EP1305384B1 - Derives acetonitrile concus sous forme particulaire servant d'activateurs de blanchiment dans des lessives solides - Google Patents

Derives acetonitrile concus sous forme particulaire servant d'activateurs de blanchiment dans des lessives solides Download PDF

Info

Publication number
EP1305384B1
EP1305384B1 EP01938265A EP01938265A EP1305384B1 EP 1305384 B1 EP1305384 B1 EP 1305384B1 EP 01938265 A EP01938265 A EP 01938265A EP 01938265 A EP01938265 A EP 01938265A EP 1305384 B1 EP1305384 B1 EP 1305384B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
weight
formula
mixtures
acid
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
EP01938265A
Other languages
German (de)
English (en)
Other versions
EP1305384A1 (fr
Inventor
Birgit Middelhauve
Horst-Dieter Speckmann
Jörg Poethkow
Martina Kihn-Botulinski
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
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1305384A1 publication Critical patent/EP1305384A1/fr
Application granted granted Critical
Publication of EP1305384B1 publication Critical patent/EP1305384B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles

Definitions

  • the present invention relates to the use of particulate formulated acetonitrile derivatives as activators for, in particular, inorganic peroxygen compounds for bleaching dyed textile soils and to detergents containing such activators.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfuryl amides and cyanurates, in addition carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxybenzolsulfonat and acylated sugar derivatives, such as pentaacetyl, have become known in the literature.
  • bleach activators for the numerous proposals, especially from the classes
  • the compounds according to general formula (A) in particular in combination with other ingredients of detergents and cleaners, are usually less storage-stable and, in particular, extremely sensitive to moisture.
  • Some of the particularly well bleach-enhancing agents of the compounds according to general formula (A) are liquid at room temperature; others are obtained as part of their production in liquid form, for example as an aqueous solution, and can be converted only with considerable losses from this in the pure solid. In both cases, their use in solid, for example, particulate funds is difficult.
  • a subclass of such particulate agents are detergent tablets.
  • Tableted agents have a number of compared to powdered or liquid products Benefits: They are easier to dose and handle and, due to their compact structure, have advantages in storage and transport. There is therefore an extremely wide state of the art for detergent tablets, which is also reflected in an extensive patent literature.
  • developers of tablet-shaped products came up with the idea of releasing certain ingredients in the washing or cleaning process via differently shaped areas of the moldings in order to improve cleaning success.
  • multilayer molded bodies have prevailed that are offered today for many areas of washing and cleaning or hygiene.
  • Polyphase cleaning tablets for the toilet are used, for example, in the European Patent Application EP 0 055 100 described.
  • This document discloses toilet cleaner blocks comprising a molded body of a slow-dissolving detergent composition in which a bleach tablet is embedded.
  • This document simultaneously discloses the most varied embodiments of multiphase moldings.
  • the moldings are made according to the teachings of this invention either by inserting a compressed bleach tablet into a mold and encasing this tablet with the detergent composition, or by pouring a portion of the detergent composition into the mold, followed by insertion of the compressed bleach tablet and optionally subsequent infusion with further detergent composition.
  • EP 0 481 547 describes multi-phase detergent tablets to be used according to this document for automatic dishwashing.
  • These shaped bodies are in the form of core / shell tablets and are produced by stepwise compression of the constituents. First, the compression of a bleaching composition into a shaped body which is placed in a semi-filled with a polymer composition die, which is then filled with another polymer composition and a provided with a polymer shell bleach moldings is pressed. The process is then repeated with an alkaline detergent composition to give a three-phase molded body.
  • heterocyclic N-alkyl-ammonium nitriles of the otherwise circumscribed above by formula (A) type which have been formulated in granular form, being mentioned as support materials for the N-alkyl-ammonium nitriles, for example, silica, silicates and alumina.
  • the invention relates to the use of compounds of general formula I which have been formulated in particulate form with the aid of inorganic carrier materials which comprise silicate.
  • R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring
  • R 2 is -CH 2 CN and R 3 is selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2
  • the compound according to general formula I is used in the detergents in particulate formulated form, that is to say applied to an inorganic carrier material.
  • the application to the support material can be done in such a way that stirred into a solution of the compound of formula I, as obtained in the preparation thereof, the support material and the optionally aqueous solvent under vacuum, if desired, at elevated temperature, deducted.
  • the solution of the compound according to formula I can also be sprayed onto the support material and, if appropriate, subsequently subjected to a drying process. It is preferred if the particles resulting from the packaging process have a diameter in the range of 0.4 mm to 1.2 mm.
  • Suitable support materials are all inorganic substances which do not interact with the compound according to formula I in an unreasonably negative manner, for example alkali metal carbonates, alkali metal sulphates, alkali hydrogen sulphates, alkali hydrogen carbonates, alkali metal phosphates, alkali metal hydrogenphosphates, dialkali hydrogenphosphates and mixtures thereof.
  • such support materials are used whose inner surface is in the range of 10 m 2 / g to 500 m 2 / g, in particular 100 m 2 / g to 450 m 2 / g.
  • silicate carrier materials which are particularly suitable for the purposes of the present invention include, for example, both alkali metal silicates and also silicic acids, silica gels and clays as well as mixtures thereof.
  • the carrier material is preferably free of zeolites.
  • Silicate-containing support material optionally contains, in addition to the silicate component, further particulate inert constituents which do not unreasonably impair the stability of the compounds according to formula I.
  • Silicas prepared by a thermal process (flame hydrolysis of SiCl 4 ) (so-called fumed silicas) are useful as well as silicas prepared by wet processes.
  • Silica gels are colloidal silicas with elastic to firm consistency and a largely loose pore structure, resulting in a high Liquid absorption capacity results. They can be prepared by the action of mineral acids on water glass.
  • Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillonite and bauxite.
  • the use of aluminum silicate as a carrier material or as a component of a carrier material mixture is possible.
  • the carrier material preferably has particle sizes in the range from 100 ⁇ m to 1.5 mm.
  • the particles may also be coated with inorganic and / or organic materials, wholly or at least partially.
  • the acetonitrile derivative particulate formulated with the aid of the silicate-containing carrier material may additionally contain and / or be coated with an organic material having a melting point above 40 ° C., in particular nonionic surfactant. This can positively influence the disintegration properties of the corresponding particle in aqueous systems and / or its storage stability.
  • Such a particulate preformed acetonitrile derivative according to formula I is preferably incorporated in detergents which are intended for use in washing solutions for textiles for bleaching colored stains.
  • bleaching is understood to mean both the bleaching of dirt located on the textile surface, in particular tea, and the bleaching of dirt removed from the textile in the wash liquor.
  • the invention relates to solid detergents, and among these, preferably those for use in machine washing processes, which contain a compound of the formula I described above in appropriate particulate packaging, and a method for washing laundry using such a compound compound.
  • the use according to the invention as a bleach activator consists essentially of creating conditions under which a peroxidic oxidizing agent and the bleach-activating acetonitrile derivative can react with one another in the presence of a fabric contaminated with colored stains, with the aim of obtaining more strongly oxidizing secondary products. Such conditions are particularly present when both reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the acetonitrile derivative to an optionally detergent-containing solution.
  • the process according to the invention is particularly advantageously carried out using a detergent according to the invention which contains the bleach-activating acetonitrile derivative and optionally a peroxygen-containing oxidizing agent, preferably selected from the group comprising organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.
  • a peroxygen-containing oxidizing agent preferably selected from the group comprising organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.
  • the peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a peroxide-free detergent is used.
  • the conditions can be varied widely.
  • the amounts of peroxygen compounds are generally chosen such that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen are present in the solutions.
  • the amount of bleach-activating acetonitrile derivative used also depends on the intended use. Depending on the desired degree of activation 0.00001 mole to 0.25 mole, preferably 0.001 mole to 0.02 mole of activator per mole of peroxygen compound used, but in special cases, these limits can be exceeded or fallen short of.
  • Another object of the invention is a solid detergent, which 0.1 wt .-% to 10 wt .-%, in particular 0.22 wt .-% to 6 wt .-% of an acetonitrile derivative according to formula I in as described above particulate preformed form in addition to conventional, compatible with the compound ingredients.
  • compositions according to the invention may in principle contain, in addition to the bleach activator used according to the invention, all known ingredients customary in such agents.
  • the compositions according to the invention may contain, in particular, builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as color transfer inhibitors, foam regulators, additional bleach-boosting active ingredients and dyes and fragrances.
  • Peroxygen compounds which are suitable for use in compositions according to the invention are, in particular, hydrogen peroxide-releasing inorganic salts which include the alkali metal perborates, percarbonates, persilicates and / or persulphates such as caroate, but also organic peracids or persalts of organic acids such as phthalimidopercaproic acid , Perbenzoic acid or salts of diperdodecanedioic acid, into consideration.
  • Such solid peroxygen compounds can be used, for example, in the form of powders or granules, which can also be coated in a manner known in principle.
  • Peroxygen compounds are present in amounts of preferably up to 50% by weight, more preferably from 5% to 30% and most preferably from 8% to 25% by weight.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • compositions according to the invention may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety, as well as of alkylphenols having 5 to 12 C atoms in the alkyl radical.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols 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 of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • extremely low-foam compounds can be used. These preferably include C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • low-foam nonionic surfactants such as, for example, C 12 -C 18 -alkyl polyethylene glycol-polybutylene glycol ethers having in each case up to 8 mol of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers.
  • hydroxyl-containing alkoxylated alcohols as described in the European Patent Application EP 0 300 305 are described, so-called Hydroxy mixed.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (II) in which R 1 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (III) in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
  • R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this Restes stands.
  • [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be used, for example, according to the teaching of the international patent application WO 95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettklaamide.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in the Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • gemini surfactants not only such "dimer”, but also corresponding to "trimeric” surfactants understood.
  • suitable gemini surfactants are sulfated hydroxy mixed ethers according to US Pat German patent application DE 43 21 022 or dimer alcohol bis- and trimer alcohol trissulfates and ether sulfates according to the German patent application DE 195 03 061 ,
  • End-capped dimeric and trimeric mixed ethers according to the German patent application DE 195 13 391 They are characterized by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in international patent applications WO 95/19953 . WO 95/19954 and WO 95/19955 to be discribed.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, Olefinsulfonate, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C 12 -C 18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C -Atomen in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are prepared, into consideration.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester.
  • the methyl esters of ⁇ -sulfo fatty acids (MES), but also their saponified disalts are used.
  • Suitable anionic surfactants are sulfated fatty acid glycerol esters, which represent mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) ylsulfates of said chain length which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates are particularly preferred.
  • 2,3-alkyl sulfates which, for example, according to the US Pat. No. 3,234,258 or US 5 075 041 which can be obtained as commercial products of the Shell Oil Company under the name DAN® are suitable anionic surfactants.
  • sulfuric acid monoesters of straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 - C 18 -fatty alcohols with 1 to 4 EO.
  • EO ethylene oxide
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Further anionic surfactants are fatty acid derivatives of Amino acids, for example of N-methyl taurine (Tauride) and / or of N-methyl glycine (sarcosides) into consideration.
  • sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants are particularly soaps into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine and / or -isopropanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Surfactants are present in detergents according to the invention in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides or dextrins polycarboxylates of the European patent specification EP 0 625 992 or the international patent application WO 92/18542 or the European Patent EP 0 232 202
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers can be prepared in particular by methods which are described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 and generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those described in the German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • alkali metal silicates alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate having degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity which according to the data of German patent DE 24 12 837 can be determined, is usually in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • Such with a molar ratio Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 can be prepared by the method of European patent application EP 0 425 427 getting produced.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na 2 Si x O used 2x + 1 ⁇ y H 2 O in which x, known as the modulus, an integer of 1, 9 to 22, especially 1.9 to 4, and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and 8-sodium disilicates Na 2 Si 2 O 5 .yH 2 O
  • ⁇ -sodium disilicate can be obtained, for example, by the process described in International Patent Application WO 91/08171 is described.
  • ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can according to the Japanese Patent Application JP 04/238809 or JP 04/260 610 getting produced.
  • Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as determined by the methods of European patents EP 0 164 552 and or EP 0 294 753 are available are used in a further preferred embodiment of the invention means.
  • Crystalline layered silicates of the formula given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, makatite).
  • Na-SKS eg Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite)
  • Na-SKS-2 Na 2 Si 14 O 29 .xH 2 O, magadiite
  • Na-SKS-5 ⁇ -Na 2 Si 2 O 5
  • Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , natrosilite
  • Na-SKS-9 NaHSi 2 O 5 ⁇ 3H 2 O
  • Na-SKS-10 NaHSi 2 O 5 ⁇ 3H 2 O, kanemite
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 ⁇ -Na 2 Si 2 O 5
  • compositions according to the invention a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the abovementioned (co) polymeric polycarboxylic acid, as used, for example, in US Pat German patent application DE 198 19 187 or from alkali metal silicate and alkali metal carbonate, as described for example in the international patent application WO 95/22592 or as it is commercially available, for example, under the name Nabion® 15.
  • Builder substances may optionally be present in the compositions according to the invention in amounts of up to 90% by weight. They are preferably present in amounts of up to 75% by weight, in particular from 5% by weight to 50% by weight.
  • bleach-activating acetonitrile derivatives according to the invention according to formula I known conventional bleach activators, that is to say compounds which under perhydrolysis conditions give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, be used.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European patent application EP 0 525
  • WO 94/28102 WO 94/28103 .
  • WO 95/00626 WO 95/14759 and WO 95/17498 are known.
  • the from the German patent application DE 196 16 769 known hydrophilic substituted acyl acetals and in the German patent application DE 196 16 770 as well as the international patent application WO 95/14075 Acyllactame described are also preferably used.
  • Also from the German patent application DE 44 43 177 known combinations of conventional bleach activators can be used. If desired, such conventional bleach activators are contained in the customary amount range, preferably in amounts of from 0.1% by weight to 10% by weight, in particular from 0.5% by weight to 7% by weight, based on the total agent.
  • the candidate transition metal compounds include in particular from German patent application DE 195 29 905 known manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their from the German patent application DE 196 20 267 known N-analogues derived from the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl, which in the German patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands described in the German patent application DE 196 20 411 known cobalt, iron, copper and ruthenium ammine complexes, which are described in the German patent application DE 44 16 438 described manganese, copper and cobalt complexes, which in the European Patent Application EP 0 272 030 Cobalt complexes described in the European patent application EP 0 693 550 known manganese complex
  • EP 0 544 490 and EP 0 544 519 described manganese complexes.
  • Combinations of bleach activators and transition metal bleach catalysts are for example from German patent application DE 196 13 103 and the international patent application WO 95/27775 known.
  • Bleach-enhancing transition metal salts and / or complexes are, if desired, in conventional amounts, preferably up to 1 wt .-%, in particular of 0.0025 Wt .-% to 0.5 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt.%, Each based on the total agent used.
  • Particularly preferred bleach catalyst complexes include cobalt, iron, copper and ruthenium ammine complexes, for example [Co (NH 3 ) 5 Cl] Cl 2 and / or [Co (NH 3 ) 5 NO 21 ] Cl 2 .
  • the agents in addition to the particulate bleach activator according to formula I contain a bleach-enhancing active ingredient combination, which according to the European Patent Application EP 0 832 969 by intimately mixing a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and optionally a peroxygen-based oxidizer and inert support material, in amounts of preferably 0.25% by weight to 25 wt .-%, in particular 1 wt .-% to 10 wt .-%; A preferred use of the particulate bleach activator according to formula I takes place in the presence of such an active ingredient combination.
  • a bleach-enhancing active ingredient combination which according to the European Patent Application EP 0 832 969 by intimately mixing a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and optionally a peroxygen-based oxidizer
  • the agents according to the invention may contain enzymes such as proteases, amylases, pullulanases, mannanases, xylanases, cutinases, lipases, hemicellulases and cellulases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect® OxP and / or Durazym®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme ®, Ecostone® and / or Carezyme®.
  • proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Es
  • the optionally used enzymes can, as for example in international patent applications WO 92/11347 or WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are in the inventive compositions preferably in amounts up to 2 wt .-%, in particular from 0.1 wt .-% to 1.5 wt .-%, containing, with particular preference against oxidative degradation stabilized enzymes, such as the international patent applications WO 94/02597 . WO 94/02618 . WO 94/18314 . WO 94/23053 or WO 95/07350 , known to be used.
  • color transfer inhibitors include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole.
  • Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.
  • the detergents according to the invention may comprise soil release polymers, which are generally composed of carboxylic acid units and optionally polymeric diol units and contain, for example, ethylene terephthalate and polyoxyethylene terephthalate groups.
  • Other monomer units for example propylene glycol, polypropylene glycol, alkylene or alkenylene dicarboxylic acids, isophthalic acid, carboxy- or sulfo-substituted phthalic isomers may be included in the soil release polymer.
  • End-capped derivatives ie polymers which have neither free hydroxyl groups nor free carboxyl groups, but for example carry C 1-4 -alkyl groups or are terminally esterified with monobasic carboxylic acids, for example benzoic acid or sulfobenzoic acid, can be used.
  • Suitable are also from the European Patent Application EP 0 241 985 known polyesters which, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and also glycerol units and are end-group-capped with C 1 - to C 4 -alkyl groups who are in the means of European Patent Application EP 0 253 567 ethylene glycol terephthalate and polyethylene terephthalate having a molecular weight of 900 to 9,000, wherein the polyethylene glycol units have molecular weights of 300 to 3,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95, the from the European Patent Application EP 0 272 033 known, at least in part by C 1-4 alkyl or acyl radicals end phenomenonver violationen polyester with poly-propylene terephthalate and polyoxyethylene terephthalate units, which in the European patent
  • Detergents according to the invention may contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of identical structure which are used instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • Mixtures of the aforementioned optical brightener can be used.
  • agents foam too much during use they may still preferably contain up to 5% by weight, in particular about 0.1% by weight to 3% by weight, of a foam-regulating compound, preferably from the group of silicone oils, mixtures Silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettklareamide, and other further known commercially available defoamer may be added.
  • a foam-regulating compound preferably from the group of silicone oils, mixtures Silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettklareamide, and other further known commercially available defoamer may be added.
  • a foam-regulating compound preferably from the group of silicone oils, mixtures Silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettklareamide, and other further known commercially available defoamer may be added.
  • the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid. but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, contained in the inventive compositions.
  • the premixes to be tabletted into tablets contain from 0.5 to 10% by weight, preferably from 1 to 5% by weight and in particular from 2 to 4% by weight, of a disintegration assistant, in each case based on the premix.
  • Disintegrating agents based on cellulose are used as preferred disintegrating agents in the context of the present invention, so that preferred detergent tablets have cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 1 to 5% by weight and in particular from 2 to 4% by weight .-% contain.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which Hydroxy hydrogen atoms were substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.
  • cellulose-based disintegrating agent which is free of cellulose derivatives.
  • microcrystalline cellulose can be used as a further disintegrating agent based on cellulose or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact.
  • microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and can be compacted, for example, into granules having an average particle size of 200 ⁇ m.
  • compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach activator are expected to be prepared.
  • compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 to 1000 g / l can be carried out by increasing the builder components in a first process step with at least a proportion of liquid mixture components the bulk density of this premix is mixed and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the particulate preformed bleach catalyst according to formula I, combined with the thus obtained premix.
  • compositions according to the invention are in the form of compressed bodies, in particular tablets, for the preparation of which a compressed premix, which may contain all the ingredients suitable for compositions according to the invention, is compressed.
  • the premix can be composed of a wide variety of substances as described above. Regardless of the composition of the premixes to be compressed, physical parameters of the premixes can be chosen such that advantageous molding properties result.
  • the particulate premixes to be compressed have bulk densities above 600 g / l, preferably above 700 g / l and in particular above 800 g / l.
  • the particle size in the premixes to be compressed can also be adjusted to obtain advantageous molded body properties.
  • the compressed particulate premix has a particle size distribution wherein less than 10% by weight, preferably less than 7.5% and more preferably less than 5% by weight of the particles are greater than 1600 ⁇ m or less 200 microns are.
  • narrower particle size distributions are more preferred.
  • Particularly advantageous variants are characterized in that the particulate premix to be compressed has a particle size distribution in which more than 30 wt .-%, preferably more than 40 wt .-% and in particular more than 50 wt .-% of the particles have a particle size between 600 and 1000 microns have.
  • the premix is compressed in a so-called matrix between two punches to form a solid compressed product.
  • This process hereinafter referred to as tabletting, is divided into the four sections dosage, compression (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • the premix particles are also crushed, and even higher pressures cause sintering of the premix.
  • the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down.
  • eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected for larger throughputs, in which a larger number of dies are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • Suitable tabletting machines are available, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Berne (CH) and Courtoy NV, Halle (BE / LU).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the spatial form of another embodiment of the moldings is adapted in their dimensions of the dosing of commercial dishwashers, so that the moldings can be metered without dosing directly into the dispenser, from where they are released during the cleaning process.
  • the detergent tablets via metering aids without any problem.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the molding.
  • the method can also be extended to the effect that it produces in a conventional manner multilayer moldings by preparing two or more premixes which are pressed together.
  • the first-filled premix is slightly pre-pressed to get a smooth and parallel to the mold bottom extending top, and end-pressed after filling the second premix to the finished shaped body.
  • a further pre-compression takes place after each premix addition, before the shaped article is end-pressed after the last premix has been added.

Claims (15)

  1. Utilisation de composés confectionnés sous forme de particules à l'aide de matériaux support inorganiques qui contiennent du silicate, de formule générale I,
    Figure imgb0009
     dans laquelle R1 représente -H, -CH3, un radical C2-24-alkyle ou C2-24-alcényle, un radical C2-24-alkyle ou C2-24-alcényle substitué avec au moins un substituant du groupe formé par -Cl, -Br, -OH, -NH2, -CN, un radical alkylaryle ou alcénylaryle avec un groupe C1-24-alkyle, ou un groupe alkylaryle ou alcénylaryle substitué avec un groupe C1-24-alkyle et au moins un autre substituant sur le cycle aromatique, R2 représente -CH2-CN et R3 est choisi dans le groupe formé par -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH avec n = 1, 2, 3, 4, 5 ou 6, R4 et R5 présentent, indépendamment l'un de l'autre, une signification indiquée ci-dessus pour R1, R2 ou R3 et X est un anion équilibrant la charge, qui est choisi parmi les halogénures, tels que le chlorure, le fluorure, l'iodure et le bromure, le nitrate, l'hydroxyde, le phosphate, l'hydrogénophosphate, le dihydrogénophosphate, le pyrophosphate, le métaphosphate, l'hexafluorophosphate, le carbonate, l'hydrogénocarbonate, le sulfate, l'hydrogénosulfate, le chlorate, le perchlorate, le formiate, l'acétate, le citrate, l'éthosulfate, ou le méthosulfate ou des mélanges de ceux-ci, comme activateurs pour des composés peroxygénés en particulier inorganiques dans des agents de lavage solides pour textiles, qui sont essentiellement utilisés dans des solutions de lavage aqueuses.
  2. Utilisation selon la revendication 1, caractérisée en ce que le matériau support présente une surface interne dans la plage de 10 m2/g à 500 m2/g, en particulier de 100 m2/g à 450 m2/g.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que le matériau support contient un silicate du groupe formé par les silicates alcalins, les silices, les gels siliciques et les argiles ainsi que leurs mélanges.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la forme de confection en particules comprend 10 à 50 parties en poids du matériau support et 50 à 90 parties en poids du composé selon la formule I.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que le composé peroxygéné à activer est choisi dans le groupe formé par les peracides organiques, le peroxyde d'hydrogène, le perborate et le percarbonate ainsi que leurs mélanges.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce qu'une combinaison de substances actives renforçant le blanchiment, qui peut être obtenue par mélange intime d'un sel soluble dans l'eau d'un métal de transition divalent, choisi parmi le cobalt, le fer, le cuivre et le ruthénium ainsi que leurs mélanges, d'un sel d'ammonium soluble dans l'eau et le cas échéant d'un oxydant à base de peroxygène ainsi que d'un matériau support inerte, est présente simultanément.
  7. Agent de lavage solide, caractérisé en ce qu'il contient 0,1% en poids à 10% en poids, en particulier 0,2% en poids à 6% en poids d'un composé confectionné sous forme de particules à l'aide de matériaux support inorganiques qui contiennent du silicate, de formule générale I
    Figure imgb0010
     dans laquelle R1 représente -H, -CH3, un radical C2-24-alkyle ou C2-24-alcényle, un radical C2-24-alkyle ou C2-24-alcényle substitué avec au moins un substituant du groupe formé par -CI, -Br, -OH, -NH2, -CN, un radical alkylaryle ou alcénylaryle avec un groupe C1-24-alkyle, ou un groupe alkylaryle ou alcénylaryle substitué par un groupe C1-24-alkyle et au moins un autre substituant sur le cycle aromatique, R2 représente -CH2-CN et R3 est choisi dans le groupe formé par -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH avec n = 1, 2, 3, 4, 5 ou 6, R4 et R5 présentent, indépendamment l'un de l'autre, une signification indiquée ci-dessus pour R1, R2 ou R3 et X est un anion équilibrant la charge, qui est choisi parmi les halogénures, tels que le chlorure, le fluorure, l'iodure et le bromure, le nitrate, l'hydroxyde, le phosphate, l'hydrogénophosphate, le dihydrogénophosphate, le pyrophosphate, le métaphosphate, l'hexafluorophosphate, le carbonate, l'hydrogénocarbonate, le sulfate, l'hydrogénosulfate, le chlorate, le perchlorate, le formiate, l'acétate, le citrate, l'éthosulfate, ou le méthosulfate ou des mélanges de ceux-ci, en plus des constituants usuels compatibles avec le composé selon la formule I.
  8. Agent selon la revendication 7, caractérisé en ce qu'il contient un composé peroxygéné du groupe formé par les peracides organiques, le peroxyde d'hydrogène, le perborate et le percarbonate ainsi que leurs mélanges.
  9. Agent selon la revendication 7 ou 8, caractérisé en ce qu'il contient, en plus des composés selon la formule 1, 0,5% en poids à 7% en poids de composés dissociant des acides peroxocarboxyliques dans les conditions de perhydrolyse.
  10. Agent selon l'une quelconque des revendications 7 à 9, caractérisé en ce qu'il contient, en plus des composés selon la formule I, une combinaison de substances actives renforçant le blanchiment, qui peut être obtenue par mélange intime d'un sel soluble dans l'eau d'un métal de transition divalent, choisi parmi le cobalt, le fer, le cuivre et le ruthénium ainsi que leurs mélanges, d'un sel d'ammonium soluble dans l'eau et le cas échéant d'un oxydant à base de peroxygène ainsi que d'un matériau support inerte.
  11. Agent selon l'une quelconque des revendications 7 à 9, caractérisé en ce qu'il contient, en plus du composé selon la formule l, des sels ou des complexes de métal de transition catalysant le blanchiment, en particulier en des quantités de 0,0025% en poids à 0,5% en poids.
  12. Agent selon l'une quelconque des revendications 7 à 11, caractérisé en ce qu'il se trouve sous forme de corps façonnés en forme de comprimés.
  13. Agent selon la revendication 12, caractérisé en ce que le corps façonné en forme de comprimés est à deux couches.
  14. Agent selon la revendication 13, caractérisé en ce qu'il présente dans une couche l'agent de blanchiment sous forme du composé peroxygéné en particulier inorganique et dans la deuxième couche l'activateur de blanchiment confectionné sous forme de particules à l'aide de matériaux support inorganiques qui contiennent en particulier du silicate, selon la formule 1.
  15. Agent selon la revendication 13, caractérisé en ce qu'il présente l'agent de blanchiment sous forme du composé peroxygéné en particulier inorganique et l'activateur de blanchiment confectionné sous forme de particules à l'aide de matériaux support inorganiques qui contiennent en particulier du silicate, selon la formule 1 dans la même couche et d'autres constituants sensibles, en particulier des enzymes, dans une deuxième couche.
EP01938265A 2000-08-04 2001-06-15 Derives acetonitrile concus sous forme particulaire servant d'activateurs de blanchiment dans des lessives solides Expired - Lifetime EP1305384B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10038845 2000-08-04
DE10038845A DE10038845A1 (de) 2000-08-04 2000-08-04 Teilchenförmig konfektionierte Acetonitril-Derivate als Bleichaktivatoren in festen Waschmitteln
PCT/EP2001/006810 WO2002012425A1 (fr) 2000-08-04 2001-06-15 Derives acetonitrile conçus sous forme particulaire servant d'activateurs de blanchiment dans des lessives solides

Publications (2)

Publication Number Publication Date
EP1305384A1 EP1305384A1 (fr) 2003-05-02
EP1305384B1 true EP1305384B1 (fr) 2007-08-01

Family

ID=7651836

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01938265A Expired - Lifetime EP1305384B1 (fr) 2000-08-04 2001-06-15 Derives acetonitrile concus sous forme particulaire servant d'activateurs de blanchiment dans des lessives solides

Country Status (7)

Country Link
US (1) US20040067862A1 (fr)
EP (1) EP1305384B1 (fr)
AT (1) ATE368723T1 (fr)
AU (1) AU2001263963A1 (fr)
DE (2) DE10038845A1 (fr)
ES (1) ES2288513T3 (fr)
WO (1) WO2002012425A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003238372A1 (en) 2002-05-31 2003-12-19 Henkel Kommanditgesellschaft Auf Aktien Deodorisation of cationic ammonium acetonitrile derivatives
AU2003297077A1 (en) 2002-12-18 2004-07-29 The Procter And Gamble Company Organic activator
AU2003292165A1 (en) 2002-12-20 2004-07-22 Henkel Kommanditgesellschaft Auf Aktien Bleach-containing washing or cleaning agents
ES2290242T5 (es) † 2002-12-24 2015-07-13 Dalli-Werke Gmbh & Co. Kg Sistema de detergente y producto de limpieza optimizado para una acción blanqueante mejorada a bajas temperaturas
WO2004069978A1 (fr) * 2003-02-10 2004-08-19 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage ou de nettoyage contenant un agent de blanchiment ainsi qu'un systeme adjuvant hydrosoluble et un derive cellulosique a pouvoir nettoyant
JP4578465B2 (ja) * 2003-02-10 2010-11-10 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 繊維製品の水吸収力の増大
DE10351325A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat
EP1592765B1 (fr) * 2003-02-10 2007-05-30 Henkel Kommanditgesellschaft auf Aktien Augmentation de la puissance de nettoyage de produits de lavage a l'aide d'un derive cellulosique et d'un polymere hygroscopique
WO2004069976A2 (fr) * 2003-02-10 2004-08-19 Henkel Kommanditgesellschaft Auf Aktien Utilisation de derives cellulosiques en tant que regulateurs de moussage
DE10351321A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch eine Kombination von Cellulosderivaten
WO2005116179A1 (fr) * 2004-05-17 2005-12-08 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage comprenant un complexe de metal de transition qui renforce le blanchiment et est produit eventuellement in situ
DE102005026522B4 (de) * 2005-06-08 2007-04-05 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch Polymer
DE102005026544A1 (de) 2005-06-08 2006-12-14 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch Polymer
GB0917951D0 (en) * 2009-10-14 2009-11-25 Chemlink Specialities Ltd Composition including one or more hydrolytically unstable components
RU2533494C1 (ru) * 2013-05-13 2014-11-20 Открытое акционерное общество "НАПОР" ОАО "НАПОР" Реагент для поглощения сероводорода и легких меркаптанов (варианты)

Family Cites Families (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3234258A (en) * 1963-06-20 1966-02-08 Procter & Gamble Sulfation of alpha olefins
US4116885A (en) * 1977-09-23 1978-09-26 The Procter & Gamble Company Anionic surfactant-containing detergent compositions having soil-release properties
DE3413571A1 (de) * 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3417649A1 (de) * 1984-05-12 1985-11-14 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von kristallinen natriumsilikaten
FR2597473B1 (fr) * 1986-01-30 1988-08-12 Roquette Freres Procede d'oxydation de di-, tri-, oligo- et polysaccharides en acides polyhydroxycarboxyliques, catalyseur mis en oeuvre et produits ainsi obtenus.
DE3723873A1 (de) * 1987-07-18 1989-01-26 Henkel Kgaa Verwendung von hydroxyalkylpolyethylenglykolethern in klarspuelmitteln fuer die maschinelle geschirreinigung
YU221490A (sh) * 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
DE4000705A1 (de) * 1990-01-12 1991-07-18 Hoechst Ag Verfahren zur herstellung von kristallinen natriumsilikaten
GB9012001D0 (en) * 1990-05-30 1990-07-18 Unilever Plc Bleaching composition
US5075041A (en) * 1990-06-28 1991-12-24 Shell Oil Company Process for the preparation of secondary alcohol sulfate-containing surfactant compositions
GB9022724D0 (en) * 1990-10-19 1990-12-05 Unilever Plc Detergent compositions
DE4107230C2 (de) * 1991-03-07 1995-04-06 Hoechst Ag Verfahren zur Herstellung von Natriumsilikaten
DE4142711A1 (de) * 1991-12-21 1993-06-24 Hoechst Ag Verfahren zur herstellung von kristallinen natriumdisilikaten
DE4221381C1 (de) * 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4203923A1 (de) * 1992-02-11 1993-08-12 Henkel Kgaa Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
DE4300772C2 (de) * 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4303320C2 (de) * 1993-02-05 1995-12-21 Degussa Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür
DE4405511A1 (de) * 1994-02-22 1995-08-24 Henkel Kgaa Waschmittel mit amorphen silikatischen Buildersubstanzen
DE19503061A1 (de) * 1995-02-01 1996-08-08 Henkel Kgaa Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate
US5814242A (en) * 1995-06-07 1998-09-29 The Clorox Company Mixed peroxygen activator compositions
US5739327A (en) * 1995-06-07 1998-04-14 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5888419A (en) * 1995-06-07 1999-03-30 The Clorox Company Granular N-alkyl ammonium acetontrile compositions
DE19605688A1 (de) * 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19620411A1 (de) * 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19616693A1 (de) * 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19649375A1 (de) * 1996-11-29 1998-06-04 Henkel Kgaa Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
US6211130B1 (en) * 1997-08-21 2001-04-03 Henkel Kommanditgesellschaft Auf Aktien Use of quaternary acetonitrile compounds as activators for detergents
DE19740671A1 (de) * 1997-09-16 1999-03-18 Clariant Gmbh Bleichaktivator-Granulate
DE19819187A1 (de) * 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
DE19857596A1 (de) * 1998-12-15 2000-06-21 Henkel Kgaa Teilchenförmig konfektionierte Acetonitril-Derivate als Bleichaktivatoren in festen Reinigungsmitteln
ES2216609T3 (es) * 1998-12-15 2004-10-16 Henkel Kommanditgesellschaft Auf Aktien Derivados de acetonitrilo confeccionados en forma de particulas como activadores de blanqueo en agentes de limpieza solidos.
DE19908051A1 (de) * 1999-02-25 2000-08-31 Henkel Kgaa Verfahren zur Herstellung compoundierter Acetonitril-Derivate
DE19914811A1 (de) * 1999-03-31 2000-10-05 Henkel Kgaa Enzym- und bleichaktivatorhaltige Wasch- und Reinigungsmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
DE10038845A1 (de) 2002-02-21
EP1305384A1 (fr) 2003-05-02
ATE368723T1 (de) 2007-08-15
WO2002012425A1 (fr) 2002-02-14
ES2288513T3 (es) 2008-01-16
US20040067862A1 (en) 2004-04-08
DE50112796D1 (de) 2007-09-13
AU2001263963A1 (en) 2002-02-18

Similar Documents

Publication Publication Date Title
EP1305384B1 (fr) Derives acetonitrile concus sous forme particulaire servant d'activateurs de blanchiment dans des lessives solides
ES2483541T3 (es) Mezclas de agentes activadores del blanqueo
EP1141211B1 (fr) Derives d'acetonitrile confectionnes sous forme de particules utilises comme activateurs de blanchiment dans des detergents solides
EP1445305A1 (fr) Utilisation de complexes de métaux de transition comme catalysateurs de blanchiment
WO2010022918A1 (fr) Utilisation d'oxalates de manganèse comme catalyseur de blanchiment
EP3625319B1 (fr) Granulés enrobés, leur utilisation et produits de lavage et de nettoyage contenant ces granulés
US20040067863A1 (en) Enclosed bleach activators
EP1165737B1 (fr) Agents de lavage et de nettoyage contenant des enzymes et un activateur de blanchiment
DE19908051A1 (de) Verfahren zur Herstellung compoundierter Acetonitril-Derivate
EP1044256A1 (fr) Procede de fabrication d'un corps moule detergent pour lave-vaisselle
US6498133B2 (en) Particulate bleach activators based on acetonitriles
EP1056832B1 (fr) Corps moules a plusieurs phases presentant une division de phases optimisee
WO2000032731A1 (fr) Utilisation de complexes de metaux de transition avec des ligands heterocycliques contenant de l'azote pour renforcer l'effet blanchissant de composes peroxy
EP1165742B1 (fr) Corps moules d'agents de lavage et de nettoyage monophases ou multiphases comportant des activateurs de blanchiment speciaux
DE19755493A1 (de) Verwendung von Übergangsmetallkomplexen mit tripodalen Liganden zur Verstärkung der Bleichwirkung von Persauerstoffverbindungen
EP1794272B1 (fr) Melanges d'agents de blanchiment
EP1165741B1 (fr) Corps moules d'agents de lavage et de nettoyage avec activateurs de blanchiment speciaux
DE19857596A1 (de) Teilchenförmig konfektionierte Acetonitril-Derivate als Bleichaktivatoren in festen Reinigungsmitteln
EP1045894A1 (fr) Corps moule detergent pour lave-vaisselle a proportions volumiques specifiques
EP1159392B2 (fr) Produits de lavage et de nettoyage moules contenant une association tensioactif/agent de blanchiment/adjuvant de lavage
EP1141191B1 (fr) Composes phosphates
DE19942224A1 (de) Verwendung von Übergangsmetallkomplexverbindungen zur Verstärkung der Bleichwirkung von Persauerstoffverbindungen in sauren Systemen
DE19959589A1 (de) Mehrphasige Reinigungsmitteltabletten
DE19942796A1 (de) Builder-haltige Tablette
DE19918722A1 (de) Bleichmittel-haltige Waschmitteltabletten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030127

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KIHN-BOTULINSKI, MARTINA

Inventor name: SPECKMANN, HORST-DIETER

Inventor name: MIDDELHAUVE, BIRGIT

Inventor name: POETHKOW, JOERG

17Q First examination report despatched

Effective date: 20050506

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 50112796

Country of ref document: DE

Date of ref document: 20070913

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20071107

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2288513

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070801

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070801

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071102

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080102

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070801

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: HENKEL AG & CO. KGAA

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071101

26N No opposition filed

Effective date: 20080506

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080619

Year of fee payment: 8

Ref country code: ES

Payment date: 20080717

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20080617

Year of fee payment: 8

Ref country code: IT

Payment date: 20080625

Year of fee payment: 8

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 20080630

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080618

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080615

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090615

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080615

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20090616

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090616

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090615