preferred.
  • surfactants such as given above, anionic surfactants and in particular alk (en) yl sulfates and / or alkylbenzenesulfates are preferred.
  • the content of Soaps as above can range from 0 to about 2% by weight.
  • the partial extrudates II contain 30 to 55% by weight, advantageously 40 to 50% by weight, of peroxy bleaching agent, with perborate monohydrate, perborate tetrahydrate or percarbonate being particularly preferred.
  • peroxy bleaching agent for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the partial extrudates II can contain inorganic and organic builder substances as indicated above. It is preferred that these builder substances are present in amounts not exceeding 35% by weight, in particular in amounts of 10 to 30% by weight, based in each case on partial extrudate II.
  • the partial extrudate II is a foam inhibitor based on silicone and / or paraffin. It was surprisingly found that the effectiveness of the foam inhibitor can be raised after storage of the agent if it is not incorporated into partial extrudate I or subsequently mixed in, but is incorporated into the partial extrudate II.
  • the washing or cleaning agents according to the invention can be the partial extrudates I and II included in a wide weight ratio. It is however, it is particularly preferred that the agents partial extrudate I and partial extrudate II in a weight ratio greater than 1: 1, preferably from 1.2: 1 to 3: 1 and in particular from 1.5: 1 to 2.5: 1.
  • the partial extrudates can be made by any of the known extrusion or pelleting processes getting produced. In particular, however, it is preferred the partial extrudates according to the teaching of international patent application WO-A-91/02047 or WO-A-93/02176.
  • the partial extrudates can also contain components that increase the solubility of the densified Improve granules. Such components and the introduction of such Components are, for example, in the international patent application W0-A-93/02176 and in the older German patent application P 42 03 031.5 described.
  • the components preferably used include in particular Fatty alcohols with 10 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, as well as polyethylene glycols with a molecular weight between 200 and 2000. It has now been shown in production engineering trials that the lower pressure of at least 25 bar is not an absolutely fixed limit, but dependent on the type of extruder and throughput, for example can also fall below 7000 kg / h. At such high Throughputs obviously play a major role in apparatus technology parameters Role at smaller throughputs, for example between 600 and 2000 kg / h were unpredictable.
  • the anionic surfactants that may be present during manufacture of the solid premix intended for extrusion in the form of a spray-dried, granulated or extruded compounds. Furthermore, a method is preferred in which the surface of the partial extrudates to reduce the stickiness of the granules rich in nonionic surfactants is treated afterwards. Suitable surface modifiers are known from the prior art.
  • finely divided zeolites amorphous aluminosilicates, silicas, amorphous Silicates, fatty acids or fatty acid salts, for example calcium stearate, in particular, however, mixtures of zeolite and silica or zeolite and calcium stearate are particularly preferred.
  • the agents contain in addition to the partial extrudates I and II at least one further solid, which is preferably present as a granular component.
  • at least one further solid which is preferably present as a granular component.
  • bleach activators, enzymes and / or perfume to mix.
  • bleach activators are the N-acyl or O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonate, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate .
  • Particularly preferred bleach activators are N, N, N'N'-tetraacetylethylene diamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. They are particularly well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases, which are obtained from Bacillus lentus.
  • enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, Amylase and lipase or protease, lipase and cellulase, in particular Cellulase-containing and protease-containing mixtures of particular interest.
  • (Per) oxidases are also suitable.
  • the enzymes can on carriers adsorbed and / or embedded in enveloping substances around them protect against premature decomposition. It is also possible to use Proteases with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme, are stabilized.
  • the bulk density of the preferred granular agents is generally 300 to 1100 g / l, in particular 500 to 1000 g / l.
  • agents according to the invention which total about 10 to 35% by weight, advantageously 12 to 30% by weight of anionic and nonionic surfactants, 20 up to 60% by weight of builder substances, 10 to 25% by weight of peroxy bleach, 2 up to 15 wt .-%, in particular 5 to 10 wt .-% inorganic and alkaline acting salts such as carbonate and amorphous silicates, insofar as they do not belong to the Builder substances are to be expected, as well as foam inhibitors, bleach activators and contain enzymes.
  • the Agents according to the invention at 80 to 95% by weight from the partial extrudates, advantageously consists of the partial extrudates I and II.
  • Such agents preferably have a bulk density above 650 g / l and in particular at least 700 g / l.
  • Partial extrudate I contained 14.5% by weight of C 16 -C 18 alkyl sulfate, 8.5% by weight of C 12 -C 14 alkyl sulfate, 9.5% by weight of C 12 -C 18 fatty alcohol with 3 EO , 5.5% by weight sodium carbonate, 5% by weight Sokalan CP 5 (R) (copolymer of acrylic acid; commercial product from BASF, Federal Republic of Germany), 2.5% by weight sodium silicate with a Na 2 O: SiO 2 Ratio of 1: 2.0, 38.5 wt .-% zeolite (anhydrous active substance), 4 wt .-% sodium sulfate, 1.65 wt .-% salts from raw materials and the rest water.
  • the bulk density of extrudate I was 773 g / l.
  • Partial extrudate II contained 6.6% by weight of C 16 -C 18 alkyl sulfate, 4% by weight of C 12 -C 14 alkyl sulfate, 5.5% by weight of sodium carbonate, 5% by weight of Sokalan CP 5 ( R) , 1.7 wt .-% silicone oil, 2.2 wt .-% sodium silicate with a modulus of 2.0, 1.2 wt .-% sodium silicate with a modulus of 3.0, 7 wt .-% zeolite (based on anhydrous active substance), 49.5% by weight sodium perborate monohydrate, 9.5% by weight sodium sulfate, 0.8% by weight other salts from raw materials and the rest water.
  • the bulk density of extrudate II was 787 g / l.
  • agent M1 was produced, which consists of 65% by weight of extrudate I and consisted of 35 wt .-% of extrudate II. Another agent contained M2 59.8% by weight of extrudate 1, 32.2% by weight of extrudate II and 8% by weight of others Ingredients such as tetraacetylethylene diamine, protease, lipase and / or cellulase and perfume.
  • an agent V1 was produced from a uniform extrudate, that the ingredients of extrudates I and II in the quantitative ratio 65: 35 contained.
  • the solving time at 90% resolution was 2 for M1 Minutes and 29 seconds, for V1 3 minutes and 20 seconds.

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Abstract

Described are extruded washing or cleaning agents containing bleach, the washing or cleaning agents having an improved soil-releasing capability by virtue of the fact that they are made up of at least two extrudates. Extrudate I contains 20 to 50 % by wt. of surfactants and no bleach while extrudate II contains 0 to 15 % by wt. of surfactants and 20 to 60 % by wt. of bleach. The surfactants in extrudate II are preferably anionic surfactants such as alkyl or alkenyl sulphates and/or alkylbenzene sulphonates.

Description

Die Erfindung betrifft ein granulares Wasch- oder Reinigungsmittel, das zu einem hohen Anteil aus extrudierten Bestandteilen besteht und ein verbessertes Löseverhalten aufweist.The invention relates to a granular detergent or cleaning agent which a high proportion of extruded components and an improved Has dissolving behavior.

Aus der internationalen Patentanmeldung W0-A-91/02047 sind Granulate zur Anwendung in Wasch- oder Reinigungsmitteln bekannt, welche durch Extrusion erhalten werden. Dabei wird ein homogenes Vorgemisch unter Zusatz eines Plastifizier- und/oder Gleitmittels unter Druck strangförmig verpreßt (extrudiert). Die so hergestellten Extrudate können nachträglich mit weiteren Inhaltsstoffen von Wasch- oder Reinigungsmitteln, wobei diese Inhaltsstoffe vorzugsweise in granularer Form, insbesondere in extrudierter Form vorliegen können, aufbereitet werden.From the international patent application W0-A-91/02047 granules for Use in washing or cleaning agents known, which by extrusion be preserved. A homogeneous premix with the addition of a Plasticizer and / or lubricant extruded under pressure (extruded). The extrudates produced in this way can be retrofitted with others Ingredients of detergents or cleaning agents, these ingredients preferably in granular form, especially in extruded form Form can be prepared.

Die internationale Patentanmeldung W0-A-93/02176 offenbart, daß Extrudate ein verbessertes Löseverhalten aufweisen, wenn die eingesetzten flüssigen Niotenside in inniger Vermischung mit einem Strukturbrecher eingesetzt werden.International patent application WO-A-93/02176 discloses that extrudates have an improved dissolving behavior when the liquid used Nonionic surfactants used in intimate mixing with a structure breaker become.

Die Aufgabe der Erfindung bestand darin, sowohl das Löseverhalten Extrudat-haltiger Wasch- oder Reinigungsmittel in der Wasch- oder Reinigungsflotte als auch das Einspülverhalten Extrudat-haltiger Waschmittel weiter zu verbessern.The object of the invention was both to dissolve the extrudate Detergents or cleaning agents in the washing or cleaning liquor as well as the induction behavior of extrudate-containing detergents to improve.

Gegenstand der Erfindung ist dementsprechend in der ersten Ausführungsform ein granulares Wasch- oder Reinigungsmittel, enthaltend Granulate, welche durch Extrusion hergestellt werden, wobei das Mittel mindestens zwei Teilextrudate enthält, von denen das Teilextrudat I 20 bis 50 Gew.-%, bezogen auf das Teilextrudat I, Tenside enthält und frei von Bleichmitteln ist und das Teilextrudat II 0 bis 15 Gew.-%, bezogen auf das Teilextrudat II, Tenside und 20 bis 60 Gew.-% Bleichmittel enthält.The invention accordingly relates to the first embodiment a granular washing or cleaning agent containing granules, which be produced by extrusion, the agent having at least two partial extrudates contains, of which the partial extrudate I 20 to 50 wt .-%, based on the partial extrudate I, contains surfactants and is free from bleaching agents and the partial extrudate II 0 to 15 wt .-%, based on the partial extrudate II, surfactants and contains 20 to 60% by weight of bleach.

Die erfindungsgemäßen Mittel können noch weitere granulare, insbesondere extrudierte Bestandteile enthalten, die nachträglich zum Gemisch dieser zwei Teilextrudate hinzugemischt werden. Insbesondere sind jedoch Mittel bevorzugt, die ein Teilextrudat I enthalten, welches einen Gehalt an Tensiden von 25 bis 40 Gew.-% und einen Gehalt an Buildersubstanzen aus der Gruppe der Zeolithe (bezogen auf wasserfreie Aktivsubstanz) und sonstiger Silikate, wie der amorphen Silikate und der kristallinen Schichtsilikate, von 20 bis 60 Gew.-% aufweist.The agents according to the invention can also contain further granular ones, in particular contain extruded components that are added to the mixture of these two partial extrudates are added. In particular, however, are means preferred, which contain a partial extrudate I, which contains surfactants from 25 to 40 wt .-% and a content of builder substances from the Group of zeolites (based on anhydrous active substance) and others Silicates, such as the amorphous silicates and the crystalline layered silicates, from 20 to 60% by weight.

Als Tenside kommen dabei alle bekannten anionischen, nichtionischen, amphoteren und zwitterionischen Tenside in Betracht. Als anionische Tenside vom Sulfonat-Typ kommen vorzugsweise die bekannten C9-C13-Alkylbenzolsulfonate, α-0lefinsulfonate und Alkansulfonate in Betracht. Geeignet sind auch Ester von α-Sulfofettsäuren bzw. die Disalze der α-Sulfofettsäuren. Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester, welche Mono-, Di- und Triester sowie deren Gemische darstellen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden.All known anionic, nonionic, amphoteric and zwitterionic surfactants are suitable as surfactants. Suitable anionic surfactants of the sulfonate type are preferably the known C 9 -C 13 alkylbenzenesulfonates, α-olefinsulfonates and alkanesulfonates. Esters of α-sulfofatty acids or the disalts of α-sulfofatty acids are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those used in the production by esterification of a monoglycerol with 1 to 3 mols of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mols of glycerol be preserved.

Insbesondere sind jedoch anionische Tenside vom Sulfat-Typ wie die Salze der Schwefelsäuremonoester aus primären Alkoholen natürlichen und synthetischen Ursprungs bevorzugt.In particular, however, anionic surfactants of the sulfate type are like the salts the sulfuric acid monoester from primary alcohols natural and synthetic Origin preferred.

Als Alk(en)ylsulfate werden die Alkalisalze und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol, oder den C10-C20-Oxoalkoholen, und diejenigen sekundärer Alkohole dieser Kettenlänge bevorzugt. Weiterhin bevorzugt sind Alk(en)yl-sulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind C16-C18-Alk(en)ylsulfate insbesondere bevorzugt. Dabei kann es auch von besonderem Vorteil und insbesondere für maschinelle Waschmittel von Vorteil sein, C16-C18-Alk(en)ylsulfate in Kombination mit niedriger schmelzenden Aniontensiden und insbesondere mit solchen Aniontensiden, die einen niedrigeren Krafft-Punkt aufweisen und bei relativ niedrigen Waschtemperaturen von beispielsweise Raumtemperatur bis 40 °C eine geringe Kristallisationsneigung zeigen, einzusetzen. In einer bevorzugten Ausführungsform der Erfindung enthalten die Mittel daher Mischungen aus kurzkettigen und langkettigen Fettalkylsulfaten, vorzugsweise Mischungen aus C12-C14-Fettalkylsulfaten oder C12-C18-Fettalkylsulfaten mit C16-C18-Fettalkylsulfaten und insbesondere C12-C16-Fettalkylsulfaten mit C16-C18-Fettalkylsulfaten. In einer weiteren bevorzugten Ausführungsform der Erfindung werden jedoch nicht nur gesättigte Alkylsulfate, sondern auch ungesättigte Alkenylsulfate mit einer Alkenylkettenlänge von vorzugsweise C16 bis C22 eingesetzt. Dabei sind insbesondere Mischungen aus gesättigten, überwiegend aus C16 bestehenden sulfierten Fettalkoholen und ungesättigten, überwiegend aus C18 bestehenden sulfierten Fettalkoholen bevorzugt, beispielsweise solche, die sich von festen oder flüssigen Fettalkoholmischungen des Typs HD-Ocenol (R) (Handelsprodukt des Anmelders) ableiten. Dabei sind Gewichtsverhältnisse von Alkylsulfaten zu Alkenylsulfaten von 10:1 bis 1:2 und insbesondere von etwa 5:1 bis 1:1 bevorzugt.As alk (en) yl sulfates, the alkali metal salts and in particular the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and preferred those secondary alcohols of this chain length. 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 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 compositions 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.

Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-C21-Alkohole, wie 2-Methyl-verzweigte C9-C11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-C18-Fettalkohole mit 1 bis 4 EO, sind geeignet. Sie werden in Waschmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen eingesetzt.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. Due to their high foaming behavior, they are only used in relatively small amounts in detergents.

Geeignete Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, also known as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols represent. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or use their salts.

Weitere Bestandteile der erfindungsgemäß einzusetzenden Teilextrudate I können Seifen beispielsweise in Mengen von 0,5 bis 5 Gew.-% sein. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure der hydrierten Erucasäure oder Behensäure, sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische. Insbesondere sind solche Seifengemische bevorzugt, die zu 50 bis 100 Gew.-% aus gesättigten C12-C24-Fettsäureseifen zusammengesetzt sind.Other constituents of the partial extrudates I to be used according to the invention can be soaps, for example in amounts of 0.5 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 or 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.

Die anionischen Tenside sowie die Seifen können in Form ihrer Alkalisalze wie der Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside und Seifen in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants and the soaps can be in the form of their alkali salts such as the sodium, potassium or ammonium salts and as soluble organic salts Bases, such as mono-, di- or triethanolamine, are present. Preferably are the anionic surfactants and soaps in the form of their sodium or potassium salts, especially in the form of the sodium salts.

Der Gehalt der Teilextrudate I an anionischen Tensiden beträgt dabei vorzugsweise 10 bis 35 Gew.-%, insbesondere 15 bis 30 Gew.-% Fettalk(en)yl-sulfate und/oder Alkylbenzolsulfonat.The content of the partial extrudates I in anionic surfactants is preferably 10 to 35 wt .-%, in particular 15 to 30 wt .-% fatty alk (en) yl sulfates and / or alkylbenzenesulfonate.

Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann, bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-C14-Alkohole mit 3 EO oder 4 EO, C9-C11-Alkohol mit 7 EO, C13-C15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-Alkohol mit 5 E0. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Vorzugsweise enthalten die Teilextrudate I 2 bis 15 Gew.-% alkoxylierte C8-C18-Alkohole und insbesondere 5 bis 10 Gew.-% ethoxylierte C12-C18-Alkohole. 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 can 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 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). The partial extrudates I preferably contain 2 to 15% by weight of alkoxylated C 8 -C 18 alcohols and in particular 5 to 10% by weight of ethoxylated C 12 -C 18 alcohols.

Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP-A-58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung W0-A-90/13533 beschriebenen Verfahren hergestellt werden. Diese sowie andere in der JP 06/116599 beschriebenen Tenside, welche die Gelierung verhindern, können auch zur Verbesserung der Lösegeschwindigkeit eingesetzt werden. Weitere Strukturbrecher, die anstelle dieser Tenside oder zusätzlich eingesetzt werden können, sind der Beschreibung in der internationalen Patentanmeldung WO-A-93/02176 zu entnehmen.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-A-58/217598 are described or which are preferably according to the in the international patent application W0-A-90/13533 become. These and other surfactants described in JP 06/116599, which prevent gelation can also improve the Dissolving speed can be used. More structure breakers that instead of these surfactants or can also be used are the Description can be found in the international patent application WO-A-93/02176.

Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4. Der Gehalt der Teilextrudate I an Alkylglykosiden beträgt im allgemeinen etwa 0 bis 5 Gew.-% und vorzugsweise 0,5 bis 3 Gew.-%.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; x is preferably 1.2 to 1.4. The content of partial extrudates I in alkyl glycosides is generally about 0 to 5% by weight and preferably 0.5 to 3% by weight.

Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole und der alkoxylierten Fettsäurealkylester, insbesondere nicht mehr als die Hälfte davon.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 and the alkoxylated fatty acid alkyl esters, in particular not more than half of it.

Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel (I),

Figure 00060001
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. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
Figure 00060001
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 which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

Der als Buildersubstanz eingesetzte feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist vorzugsweise Zeolith NaA in Waschmittelqualität. Geeignet sind jedoch auch beispielsweise Zeolith X oder Zeolith P sowie Mischungen aus NaA und NaX. Der Zeolith kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, daß der Zeolith als Suspension eingesetzt wird, kann diese geringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten C12-C18-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen oder ethoxylierte Isotridecanole. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 µm (Volumenverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser.The finely crystalline, synthetic and bound water-containing zeolite used as builder substance is preferably zeolite NaA in detergent quality. However, zeolite X or zeolite P and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. 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 or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.

Geeignete Substitute bzw. Teilsubstitute für den Zeolith sind Schichtsilikate natürlichen und synthetischen Ursprungs. Derartige Schichtsilikate sind beispielsweise aus den Patentanmeldungen DE-B-23 34 899, EP-A-0 026 529 und DE-A-35 26 405 bekannt. Ihre Verwendbarkeit ist nicht auf eine spezielle Zusammensetzung bzw. Strukturformel beschränkt. Bevorzugt sind hier jedoch Smectite, insbesondere Bentonite. Layer substitutes are suitable substitutes or partial substitutes for the zeolite natural and synthetic origin. Such layered silicates are, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. Their usability is not one special composition or structural formula limited. Are preferred here, however, smectites, especially bentonites.

Weitere geeignete Substitute bzw. Teilsubstitute für den Zeolith sind kristalline, schichtförmige Natriumsilikate der allgemeinen Formel (II) NaMSixO2x+1·yH2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilikate werden beispielsweise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der Formel (II) sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate Na2Si2O5·yH2O bevorzugt.Further suitable substitutes or partial substitutes for the zeolite are crystalline, layered sodium silicates of the general formula (II) 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 Number is from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula (II) are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.

Außerdem eignen sich auch amorphe Silikate, insbesondere Natriumsilikate mit einem Na2O: SiO2-Verhältnis von 1 : 2,0 bis 1 : 3,0, vorzugsweise bis 1 : 2,5, und/oder Carbonat-Silikat-Compounds, wie sie im Handel erhältlich sind, als Substitute bzw. Teilsubstitute für den Zeolith.Amorphous silicates, in particular sodium silicates with an Na 2 O: SiO 2 ratio of 1: 2.0 to 1: 3.0, preferably up to 1: 2.5, and / or carbonate-silicate compounds such as are also suitable they are commercially available as substitutes for the zeolite.

Unter dem Begriff "amorph" wird im Rahmen der Erfindung auch "röntgenamorph" verstanden. Dies heißt, daß die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen. Es kann jedoch sehr wohl sogar zu besonders guten Buildereigenschaften führen, wenn die Silikatpartikel bei Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, daß die Produkte mikrokristalline Bereiche der Größe 10 bis einige Hundert nm aufweisen.In the context of the invention, the term “amorphous” also means “X-ray amorphous” Roger that. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections as they do for crystalline ones Substances are typical, but at most one or more maxima scattered x-rays that are several units wide of the diffraction angle. However, it may very well be too special good builder properties lead when the silicate particles in electron diffraction experiments provide washed-out or even sharp diffraction maxima. This is to be interpreted as meaning that the products are microcrystalline Have ranges of size 10 to a few hundred nm.

Der Gehalt der Teilextrudate I an Zeolith (bezogen auf wasserfreie Aktivsubstanz) und/oder an amorphen Silikaten und/oder Carbonat-Silikat-Compounds und/oder gegebenenfalls kristallinen Schichtsilikaten beträgt vorzugsweise 25 bis 50 Gew.-% und insbesondere 25 bis 45 Gew.-%, wobei beim Einsatz von Zeolith und kristallinen Schichtsilikaten (II) ein Gewichtsverhältnis 4:1 bis 1:2, vorteilhafterweise von 3:1 bis 1:1, insbesondere bevorzugt ist. Bei Mischungen aus Zeolith und röntgenamorphen Silikaten oder Carbonat-Silikat-Compounds sind Gewichtsverhältnisse von 3 : 1 bis 1 : 3 und insbesondere von 2 : 1 bis 1 : 2 bevorzugt. The zeolite content of the partial extrudates I (based on anhydrous active substance) and / or on amorphous silicates and / or carbonate-silicate compounds and / or optionally crystalline layered silicates is preferably 25 to 50 wt .-% and in particular 25 to 45 wt .-%, with the Use of zeolite and crystalline layered silicates (II) a weight ratio 4: 1 to 1: 2, advantageously from 3: 1 to 1: 1, in particular is preferred. For mixtures of zeolite and X-ray amorphous silicates or carbonate-silicate compounds are weight ratios of 3: 1 to 1 : 3 and in particular from 2: 1 to 1: 2 are preferred.

Zusätzlich können auch organische Buildersubstanzen eingesetzt werden. Brauchbare organische Buildersubstanzen sind beispielsweise die bevorzugt in Form ihrer Salze eingesetzten Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Natriumsalze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zukkersäuren und Mischungen aus diesen. Ihr Gehalt in den Teilextrudaten I kann im allgemeinen 0 bis 15 Gew.-% betragen.In addition, organic builder substances can also be used. Useful organic builder substances are preferred, for example polycarboxylic acids used in the form of their salts, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the sodium salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Their content in the partial extrudates I can generally 0 to 15 wt .-%.

Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150000 (auf Säure bezogen). Geeignete copolymere Polycarboxylate sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbesondere 50000 bis 100000. Insbesondere sind als polymere Polycarboxylate auch Terpolymere bevorzugt, die in dem älteren deutschen Patent DE-C-42 21 381 und der älteren deutschen Patentanmeldung DE-A-43 00 722 beschrieben werden. Der Gehalt der polymeren Polycarboxylate und einschließlich der Terpolymere beträgt vorzugsweise 2 bis 7 Gew.-%.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. In particular, polymeric polycarboxylates also preferred terpolymers described in the older German patent DE-C-42 21 381 and the older German patent application DE-A-43 00 722 to be discribed. The content of polymeric polycarboxylates and inclusive the terpolymers is preferably 2 to 7% by weight.

Weitere geeignete Inhaltsstoffe der Teilextrudate I sind - wie zum Teil bereits erwähnt - wasserlösliche anorganische Salze wie Bicarbonate, Carbonate, amorphe Silikate oder Mischungen aus diesen; insbesondere werden Alkalicarbonat und amorphes Alkalisilikat, vor allem Natriumsilikat mit einem molaren Verhältnis Na2O: SiO2 von 1:1 bis 1:4,5, vorzugsweise von 1:2 bis 1:3,5, eingesetzt. Der Gehalt der Teilextrudate I an Natriumcarbonat beträgt dabei vorzugsweise bis zu 20 Gew.-%, vorteilhafterweise zwischen 2 und 15 Gew.-%. Der Gehalt der Mittel an amorphem Natriumsilikat beträgt im allgemeinen bis zu 10 Gew.-% und vorzugsweise zwischen 1 und 5 Gew.-%, wenn das Silikat nicht als Builder eingesetzt wird, denn dann kann der Gehalt 10 Gew.-% auch deutlich überschreiten.Other suitable ingredients of the partial extrudates I are - as already mentioned in part - water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; In particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The sodium carbonate content of the partial extrudates I is preferably up to 20% by weight, advantageously between 2 and 15% by weight. The content of amorphous sodium silicate in the agents is generally up to 10% by weight and preferably between 1 and 5% by weight if the silicate is not used as a builder, because then the content can also significantly exceed 10% by weight .

Außer den genannten Inhaltsstoffen können die Teilextrudate I weitere bekannte, in Waschmitteln üblicherweise eingesetzte Zusatzstoffe, beispielsweise Vergrauungsinhibitoren, Salze von Polyphosphonsäuren, Enzyme, Enzymstabilisatoren, geringe Mengen an neutralen Füllsalzen sowie gegebenenfalls Farb- und Duftstoffe, Trübungsmittel oder Perglanzmittel und optische Aufheller enthalten. Vorteilhafterweise werden die Enzyme jedoch nicht als Bestandteile der Teilextrudate I oder II, sondern als Bestandteil einer weiteren vorzugsweisen granularen Komponente, die auch extrudiert sein kann, eingesetzt.In addition to the ingredients mentioned, the partial extrudates I can contain other known additives commonly used in detergents, for example Graying inhibitors, salts of polyphosphonic acids, enzymes, enzyme stabilizers, small amounts of neutral filling salts and, if necessary Dyes and fragrances, opacifiers or pearlescent and optical Brightener included. However, the enzymes are advantageous not as components of partial extrudates I or II, but as a component another preferred granular component that also extrudes can be used.

Zusätzlich können die Mittel auch Komponenten enthalten, welche die Ölund Fettauswaschbarkeit aus Textilien positiv beeinflussen. Dieser Effekt wird besonders deutlich, wenn ein Textil verschmutzt wird, das bereits vorher mehrfach mit einem erfindungsgemäßen Waschmittel, das diese öl- und fettlösende Komponente enthält, gewaschen wird. Zu den bevorzugten öl- und fettlösenden Komponenten zählen beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxypropylcellulose mit einem Anteil an Methoxyl-Gruppen von 15 bis 30 Gew.-% und an Hydroxypropoxyl-Gruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether, sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder der Terephthalsäure bzw. von deren Derivaten, insbesondere Polymere aus Ethylenterephthalaten und/oder Polyethylenglykolterephthalaten.In addition, the agents can also contain components that the oil and Influencing fat washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent 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 of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates.

Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Vergrauen zu verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die obengenannten Stärkeprodukte verwenden, z.B. abgebaute Stärke, Aldehydstärken usw.. Auch Polyvinylpyrrolidon ist brauchbar. Bevorzugt werden jedoch Celluloseether, wie Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische eingesetzt. Carboxymethylcellulose (Na-Salz), Methylcellulose, Methylhydroxyethylcellulose und deren Gemische sowie Polyvinylpyrrolidon werden bevorzugt, beispielsweise in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Teilextrudate I, eingesetzt.Graying inhibitors have the task of detaching from 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, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose are preferred. Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures used. Carboxymethyl cellulose (sodium salt), Methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinyl pyrrolidone are preferred, for example in amounts of 0.1 to 5 % By weight, based on the partial extrudates I, used.

Als Salze von Polyphosphonsäuren werden vorzugsweise die neutral reagierenden Natriumsalze von beispielsweise 1-Hydroxyethan-1,1-diphosphonat und Diethylentriaminpentakis-(methylenphosphonat) in Mengen von 0,1 bis 1,5 Gew.-% verwendet.The salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and Diethylenetriaminepentakis (methylenephosphonate) in amounts of 0.1 to 1.5 % By weight used.

Die Mittel können als optische Aufheller Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden.The agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid 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.

Das Teilextrudat II enthält vorzugsweise 0,1 bis 15 Gew.-% und insbesondere 2 bis 12 Gew.-%, jeweils bezogen auf das Teilextrudat II, Tenside wie oben angegeben, wobei anionische Tenside und insbesondere wiederum Alk(en)ylsulfate und/oder Alkylbenzolsulfate bevorzugt sind. Der Gehalt an Seifen wie oben kann 0 bis etwa 2 Gew.-% betragen.The partial extrudate II preferably contains 0.1 to 15% by weight and in particular 2 to 12 wt .-%, each based on the partial extrudate II, surfactants such as given above, anionic surfactants and in particular alk (en) yl sulfates and / or alkylbenzenesulfates are preferred. The content of Soaps as above can range from 0 to about 2% by weight.

Insbesondere enthalten die Teilextrudate II 30 bis 55 Gew.-%, vorteilhafterweise 40 bis 50 Gew.-% Peroxy-Bleichmittel, wobei Perboratmonohydrat, Perborattetrahydrat oder Percarbonat besonders bevorzugt sind. Weitere brauchbare Peroxy-Bleichmittel sind aber auch beispielsweise, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure oder Diperdodecandisäure. Weiterhin können die Teilextrudate II anorganische und organische Buildersubstanzen wie oben angegeben enthalten. Dabei ist es bevorzugt, daß diese Buildersubstanzen in Mengen nicht oberhalb 35 Gew.-%, insbesondere in Mengen von 10 bis 30 Gew.-%, jeweils bezogen auf das Teilextrudat II, vorhanden sind.In particular, the partial extrudates II contain 30 to 55% by weight, advantageously 40 to 50% by weight, of peroxy bleaching agent, with perborate monohydrate, perborate tetrahydrate or percarbonate being particularly preferred. However, other useful peroxy bleaches are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. Furthermore, the partial extrudates II can contain inorganic and organic builder substances as indicated above. It is preferred that these builder substances are present in amounts not exceeding 35% by weight, in particular in amounts of 10 to 30% by weight, based in each case on partial extrudate II.

In einer weiteren besonders bevorzugten Ausführungsform der Erfindung enthält das Teilextrudat II einen Schauminhibitor auf Silikon- und/oder Paraffin-Basis. Es wurde überraschenderweise gefunden, daß die Wirksamkeit des Schauminhibitors nach Lagerung des Mittels angehoben werden kann, wenn er nicht in das Teilextrudat I eingearbeitet oder nachträglich zugemischt, sondern in das Teilextrudat II eingearbeitet wird.In a further particularly preferred embodiment of the invention the partial extrudate II is a foam inhibitor based on silicone and / or paraffin. It was surprisingly found that the effectiveness of the foam inhibitor can be raised after storage of the agent if it is not incorporated into partial extrudate I or subsequently mixed in, but is incorporated into the partial extrudate II.

Die erfindungsgemäßen Wasch- oder Reinigungsmittel können die Teilextrudate I und II in einem breiten Gewichtsverhältnis enthalten. Dabei ist es jedoch insbesondere bevorzugt, daß die Mittel Teilextrudat I und Teilextrudat II in einem Gewichtsverhältnis von größer als 1 : 1, vorzugsweise von 1,2 : 1 bis 3 : 1 und insbesondere von 1,5 : 1 bis 2,5 : 1 enthalten.The washing or cleaning agents according to the invention can be the partial extrudates I and II included in a wide weight ratio. It is however, it is particularly preferred that the agents partial extrudate I and partial extrudate II in a weight ratio greater than 1: 1, preferably from 1.2: 1 to 3: 1 and in particular from 1.5: 1 to 2.5: 1.

Die Teilextrudate können nach jedem der bekannten Extrudier- bzw. Pelletierverfahren hergestellt werden. Insbesondere ist es jedoch bevorzugt, die Teilextrudate nach der Lehre der internationalen Patentanmeldung WO-A-91/02047 bzw. der WO-A-93/02176 herzustellen. Die Teilextrudate können außerdem Bestandteile enthalten, welche die Löslichkeit der verdichteten Granulate verbessern. Derartige Bestandteile und das Einbringen derartiger Bestandteile werden beispielsweise in der internationalen Patentanmeldung W0-A-93/02176 und in der älteren deutschen Patentanmeldung P 42 03 031.5 beschrieben. Zu den bevorzugt eingesetzten Bestandteilen gehören insbesondere Fettalkohole mit 10 bis 80 Mol Ethylenoxid pro Mol Fettalkohol, beispielsweise Talgfettalkohol mit 30 EO und Talgfettalkohol mit 40 EO, sowie Polyethylenglykole mit einer relativen Molekülmasse zwischen 200 und 2000. Es hat sich mittlerweile in produktionstechnischen Versuchen gezeigt, daß der in den genannten Anmeldungen offenbarte untere Druck von mindestens 25 bar keine absolut feste Grenze darstellt, sondern in Abhängigkeit von der Art des Extruders und des Durchsatzes von beispielsweise oberhalb 7000 kg/h auch unterschritten werden kann. Bei derartig hohen Durchsätzen spielen offensichtlich apparatetechnische Parameter eine große Rolle, die bei kleineren Durchsätzen, beispielsweise zwischen 600 und 2000 kg/h nicht vorhersehbar waren. In einer bevorzugten Ausführungsform der Erfindung werden die gegebenenfalls vorhandenen Aniontenside bei der Herstellung des zur Extrusion bestimmten festen Vorgemisches in Form eines sprühgetrockneten, granulierten oder extrudierten Compounds eingesetzt. Weiterhin ist ein Verfahren bevorzugt, bei dem die Oberfläche der Teilextrudate zur Reduzierung der Klebrigkeit der an Niotensiden reichen Granulate nachträglich behandelt wird. Geeignete Oberflächenmodifizierer sind dabei aus dem Stand der Technik bekannt. Neben weiteren geeigneten sind dabei feinteilige Zeolithe, amorphe Alumosilikate, Kieselsäuren, amorphe Silikate, Fettsäuren oder Fettsäuresalze, beispielsweise Calciumstearat, insbesondere jedoch Mischungen aus Zeolith und Kieselsäuren oder Zeolith und Calciumstearat besonders bevorzugt.The partial extrudates can be made by any of the known extrusion or pelleting processes getting produced. In particular, however, it is preferred the partial extrudates according to the teaching of international patent application WO-A-91/02047 or WO-A-93/02176. The partial extrudates can also contain components that increase the solubility of the densified Improve granules. Such components and the introduction of such Components are, for example, in the international patent application W0-A-93/02176 and in the older German patent application P 42 03 031.5 described. The components preferably used include in particular Fatty alcohols with 10 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, as well as polyethylene glycols with a molecular weight between 200 and 2000. It has now been shown in production engineering trials that the lower pressure of at least 25 bar is not an absolutely fixed limit, but dependent on the type of extruder and throughput, for example can also fall below 7000 kg / h. At such high Throughputs obviously play a major role in apparatus technology parameters Role at smaller throughputs, for example between 600 and 2000 kg / h were unpredictable. In a preferred embodiment of the Invention, the anionic surfactants that may be present during manufacture of the solid premix intended for extrusion in the form of a spray-dried, granulated or extruded compounds. Furthermore, a method is preferred in which the surface of the partial extrudates to reduce the stickiness of the granules rich in nonionic surfactants is treated afterwards. Suitable surface modifiers are known from the prior art. In addition to other suitable ones finely divided zeolites, amorphous aluminosilicates, silicas, amorphous Silicates, fatty acids or fatty acid salts, for example calcium stearate, in particular, however, mixtures of zeolite and silica or zeolite and calcium stearate are particularly preferred.

In einer bevorzugten Ausführungsform der Erfindung enthalten die Mittel zusätzlich zu den Teilextrudaten I und II mindestens einen weiteren Feststoff, der vorzugsweise als granulare Komponente vorliegt. Insbesondere ist es dabei bevorzugt, Bleichaktivatoren, Enzyme und/oder Parfüm nachträglich zuzumischen. Ebenso ist es auch möglich und kann in Abhängigkeit von der Rezeptur von Vorteil sein, wenn weitere einzelne Bestandteile des Mittels, beispeilsweise Carbonat, Citrat bzw. Citronensäure oder andere Polycarboxylate bzw. Polycarbonsäuren, polymere Polycarboxylate, Zeolith und/oder Schichtsilikate, die gegebenenfalls kristallin sein können, nachträglich zu den Teilextrudaten hinzuzugeben.In a preferred embodiment of the invention, the agents contain in addition to the partial extrudates I and II at least one further solid, which is preferably present as a granular component. In particular it is preferred to subsequently add bleach activators, enzymes and / or perfume to mix. It is also possible and can be dependent be of advantage from the recipe if other individual components of the By means of, for example, carbonate, citrate or citric acid or others Polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, which can optionally be crystalline, subsequently to be added to the partial extrudates.

Beispiele für geeignete Bleichaktivatoren sind die mit H2O2 organische Persäuren bildenden N-Acyl- bzw. O-Acyl-Verbindungen, vorzugsweise N,N'-tetraacylierte Diamine, p-(Alkanoyloxy)benzolsulfonat, ferner Carbonsäureanhydride und Ester von Polyolen wie Glucosepentaacetat. Besonders bevorzugte Bleichaktivatoren sind N,N,N'N'-Tetraacetylethylendiamin und 1,5-Diacetyl-2,4-dioxo-hexahydro-1,3,5-triazin. Examples of suitable bleach activators are the N-acyl or O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonate, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate . Particularly preferred bleach activators are N, N, N'N'-tetraacetylethylene diamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind die aus Bakterienstämmen oder Pilzen wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase oder Protease und Cellulase oder aus Cellulase und Lipase oder aus Protease, Amylase und Lipase oder Protease, Lipase und Cellulase, insbesondere Cellulase-haltige und Protease-haltige Mischungen von besonderem Interesse. Auch (Per-)Oxidasen sind geeignet. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen und einem Calciumgehalt von vorzugsweise etwa 1,2 Gew.-%, bezogen auf das Enzym, stabilisiert sind.Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. They are particularly well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases, which are obtained from Bacillus lentus. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, Amylase and lipase or protease, lipase and cellulase, in particular Cellulase-containing and protease-containing mixtures of particular interest. (Per) oxidases are also suitable. The enzymes can on carriers adsorbed and / or embedded in enveloping substances around them protect against premature decomposition. It is also possible to use Proteases with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme, are stabilized.

Das Schüttgewicht der bevorzugten granularen Mittel beträgt im allgemeinen 300 bis 1100 g/l, insbesondere 500 bis 1000 g/l. Insbesondere bevorzugt sind erfindungsgemäße Mittel, welche insgesamt etwa 10 bis 35 Gew.-%, vorteilhafterweise 12 bis 30 Gew.-% anionische und nichtionische Tenside, 20 bis 60 Gew.-% Buildersubstanzen, 10 bis 25 Gew.-% Peroxy-Bleichmittel, 2 bis 15 Gew.-%, insbesondere 5 bis 10 Gew.-% anorganische und alkalisch wirkende Salze wie Carbonat und amorphe Silikate, soweit sie nicht zu den Buildersubstanzen gerechnet werden, sowie Schauminhibitoren, Bleichaktivatoren und Enzyme enthalten. Dabei ist es insbesondere bevorzugt, daß das erfindungsgemäße Mittel zu 80 bis 95 Gew.-% aus den Teilextrudaten, vorteilhafterweise aus den Teilextrudaten I und II, besteht.The bulk density of the preferred granular agents is generally 300 to 1100 g / l, in particular 500 to 1000 g / l. Particularly preferred are agents according to the invention, which total about 10 to 35% by weight, advantageously 12 to 30% by weight of anionic and nonionic surfactants, 20 up to 60% by weight of builder substances, 10 to 25% by weight of peroxy bleach, 2 up to 15 wt .-%, in particular 5 to 10 wt .-% inorganic and alkaline acting salts such as carbonate and amorphous silicates, insofar as they do not belong to the Builder substances are to be expected, as well as foam inhibitors, bleach activators and contain enzymes. It is particularly preferred that the Agents according to the invention at 80 to 95% by weight from the partial extrudates, advantageously consists of the partial extrudates I and II.

Derartige Mittel weisen vorzugsweise ein Schüttgewicht oberhalb von 650 g/l und insbesondere mindestens von 700 g/l auf. Such agents preferably have a bulk density above 650 g / l and in particular at least 700 g / l.

BeispieleExamples

In einem kontinuierlich arbeitenden Mischer, der mit einem Messerkopf-Zerkleinerer (Zerhacker) ausgerüstet war, wurden zwei Vorgemische I und II hergestellt und gemäß der Lehre der internationalen Patentanmeldung WO-A-91/02047 extrudiert. Die fertigen Teilextrudate I und II, deren Zusammensetzungen unten angegeben sind, wurden getrocknet, jedoch nicht weiter aufgearbeitet.In a continuously working mixer with a cutter head shredder (Chopper) was equipped, two premixes I and II produced and according to the teaching of international patent application WO-A-91/02047 extruded. The finished partial extrudates I and II, their compositions were dried, but not further worked up.

Teilextrudat I enthielt 14,5 Gew.-% C16-C18-Alkylsulfat, 8,5 Gew.-% C12-C14-Alkylsulfat, 9,5 Gew.-% C12-C18-Fettalkohol mit 3 EO, 5,5 Gew.-% Natriumcarbonat, 5 Gew.-% Sokalan CP 5(R) (copolymeres der Acrylsäure; Handelsprodukt der BASF, Bundesrepublik Deutschland), 2,5 Gew.-% Natriumsilikat mit einem Na2O: SiO2-Verhältnis von 1 : 2,0, 38,5 Gew.-% Zeolith (wasserfreie Aktivsubstanz), 4 Gew.-% Natriumsulfat, 1,65 Gew.-% Salze aus Rohstoffen und Rest Wasser. Das Schüttgewicht des Extrudats I betrug 773 g/l. Das Teilextrudat II enthielt 6,6 Gew.-% C16-C18-Alkylsulfat, 4 Gew.-% C12-C14-Alkylsulfat, 5,5 Gew.-% Natriumcarbonat, 5 Gew.-% Sokalan CP 5(R), 1,7 Gew.-% Silikonöl, 2,2 Gew.-% Natriumsilikat mit einem Modul von 2,0, 1,2 Gew.-% Natriumsilikat mit einem Modul von 3,0, 7 Gew.-% Zeolith (bezogen auf wasserfreie Aktivsubstanz), 49,5 Gew.-% Natriumperboratmonohydrat, 9,5 Gew.-% Natriumsulfat, 0,8 Gew.-% sonstige Salze aus Rohstoffen und Rest Wasser. Das Schüttgewicht des Extrudats II betrug 787 g/l.Partial extrudate I contained 14.5% by weight of C 16 -C 18 alkyl sulfate, 8.5% by weight of C 12 -C 14 alkyl sulfate, 9.5% by weight of C 12 -C 18 fatty alcohol with 3 EO , 5.5% by weight sodium carbonate, 5% by weight Sokalan CP 5 (R) (copolymer of acrylic acid; commercial product from BASF, Federal Republic of Germany), 2.5% by weight sodium silicate with a Na 2 O: SiO 2 Ratio of 1: 2.0, 38.5 wt .-% zeolite (anhydrous active substance), 4 wt .-% sodium sulfate, 1.65 wt .-% salts from raw materials and the rest water. The bulk density of extrudate I was 773 g / l. Partial extrudate II contained 6.6% by weight of C 16 -C 18 alkyl sulfate, 4% by weight of C 12 -C 14 alkyl sulfate, 5.5% by weight of sodium carbonate, 5% by weight of Sokalan CP 5 ( R) , 1.7 wt .-% silicone oil, 2.2 wt .-% sodium silicate with a modulus of 2.0, 1.2 wt .-% sodium silicate with a modulus of 3.0, 7 wt .-% zeolite (based on anhydrous active substance), 49.5% by weight sodium perborate monohydrate, 9.5% by weight sodium sulfate, 0.8% by weight other salts from raw materials and the rest water. The bulk density of extrudate II was 787 g / l.

Zur Bestimmung des Löseverhaltens wurden in einem 1-Liter-Gefäß 500 ml demineralisiertes Wasser (20 °C) eingefüllt, der Propellerrührer mit einer Drehzahl von 900 U/pm eingeschaltet und die Leitfähigkeitsmeßzelle eingetaucht. Danach wurden jeweils 5 g des Extrudats I bzw. II zugegeben. Die Änderung der Leitfähigkeit wurde über einen Schreiber festgehalten; die Messung erfolgte, bis kein Anstieg der Leitfähigkeit mehr feststellbar war. Die Zeit zum Erreichen der Leitfähigkeitskonstanz ist die Lösezeit des jeweiligen Extrudats (100 %). Die Zeit zum Erreichen einer 90%igen Auflösung wurde rechnerisch ermittelt. Die Lösezeit (90 %) des Extrudats I betrug nur 2 Minuten. Die Lösezeit (90 %) des Extrudats II betrug sogar nur 1 Minute und 20 Sekunden.To determine the dissolving behavior, 500 ml were in a 1 liter vessel demineralized water (20 ° C) filled, the propeller with a Speed of 900 U / pm switched on and the conductivity measuring cell immersed. Then 5 g of extrudate I and II were added in each case. The Changes in conductivity were recorded by a clerk; the Measurement was carried out until the conductivity no longer increased was. The time to reach constant conductivity is the dissolving time of the respective extrudate (100%). The time to reach a 90% The resolution was calculated. The dissolution time (90%) of extrudate I was only 2 minutes. The dissolution time (90%) of extrudate II was even only 1 minute and 20 seconds.

Es wurde ein Mittel M1 hergestellt, welches zu 65 Gew.-% aus Extrudat I und zu 35 Gew.-% aus Extrudat II bestand. Ein weiteres Mittel M2 enthielt 59,8 Gew.-% Extrudat 1, 32,2 Gew.-% Extrudat II sowie 8 Gew.-% weitere Inhaltsstoffe wie Tetraacetylethylendiamin, Protease, Lipase und/oder Cellulase und Parfüm.An agent M1 was produced, which consists of 65% by weight of extrudate I and consisted of 35 wt .-% of extrudate II. Another agent contained M2 59.8% by weight of extrudate 1, 32.2% by weight of extrudate II and 8% by weight of others Ingredients such as tetraacetylethylene diamine, protease, lipase and / or cellulase and perfume.

Zum Vergleich wurde ein Mittel V1 aus einem einheitlichen Extrudat hergestellt, das die Inhaltsstoffe der Extrudate I und II in dem Mengenverhältnis 65 : 35 enthielt. Die Lösezeit bei 90%iger Auflösung betrug für M1 2 Minuten und 29 Sekunden, für V1 3 Minuten und 20 Sekunden.For comparison, an agent V1 was produced from a uniform extrudate, that the ingredients of extrudates I and II in the quantitative ratio 65: 35 contained. The solving time at 90% resolution was 2 for M1 Minutes and 29 seconds, for V1 3 minutes and 20 seconds.

Claims (12)

  1. A granular detergent containing granules produced by extrusion, characterized in that it contains at least two extrudates, extrudate I containing 20 to 50% by weight, based on extrudate I, of surfactants and being free from bleaching agent and extrudate II containing 0 to 15% by weight, based on extrudate II, of surfactants and 20 to 60% by weight of bleaching agent.
  2. A detergent as claimed in claim 1, characterized in that extrudate I contains 25 to 40% by weight of surfactants and 20 to 60% by weight, preferably 25 to 50% by weight, of builders from the group of zeolites (based on water-free active substance), amorphous silicates and crystalline layered silicates.
  3. A detergent as claimed in claim 1 or 2, characterized in that extrudate I contains zeolite and crystalline layered silicates (II) NaMSixO2x+1 ·yH2O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4, in quantities of 25 to 45% by weight, a ratio by weight of 4:1 to 1:2 being preferred.
  4. A detergent as claimed in claim 1 or 2, characterized in that extrudate I contains zeolite and X-ray amorphous silicates or carbonate/silicate compounds in a ratio by weight of 3:1 to 1:3 and, more particularly, 2:1 to 1:2.
  5. A detergent as claimed in any of claims 1 to 4, characterized in that extrudate II contains 0.1 to 15% by weight and preferably 2 to 12% by weight, based on extrudate II, of surfactants and 30 to 55% by weight and preferably 40 to 50% by weight of peroxy bleaching agent, more especially perborate monohydrate, perborate tetrahydrate or percarbonate.
  6. A detergent as claimed in any of claims 1 to 5, characterized in that extrudate II contains inorganic or organic builders in quantities of not more than 35% by weight and preferably in quantities of 10 to 30% by weight, based on extrudate II.
  7. A detergent as claimed in any of claims 1 to 6, characterized in that extrudate II contains a silicone- and/or paraffin-based foam inhibitor.
  8. A detergent as claimed in any of claims 1 to 7, characterized in that it contains extrudate I and extrudate II in a ratio by weight of greater than 1:1, preferably in a ratio by weight of 1.2:1 to 3:1 and more preferably in a ratio by weight of 1.5:1 to 2.5:1.
  9. A detergent as claimed in any of claims 1 to 8, characterized in that at least one extrudate was subsequently treated with a surface modifier preferably selected from fine-particle zeolites, amorphous alumosilicates, silicas, amorphous silicates, fatty acids or fatty acid salts and, more particularly, mixtures of zeolite and silicas or zeolite and calcium stearate.
  10. A detergent as claimed in any of claims 1 to 9, characterized in that it contains at least one other solid, preferably a granular component.
  11. A detergent as claimed in claim 10, characterized in that another granular component contains enzymes.
  12. A detergent as claimed in any of claims 1 to 11, characterized in that 80 to 95% by weight of the detergent consists of extrudates, advantageously of extrudates I and II.
EP95910492A 1994-02-25 1995-02-16 Granular washing or cleaning agent Expired - Lifetime EP0746601B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4406210 1994-02-25
DE4406210A DE4406210A1 (en) 1994-02-25 1994-02-25 Granular detergent or cleaning agent
PCT/EP1995/000567 WO1995023207A1 (en) 1994-02-25 1995-02-16 Granular washing or cleaning agent

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Publication Number Publication Date
EP0746601A1 EP0746601A1 (en) 1996-12-11
EP0746601B1 true EP0746601B1 (en) 2000-01-12

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EP95910492A Expired - Lifetime EP0746601B1 (en) 1994-02-25 1995-02-16 Granular washing or cleaning agent

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EP (1) EP0746601B1 (en)
AT (1) ATE188730T1 (en)
AU (1) AU1757895A (en)
DE (2) DE4406210A1 (en)
DK (1) DK0746601T3 (en)
ES (1) ES2143044T3 (en)
HU (1) HUT75202A (en)
PL (1) PL315976A1 (en)
WO (1) WO1995023207A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4429550A1 (en) * 1994-08-19 1996-02-22 Henkel Kgaa Process for the production of detergent tablets
DE19501117A1 (en) * 1995-01-17 1996-07-18 Henkel Kgaa Bleaching detergent in granular form
DE19519139A1 (en) * 1995-05-30 1996-12-05 Henkel Kgaa Granular detergent or cleaning agent with high bulk density
DE19524722A1 (en) * 1995-07-12 1997-01-16 Henkel Kgaa Granular washing or cleaning agent with high bulk density
GB9711356D0 (en) 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
WO2019130146A1 (en) * 2017-12-29 2019-07-04 Zobele Holding S.P.A. Laundry additive for removing stains

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0672237B2 (en) * 1984-09-14 1994-09-14 花王株式会社 Process for making high density granular detergents with improved fluidity.
US4678594A (en) * 1985-07-19 1987-07-07 Colgate-Palmolive Company Method of encapsulating a bleach and activator therefor in a binder
GB8625474D0 (en) * 1986-10-24 1986-11-26 Unilever Plc Soap noodles
ES2055441T3 (en) * 1989-08-09 1994-08-16 Henkel Kgaa OBTAINING COMPACT GRANULATES FOR DETERGENTS.

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DE59507614D1 (en) 2000-02-17
DE4406210A1 (en) 1995-08-31
ATE188730T1 (en) 2000-01-15
EP0746601A1 (en) 1996-12-11
DK0746601T3 (en) 2000-05-29
WO1995023207A1 (en) 1995-08-31
AU1757895A (en) 1995-09-11
HUT75202A (en) 1997-04-28
ES2143044T3 (en) 2000-05-01
PL315976A1 (en) 1996-12-23
HU9602333D0 (en) 1996-10-28

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