WO1995023207A1 - Granulares wasch- oder reinigungsmittel - Google Patents

Granulares wasch- oder reinigungsmittel Download PDF

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Publication number
WO1995023207A1
WO1995023207A1 PCT/EP1995/000567 EP9500567W WO9523207A1 WO 1995023207 A1 WO1995023207 A1 WO 1995023207A1 EP 9500567 W EP9500567 W EP 9500567W WO 9523207 A1 WO9523207 A1 WO 9523207A1
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WO
WIPO (PCT)
Prior art keywords
extrudate
partial
weight
composition according
zeolite
Prior art date
Application number
PCT/EP1995/000567
Other languages
German (de)
English (en)
French (fr)
Inventor
Eduard Smulders
Jochen Jacobs
Manfred Greger
Monika Böcker
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to PL95315976A priority Critical patent/PL315976A1/xx
Priority to DK95910492T priority patent/DK0746601T3/da
Priority to EP95910492A priority patent/EP0746601B1/de
Priority to DE59507614T priority patent/DE59507614D1/de
Priority to AT95910492T priority patent/ATE188730T1/de
Priority to AU17578/95A priority patent/AU1757895A/en
Publication of WO1995023207A1 publication Critical patent/WO1995023207A1/de

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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 washing or cleaning agent which consists to a large extent of extruded components and has an improved dissolving behavior.
  • the object of the invention was to further improve both the dissolving behavior of extrudate-containing detergents or cleaning agents in the washing or cleaning liquor and the induction behavior of extrudate-containing detergents.
  • the invention in the first embodiment relates to a granular washing or cleaning agent containing granules which are produced by extrusion, the agent containing at least two partial extrudates, of which the partial extrudate I 20 to 50% by weight, based on the partial extrudate I contains surfactants and is free of bleaching agents and the partial extrudate II contains 0 to 15% by weight, based on the partial extrudate II, tenides and 20 to 60% by weight of bleaching agent.
  • the agents according to the invention can also contain further granular, in particular extruded, components which are subsequently mixed into the mixture of these two partial extrudates.
  • a partial extrudate I which contains a surfactant content of 25 to 40% by weight and a content of fluoride substances from the group of the zeolites (based on anhydrous active substance) and other silicates, such as the amorphous silicates and crystalline layered silicates, from 20 to 60 wt .-% has.
  • anionic, nonionic, amphoteric and zwitterionic surfactants are suitable as surfactants.
  • the known Cg-Ci3-alkylbenzenesulfonates, ⁇ -olefin sulfonates and alkanesulfonates are preferably suitable as anionic surfactants of the sulfonate type.
  • Esters of oc-sulfofatty acids or the disalts of ⁇ -sulfofatty acids are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 Moles of glycerol can be obtained.
  • anionic surfactants of the sulfate type such as the salts of the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, are preferred.
  • alk (en) yl sulfates the alkali metal salts and in particular the sodium salts of the sulfuric acid semiesters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ⁇ o-C2 ⁇ _ 0xoalcohols, and those secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • Ci6-Ci8-alk (en) yl sulfates are particularly preferred for washing technology reasons. It can also be of particular advantage, and particularly advantageous for machine washing agents, that Ciö-Ci8-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 at relatively low washing temperatures of, for example, room temperature to 40 ° C. a low crystalline show tendency to use.
  • the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of Ci2-i4-fatty alkyl sulfates or C ⁇ 2-Ci8-fatty alkyl sulfates with Ciö-Cis-fatty alkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with Ciö-Cis -Fatty alkyl sulfates.
  • not only saturated alkyl sulfates, but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably (5 to C22) are used.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (E0) or C ⁇ - Ci ⁇ fatty alcohols with 1 to 4 E0 are suitable. Because of their high foaming behavior, they are only used in relatively small amounts in detergents.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • compositions of the partial extrudates I according to the invention can be soaps, for example in amounts of 0.5 to 5% by weight.
  • Saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid or behenic acid, and in particular from natural fatty acids, for example coconut oil, palm kernel oil or tallow oil, are suitable.
  • fatty acids, derived soap mixtures are suitable which are composed of 50 to 100% by weight of saturated Ci2-24 _ * r ettic acid soaps.
  • the anionic surfactants and the soaps can be present in the form of their alkali metal salts, such as the sodium, potassium or ammonium salts, and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants and soaps are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of anionic surfactants in the partial extrudates I is preferably 10 to 35% by weight, in particular 15 to 30% by weight, of 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 (E0) per mole of alcohol in which the alcohol radical has a methyl or linear branching, preferably in the 2-position may be, or may contain linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 E0, Cg-Cn alcohol with 7 E0, Ci3-Ci5 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, Ci2-Ci8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of Ci2 ⁇ Ci4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical mean values which can be an integer or a fractional number for a special 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 1 -C 4 -alcohols and in particular 5 to 10% by weight of ethoxylated C 1 -C 8 -alcohols.
  • Another class of preferably used nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP-A-58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533 ⁇ be put.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, C. -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligo erization 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-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols and the alkoxylated fatty acid alkyl esters, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid of the formula (I), R3
  • R- ⁇ CO for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanol and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • 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 which is still moist from its production.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-Ci8 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.
  • Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin.
  • Layered silicates of this type are known, 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 limited to a special composition or structural formula.
  • smectites, in particular bentonites, are preferred here.
  • Suitable substitutes or partial substitutes for the zeolite are crystalline, layered sodium silicates of the general formula (II) NaMSi x ⁇ 2 ⁇ + yH2 ⁇ , where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline sheet silicates of the formula (II) are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and fr-sodium disilicate Na2Si2 ⁇ 5-yH2 ⁇ are preferred.
  • amorphous is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experts do not provide sharp X-ray reflections as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays which have a width of several degree units of the diffraction angle. However, it can very well even lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size 10 to a few hundred nm.
  • the content of the partial extrudates I in zeolite (based on anhydrous active substance) and / or in amorphous silicates and / or carbonate-silicate compounds and / or optionally crystalline sheet silicates is preferably 25 to 50% by weight and in particular 25 to 45% by weight, a weight ratio of 4: 1 to 1: 2, advantageously of 3: 1 to 1: 1 being particularly preferred when using zeolite and crystalline layered silicates (II).
  • weight ratios of 3: 1 to 1: 3 and in particular of 2: 1 to 1: 2 are preferred.
  • organic builder substances can also be used.
  • Usable organic builder substances are, for example, the polycarboxylic acids preferably used in the form of their salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons , and mixtures of these.
  • Preferred salts are the sodium salts of the 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 be 0 to 15% by weight.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polyethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • terpolymers which are described in the older German patent DE-C-4221 381 and the older German patent application DE-A-4300722 can be described.
  • the content of the polymeric polycarboxylates and including 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 Na2 ⁇ : SiÜ2 from 1: 1 to 1: 4.5, preferably from 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 amorphous sodium silicate content of 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 further known additives which are usually used in detergents, for example graying inhibitors, salts of polyphosphonic acids, enzymes, enzyme stabilizers, small amounts of neutral filling salts and, if appropriate, colorants and fragrances, opacifiers or Pearlescent agents and optical brighteners contain.
  • the enzymes are advantageously not used as constituents of partial extrudates I or II, but rather as constituents of a further, preferably granular component, which can also be extruded.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, eg degraded starch, aldehyde starches etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used.
  • Carboxyethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinylpyrrolidone are preferred, for example in amounts of 0.1 to 5% by weight, based on the partial extrudates I, are used.
  • the salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate and diethylenetriaminepentakis (methylenephosphonate) in amounts of 0.1 to 1.5% by weight.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds, instead of morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
  • the partial extrudate II preferably contains 0.1 to 15% by weight and in particular 2 to 12% by weight, in each case based on the partial extrudate II, surfactants as indicated above, anionic surfactants and in particular alkene (s) in turn yl sulfates and / or alkylbenzene sulfates are preferred.
  • the soap content 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 agents, with perborate monohydrate, perborate tetrahydrate or percarbonate being particularly preferred.
  • peroxy bleaching agents are, for example, peroxy pyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperododecanedioic 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 contains a foam inhibitor based on silicone and / or paraffin. It has surprisingly been found that the effectiveness of the foam inhibitor can be increased after storage of the composition if it is not incorporated into the partial extrudate I or subsequently admixed, but instead is incorporated into the partial extrudate II.
  • the washing or cleaning agents according to the invention can contain the partial extrudates I and II in a broad weight ratio. However, it is particularly preferred that the agents partial extrudate I and partial extrudate II in a weight ratio of greater than 1: 1, preferably from 1.2: 1 to 3: 1 and in particular from 1.5: 1 to 2.5 : 1 included.
  • the partial extrudates can be produced by any of the known extrusion or pelletizing processes. In particular, however, it is preferred to produce 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 constituents which improve the solubility of the compacted granules. Such components and the introduction of such components are described, for example, in international patent application WO-A-93/02176 and in older German patent application P 42 03 031.5.
  • the preferred ingredients 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 E0 and tallow alcohol with 40 E0, and polyethylene glycols with a relative molecular weight between 200 and 2000.
  • fatty alcohols with 10 to 80 moles of ethylene oxide per mole of fatty alcohol for example tallow fatty alcohol with 30 E0 and tallow alcohol with 40 E0
  • polyethylene glycols with a relative molecular weight between 200 and 2000.
  • the anionic surfactants which may be present are used in the production of the solid premix intended for extrusion in the form of a spray-dried, granulated or extruded compound. Furthermore, a method is preferred in which the surface of the partial extrudates is subsequently treated to reduce the stickiness of the granules rich in nonionic surfactants. Suitable surface modifiers are known from the prior art.
  • zeolites In addition to other suitable, finely divided zeolites, amorphous aluminosilicates, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but especially mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.
  • the compositions 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.
  • further individual constituents of the agent for example carbonate, citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, which may be crystalline can subsequently add to the partial extrudates.
  • bleach activators are the N-acyl or O-acyl compounds which form organic peracids with H2O2, 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-di-acetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Suitable enzymes are those from the class of proteases, lipases, aylases, cellulases or mixtures thereof.
  • the enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • 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 be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • the bulk density of the preferred granular agents is generally 300 to 1100 g / 1, in particular 500 to 1000 g / 1.
  • agents according to the invention which contain a total of about 10 to 35% by weight, advantageously 12 to 30% by weight of anionic and nonionic surfactants, 20 to 60% by weight of builder substances, 10 to 25% by weight of peroxy- Bleaching agents, 2 to 15% by weight, in particular 5 to 10% by weight, of inorganic and alkaline salts such as carbonate and amorphous silicates, insofar as they are not included in the builder substances, and foam inhibitors, bleach activators and enzymes.
  • the agent according to the invention consists of 80 to 95% by weight of the partial extrudates, advantageously of partial extrudates I and II.
  • Such agents preferably have a bulk density above 650 g / 1 and in particular at least 700 g / 1.
  • Partial extrudate I contained 14.5% by weight of Ci6-Ci8-alkyl sulfate, 8.5% by weight of C ⁇ 2-Ci4-alkyl sulfate, 9.5% by weight of Ci2-Ci8-fatty alcohol with 3 EO, 5.5% by weight. % Sodium carbonate, 5% by weight Sokalan CP ⁇ ( R ) (copoly eres of acrylic acid; commercial product from BASF, Federal Republic of Germany), 2.5% by weight sodium silicate with a Na2 ⁇ : Si ⁇ 2 ratio of 1: 2.0, 38.5% by weight zeolite (anhydrous active substance), 4% by weight sodium sulfate, 1.65% by weight salts from raw materials and the rest water.
  • the bulk weight of extrudate I was 773 g / 1.
  • Partial extrudate II contained 6.6% by weight of Ciö-Cis-alkyl sulfate, 4% by weight of Ci2-Ci4-alkyl sulfate, 5.5% by weight of sodium carbonate, 5% by weight of Sokalan CP ⁇ ( R ), 1 , 7% by weight silicone oil, 2.2% by weight sodium silicate with a modulus of 2.0, 1.2% by weight sodium silicate with a module of 3.0, 7% by weight zeolite (referred to 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 / 1.
  • agent Ml was produced which consisted of 65% by weight of extrudate I and 35% by weight of extrudate II.
  • Another agent M2 contained 59.8% by weight of extrudate I, 32.2% by weight of extrudate II and 8% by weight of further ingredients such as tetraacetylethylene diamine, protease, lipase and / or cellulose and perfume.
  • an agent VI was produced from a uniform extrudate, which contained the ingredients of extrudates I and II in a ratio of 65:35.
  • the dissolution time at 90% resolution was 2 minutes and 29 seconds for MI, 3 minutes and 20 seconds for VI.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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PCT/EP1995/000567 1994-02-25 1995-02-16 Granulares wasch- oder reinigungsmittel WO1995023207A1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PL95315976A PL315976A1 (en) 1994-02-25 1995-02-16 Granular washing or cleaning agent
DK95910492T DK0746601T3 (da) 1994-02-25 1995-02-16 Granulært vaske- eller rengøringsmiddel
EP95910492A EP0746601B1 (de) 1994-02-25 1995-02-16 Granulares wasch- oder reinigungsmittel
DE59507614T DE59507614D1 (de) 1994-02-25 1995-02-16 Granulares wasch- oder reinigungsmittel
AT95910492T ATE188730T1 (de) 1994-02-25 1995-02-16 Granulares wasch- oder reinigungsmittel
AU17578/95A AU1757895A (en) 1994-02-25 1995-02-16 Granular washing or cleaning agent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4406210.9 1994-02-25
DE4406210A DE4406210A1 (de) 1994-02-25 1994-02-25 Granulares Wasch- oder Reinigungsmittel

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WO1995023207A1 true WO1995023207A1 (de) 1995-08-31

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

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EP0840780B1 (de) * 1995-07-12 2000-11-15 Henkel Kommanditgesellschaft auf Aktien Granulares wasch- oder reinigungsmittel mit hoher schüttdichte
EP0985014B2 (en) 1997-05-30 2005-10-19 Unilever Plc Detergent compositions
WO2019130146A1 (en) * 2017-12-29 2019-07-04 Zobele Holding S.P.A. Laundry additive for removing stains

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
DE4429550A1 (de) * 1994-08-19 1996-02-22 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten
DE19501117A1 (de) * 1995-01-17 1996-07-18 Henkel Kgaa Bleichendes Waschmittel in Granulatform
DE19519139A1 (de) * 1995-05-30 1996-12-05 Henkel Kgaa Granulares Wasch- oder Reinigungsmittel mit hoher Schüttdichte

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JPS6169899A (ja) * 1984-09-14 1986-04-10 花王株式会社 流動性の改良された高密度の粒状洗剤の製法
GB2178075A (en) * 1985-07-19 1987-02-04 Colgate Palmolive Co Bleach active detergent additive composition
EP0265258A2 (en) * 1986-10-24 1988-04-27 Unilever Plc Detergent composition with soap noodles
WO1991002047A1 (de) * 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Herstellung verdichteter granulate für waschmittel

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JPS6169899A (ja) * 1984-09-14 1986-04-10 花王株式会社 流動性の改良された高密度の粒状洗剤の製法
GB2178075A (en) * 1985-07-19 1987-02-04 Colgate Palmolive Co Bleach active detergent additive composition
EP0265258A2 (en) * 1986-10-24 1988-04-27 Unilever Plc Detergent composition with soap noodles
WO1991002047A1 (de) * 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Herstellung verdichteter granulate für waschmittel

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DATABASE WPI Section Ch Week 8621, Derwent World Patents Index; Class A81, AN 86-133906 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0840780B1 (de) * 1995-07-12 2000-11-15 Henkel Kommanditgesellschaft auf Aktien Granulares wasch- oder reinigungsmittel mit hoher schüttdichte
EP0985014B2 (en) 1997-05-30 2005-10-19 Unilever Plc Detergent compositions
WO2019130146A1 (en) * 2017-12-29 2019-07-04 Zobele Holding S.P.A. Laundry additive for removing stains

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HU9602333D0 (en) 1996-10-28
HUT75202A (en) 1997-04-28
EP0746601A1 (de) 1996-12-11
ES2143044T3 (es) 2000-05-01
EP0746601B1 (de) 2000-01-12
DK0746601T3 (da) 2000-05-29
DE4406210A1 (de) 1995-08-31
AU1757895A (en) 1995-09-11
DE59507614D1 (de) 2000-02-17
PL315976A1 (en) 1996-12-23
ATE188730T1 (de) 2000-01-15

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