EP1305384A1 - Teilchenförmig konfektionierte acetonitril-derivate als bleichaktivatoren in festen waschmitteln - Google Patents
Teilchenförmig konfektionierte acetonitril-derivate als bleichaktivatoren in festen waschmittelnInfo
- Publication number
- EP1305384A1 EP1305384A1 EP01938265A EP01938265A EP1305384A1 EP 1305384 A1 EP1305384 A1 EP 1305384A1 EP 01938265 A EP01938265 A EP 01938265A EP 01938265 A EP01938265 A EP 01938265A EP 1305384 A1 EP1305384 A1 EP 1305384A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- formula
- weight
- acid
- compound
- 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.)
- Granted
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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 colored textile soils and detergents which contain such activators.
- Inorganic peroxygen compounds in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes.
- the oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H 2 O 2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C.
- the oxidation effect of the inorganic peroxygen compounds can be improved by the addition of so-called bleach activators, for which numerous suggestions, especially from the classes of the ⁇ - or O-acyl compounds, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, ⁇ - acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, moreover carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate, sodium isononanate sulfonate and benzyl ingenoacetate benzyl acyl benzyl acylate, as well as known became.
- bleach activators for which numerous suggestions,
- the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C.
- application temperatures significantly below 60 ° C, in particular below 45 ° C, down to the cold water temperature have become increasingly important in recent years.
- the compounds of the general formula (A) are usually not very stable in storage, in particular in combination with further ingredients of detergents and cleaning agents and especially extremely sensitive to moisture.
- Some of the particularly good bleach enhancers kend active representatives of the compounds of general formula (A) are liquid at room temperature; others occur in the course of their production in liquid form, for example as an aqueous solution, and can only be converted from this into the pure solid with considerable losses. In both cases, their use in solid, for example particulate, media is difficult.
- a subclass of such particulate agents are tablet detergents.
- Tableted agents have a number of properties compared to powdered or liquid products Advantages: They are easier to dose and handle and, thanks to their compact structure, have advantages for storage and transport. There is therefore an extremely broad state of the art for detergent tablets, which is also reflected in an extensive patent literature.
- the developers of tablet-shaped products came up with the idea of releasing certain ingredients through differently composed areas of the molded bodies only under defined conditions in the washing or cleaning cycle, in order to improve cleaning success.
- multi-layered shaped articles have become established, which are now offered for many areas of washing and cleaning or hygiene.
- Multi-phase cleaning tablets for the toilet are described, for example, in European patent application EP 0 055 100.
- This document discloses toilet block detergents which comprise a molded body of a slowly dissolving detergent composition in which a bleach tablet is embedded.
- this document discloses the most varied forms of configuration of multiphase shaped bodies.
- the moldings are produced either by inserting a compressed bleach tablet into a mold and pouring the detergent composition into this tablet, or by pouring part of the detergent composition into the mold, followed by inserting the compressed bleach tablet and possibly subsequently pouring over it with another detergent composition.
- European patent application EP 0481 547 also describes multi-phase detergent tablets which, according to this document, are to be used for automatic dishwashing.
- These shaped bodies are in the form of core / shell tablets and are produced by gradually compressing the constituents: first, a bleaching agent composition is pressed into a shaped body, which is placed in a matrix half-filled with a polymer composition, which is then filled with another polymer composition and into one provided with a polymer jacket middle molded body is pressed. The process is then repeated with an alkaline detergent composition, so that a three-phase shaped body results.
- the invention relates to the use of compounds of the general formula I which have been made up in particulate form with the aid of inorganic carrier materials which contain, in particular, silicate,
- R 1 for -H, -CH 3 a C 2 . 24 alkyl or alkenyl radical, a substituted C 2 . 24 - alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN, an alkyl or alkenylaryl radical with a. ⁇ - alkyl group, or for a substituted alkyl or alkenylaryl radical with a C ,.
- the anions X " include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, C,. 20 alkyl sulfate , C ,.
- halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, C,. 20 alkyl sulfate , C ,.
- C ⁇ ⁇ alkyl substituted aryl sulfonate optionally C ⁇ ⁇ alkyl substituted aryl sulfonate, chlorate, perchlorate and / or the anions of C ⁇ -carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.
- X is chloride, sulfate, hydrogen sulfate, ethosulfate, lauryl sulfate, dodecylbenzenesulfonate, toluenesulfonate, cumene sulfonate, xylene sulfonate or methosulfate or mixtures thereof.
- the anion is toluene sulfonate or cumene sulfonate ortho, meta or ⁇ r ⁇ isomers of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and understood any mixtures of these. ⁇ ra-isopropylbenzenesulfonic acid is particularly preferred.
- the compound according to general formula I is used in the detergents in particulate form, that is to say applied to an inorganic carrier material.
- the application to the support material can be such that the support material is stirred into a solution of the compound of the formula I, as is obtained in the course of its preparation, and the aqueous solvent, if appropriate, is removed in vacuo, if desired at elevated temperature.
- the solution of the compound of the formula I can also be sprayed onto the support material and, if appropriate, or subsequently, subjected to a drying process. It is preferred if the particles resulting from the packaging process have a diameter in the range from 0.4 mm to 1.2 mm.
- Suitable carrier materials are all inorganic substances which do not interact in an unacceptably negative manner with the compound of the formula I, for example alkali metal carbonates, alkali metal sulfates, alkali metal hydrogen sulfates, alkali metal hydrogen carbonates, alkali metal phosphates, alkali metal hydrogen phosphates, dialkali metal hydrogen phosphates and alkali metal silicates and mixtures thereof.
- Support materials are preferably used whose inner surface is in the range from 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 in the context of the present invention include, for example, both alkali silicates and also silicas, silica gels and clays and mixtures thereof.
- the carrier material is preferably free of zeolites.
- silicate-containing carrier material optionally contains further particulate inert constituents which do not unreasonably impair the stability of the compounds of the formula I.
- Silicas which have been produced by a thermal process can be used as well as silicas produced by wet processes.
- Silica gels are colloidal silicas with elastic to firm consistency and a largely loose pore structure, which results in a high Results in fluid absorption. They can be produced 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, montmorillionite and bauxite.
- the use of aluminum silicate as a carrier material or as a component of a carrier material mixture is also possible.
- the carrier material preferably has particle sizes in the range from 100 ⁇ m to 1.5 mm.
- the particulate compounds of formula I preferably contain 10 to 50 parts by weight of the carrier material and 50 to 90 parts by weight of the compound of formula I.
- the particles can also be completely or at least partially coated with inorganic and / or organic materials.
- the acetonitrile derivative which is made up in particulate form with the aid of the silicate-containing carrier material in particular, can additionally contain an organic material with a melting point above 40 ° C., in particular nonionic surfactant, or be encased with one. This can have a positive effect on the disintegration properties of the corresponding particle in aqueous systems and / or its storage stability.
- Such a particulate-made acetonitrile derivative according to formula I is preferably incorporated into detergents which are intended for use in washing solutions for textiles for bleaching colored stains.
- bleaching means both the bleaching of dirt on the textile surface, in particular tea, and the bleaching of dirt detached from the textile in the washing liquor.
- the invention relates to solid detergents, and preferably to those for use in machine washing processes, which contain a compound of the formula I described above in appropriate particulate formulations, and to a method for washing laundry using such a compound.
- the use according to the invention as a bleach activator essentially consists in creating, in the presence of a textile contaminated with colored soils, conditions under which a peroxidic oxidizing agent and the bleach activating acetonitrile derivative can react with one another with the aim of obtaining secondary products with a stronger oxidizing action. Such conditions exist in particular when both reactants meet in aqueous solution. This can be done by adding the peroxygen compound and the acetonitrile derivative separately 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 can 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 depending on the intended use. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents are also suitable as the reaction medium.
- the amounts of peroxygen compounds are generally chosen so 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 mol to 0.25 mol, preferably 0.001 mol to 0.02 mol, of activator per mol of peroxygen compound are used, but in special cases these limits can also be exceeded or fallen short of.
- the invention further relates to a solid detergent which comprises 0.1% by weight to 10% by weight, in particular 0.22% by weight to 6% by weight, of an acetonitrile derivative of the formula I as described above contains particulate form in addition to the usual ingredients compatible with the compound.
- the solid agents according to the invention which can be present, for example, as powdered or tablet-like solids, can in principle contain all known ingredients that are customary in such agents.
- the agents according to the invention can in particular contain builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and further auxiliaries, such as color transfer inhibitors, foam regulators, additional bleach-enhancing active ingredients and colorants and fragrances.
- Suitable peroxygen compounds for use in agents according to the invention are, in particular, inorganic salts which give off hydrogen peroxide under the washing conditions, which include the alkali perborates, percarbonates, persilicates and / or persulfates such as caroate, but also organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperododecanedioic acid.
- Solid peroxygen compounds of this type 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, in particular from 5% by weight to 30% by weight and particularly preferably from 8% by weight to 25% by weight.
- bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may be useful.
- the agents according to the invention can contain 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 products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups.
- alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups Corresponding ethoxylation and / or propoxylation products of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and of alkyl phenols having 5 to 12 carbon 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 an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, -C, r alcohols with 7 EO, C 13 -C ⁇ 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C lg - 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 2 -C 18 alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
- Extremely low-foam connections can be used in particular in compositions for use in mechanical processes. These preferably include C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
- low-foaming nonionic surfactants can also be used, such as, for example, C 12 -C ] 8- alkylpolyethylene glycol-polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, and also end group-capped alkylpolyalkylene glycol mixed ethers.
- the hydroxyl-containing alkoxylated alcohols as described in European patent application EP 0 300 305, are also particularly preferred 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 methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and ohgoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
- polyhydroxy fatty acid amides of the formula (II) in which R'CO is 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 with 5 or 6 carbon atoms, in particular from glucose.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (III)
- R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 4 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
- R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred
- [Z] is also preferably obtained here 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, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- 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 and or alkylglycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 up to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533.
- 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, in particular not more than half of them.
- So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are generally separated from one another by a so-called “spacer”.
- This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another.
- Such surfactants are distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
- gemini surfactants is understood not only to mean “dimeric” in this way, but also correspondingly “trimeric” surfactants.
- Surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis- and trimer alcohol trisulfates and ether sulfates according to German patent application DE 195 03 061.
- End group-capped dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are distinguished in particular by their bi- and multifunctionality.
- 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.
- 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 can also be used.
- Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups.
- Preferred surfactants of the sulfonate type are C 9 -C 3 alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkane sulfonates, and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered.
- alkanesulfonates obtained from C 12 -C 8 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are produced by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 ° C -Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered.
- ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. %, can be present.
- ⁇ -sulfo fatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
- the methyl esters of ⁇ -sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.
- Suitable anionic surfactants are sulfated fat Acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxoal alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 4 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology.
- 2,3-Alkyl sulfates which are produced, for example, in accordance with US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
- sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl branched C 9 -C ⁇ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 - C ] 8 fatty alcohols with 1 to 4 EO.
- 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 especially ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 -C 8 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
- sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives come from as further anionic surfactants Amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides).
- the sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred.
- Soaps are particularly suitable as further anionic surfactants.
- Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
- the known alkenyl succinic acid salts can also be used together with these soaps or as a substitute for soaps.
- the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine and / or isopropanolamine.
- the anionic surfactants are preferably 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 5% by weight to 50% by weight, in particular 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 as well as polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosendiaminephosphonic acid), ethylenediophynephosphonic acid, ethylenediophosphonic acid, ethylenediophosphonic acid, ethylenediophosphonic acid, ethylenediophosphonic acid, ethylenediophosphonic acid, ethylenediophosphonic acid, ethylenediophosphonic acid, ethylenediophosphonic acid, ethylenediophosphonic acid, ethylenediophosphonic acid, ethylenediophosphonic acid,
- the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 30,000 to 100,000.
- Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
- Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
- Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer.
- 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 can be a derivative of a C 4 -C 8 dicarboxylic acid, 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 ,
- Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000.
- Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
- All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
- Such organic builder substances can, if desired, 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.
- Particularly suitable water-soluble inorganic builder materials are alkali silicates, alkali carbonates and alkali phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts.
- alkali silicates alkali carbonates and alkali phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts.
- examples of this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium tri-phosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts.
- crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid compositions in particular from 1% by weight to 5% by weight. used.
- the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the zeolites A and X (Negobond® AX, a commercial product of Condea Augusta SpA), are preferred
- Amounts close to the above upper limit are preferably used in solid, particulate compositions.
- Suitable aluminosilicates in particular have no particles with a grain size of more than 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size of less than 10 ⁇ m.
- Their calcium binding capacity which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram.
- Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates.
- the alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
- Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio ⁇ a 2 O: SiO 2 of 1: 2 to 1: 2.8.
- Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
- ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 'yH 2 O
- ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171
- ⁇ -sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
- Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0452 428 , can be used in agents according to the invention.
- a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0 436 835.
- Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention.
- Crystalline layered silicates of the above formula are sold by Clariant GmbH under the trade name Na-SKS, for example Na-SKS-1 (Na 2 Si 22 O 45 xH 2 O, Kenyait), Na-SKS-2 (Na 2 Si ] 4 O 29 xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 xH 2 O) or Na-SKS-4 (NajS Og-xH makatite).
- 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, Kanemit), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ).
- Builder substances can optionally be present in the agents according to the invention in amounts of up to 90% by weight. They are preferably contained in amounts of up to 75% by weight, in particular from 5% by weight to 50% by weight.
- bleach activating acetonitrile derivatives according to formula I which are essential to the invention
- known conventional bleach activators that is to say compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic 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 number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
- Multi-acylated 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), are preferred.
- TAED tetraacetylethylenediamine
- DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
- TAGU tetraacetylglycoluril
- N-acylimides especially N-nonanoylsuccinimide (NOSI), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams
- hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
- the combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. If desired, such conventional bleach activators are present in the usual range of amounts, preferably in amounts of 0.1% by weight to 10% by weight, in particular 0.5% by weight to 7% by weight, based on the total agent.
- the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446 982 and EP 0453 003 may also be present as so-called bleaching catalysts.
- the transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411, the manganese and copper described in German patent application DE 44 16438 - and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese comp.
- EP 0 693 550 lexes known from European patent EP 0 392 592 Manganese, iron, cobalt and copper complexes and / or those described in European patent EP 0443 651 or European patent applications EP 0 458 397, EP 0458 398, EP 0 549271, EP 0549272, EP 0 544490 and EP 0 544 519 manganese complexes described.
- Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775.
- Bleach-enhancing transition metal salts and / or complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are, if desired, in customary amounts, preferably up to 1% by weight, in particular from 0.0025 % By weight to 0.5% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
- the particularly preferred bleach catalyst complexes include cobalt, iron, copper and ruthenium-amine complexes, for example [Co (NH 3 ) 5 Cl] Cl 2 and / or [Co (NH 3 ) 5 NO 2 ] Cl 2 .
- the agents contain, in addition to the bleach activator of the formula I, which has been made up in particulate form, a bleach-intensifying active ingredient combination which, according to European patent application EP 0 832 969, consists of intimately mixing a water-soluble salt of a divalent transition metal, selected from cobalt, iron, copper and ruthenium, and also whose mixtures, a water-soluble ammonium salt and optionally an oxidizing agent based on peroxygen and inert carrier material are available in amounts of preferably 0.25% by weight to 25% by weight, in particular 1% by weight to 10% by weight ; a preferred use of the bleach activator according to formula I, which is made up in particulate form, takes place in the presence of such a combination of active substances.
- a bleach-intensifying active ingredient combination which, according to European patent application EP 0 832 969, consists of intimately mixing a water-soluble salt of a divalent transition metal, selected from cobalt, iron, copper and ruthenium,
- the agents according to the invention can 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 enzymes that may be used such as described, for example, in international patent applications WO 92/11347 or WO 94/23005, adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in the agents according to the invention preferably in amounts of up to 2% by weight, in particular from 0.1% by weight to 1.5% by weight, particular preference being given to enzymes stabilized against oxidative degradation, for example from the international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known.
- the color transfer inhibitors that are suitable for use in textile detergents according to the invention 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 the dirt detached from the textile fibers suspended in the liquor.
- Water-soluble colloids of mostly organic nature are suitable for this, for example starch, 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.
- Starch derivatives other than those mentioned above can also be used, for example aldehyde starches.
- Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferred , used.
- the detergents according to the invention can in particular contain soil release polymers, so-called 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.
- 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, car- Boxy or sulfo substituted phthalic acid isomers can be included in the soil release polymer.
- End-capped derivatives that is to say polymers which have neither free hydroxyl groups nor free carboxyl groups but instead carry, for example, C M alkyl groups or are terminally esterified with monobasic carboxylic acids, for example benzoic acid or sulfobenzoic acid, can be used.
- polyesters known from European patent application EP 0 241 985 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 glycerol units and are end-capped with C r to C 4 alkyl groups, the soil release polymers of ethylene terephthalate and polyethylene oxide terephthalate with a molecular weight of 900 to 9000 used in the means of European patent application EP 0253 567, the polyethylene glycol units having molecular weights have from 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95, the polyesters with poly-propylene terephthalate which are at least partially end-capped by C-alkyl or acyl radicals and are known from European patent application EP 0272 033 - And polyoxyethylene terephthalate units, the sulfoethyl end group
- Polymers are also suitable from ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights from 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10 and their use in detergents is described in German patent DE 28 57292 , and polymers with a molecular weight of 15,000 to 50,000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1000 to 10,000 and the molar ratio of Ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, which can be used in detergents according to German patent application DE 33 24258.
- Textile detergents according to the invention can contain, as optical brighteners, derivatives of diamino stilbene disulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which are used 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 can also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned optical brighteners can also be used.
- agents foam too much during use they can preferably contain up to 5% by weight, in particular approximately 0.1% by weight to 3% by weight, of a foam-regulating compound, preferably from the group of silicone oils Silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bis fatty acid amides, and other other known commercially available defoamers can be added.
- a foam-regulating compound preferably from the group of silicone oils
- silicone oils silicone oils
- hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bis fatty acid amides, and other other known commercially available defoamers can be added.
- Other optional ingredients in the agents according to the invention are, for example, perfume oils.
- the agents 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 contain mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides.
- Such pH regulators are preferably contained in the agents according to the invention not more than 10% by weight, in particular from 0.5% by weight to 6% by weight.
- disintegration aids so-called tablet disintegrants
- disintegration accelerators are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
- the premixes to be compressed into tablets contain 0.5 to 10% by weight, preferably 1 to 5% by weight and in particular 2 to 4% by weight, of a disintegration aid, in each case based on the premix.
- Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 1 to 5% by weight and in particular 2 to 4% by weight .-% contain.
- Pure cellulose has the formal gross composition (C 6 H j0 O 5 ) n and, viewed formally, is a ß- 1,4 -polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which Hydroxy hydrogen atoms have been substituted.
- celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
- CMC carboxymethyl cellulose
- the cellulose derivatives mentioned are preferably not used alone as disintegrants, but are used in a mixture with cellulose.
- the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
- Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
- This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
- a subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
- the agents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which are known in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally loadable components and admixing the more sensitive components, in particular enzymes, Bleach and the bleach activator can be expected to be produced.
- Agents according to the invention can be produced in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / 1 by carrying out the builder components with at least a portion of liquid mixture components in a first process stage He- Increase in the bulk density of this premix and then - if desired after an intermediate drying - the further components of the agent, including the particulate confectioned bleaching catalyst according to formula I, combined with the premix obtained in this way.
- agents according to the invention are in the form of compressed bodies, in particular tablets, for the manufacture of which a premix is pressed which can contain all the ingredients suitable for agents according to the invention above.
- the premix can be composed of a wide variety of substances. Regardless of the composition of the premixes to be compressed, physical parameters of the premixes can be selected so that advantageous molded body properties result.
- the particulate premixes to be compressed have bulk densities above 600 g / 1, preferably above 700 g / 1 and in particular above 800 g / 1.
- the compressed particulate premix has a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5% by weight of the particles are larger than 1600 ⁇ m or smaller than Are 200 ⁇ m. Narrower particle size distributions are further preferred here. Particularly advantageous variants are characterized in that the particulate premix to be compressed has a particle size distribution in which more than 30% by weight, preferably more than 40% by weight and in particular more than 50% by weight of the particles have a particle size between 600 and 1000 ⁇ m.
- the premix is compacted in a so-called die between two punches to form a solid compressed product.
- This process which is briefly referred to below as tabletting, is divided into the four sections of metering, compression (elastic deformation), plastic deformation and ejection.
- the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool.
- the constant metering, even at high molding throughputs, is preferably achieved by volumetric metering of the premix.
- the upper punch touches the premix and lowers further in the direction of the lower punch.
- the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix) the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).
- Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper punch used to build up the drain, the lower punch also moves towards the upper punch during the pressing process, while the upper punch presses down.
- eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine.
- the Ver- Pressing can be done with one upper and one lower punch, but several punches can also be attached to one eccentric disc, the number of die holes being expanded accordingly.
- the throughputs of eccentric presses vary from a few hundred to a maximum of 3000 tablets per hour, depending on the type.
- rotary tablet presses are generally selected 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 also commercially available.
- Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
- the die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
- these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
- the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
- the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable drape rollers.
- Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
- Suitable tableting 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, Bern (CH) and Courtoy NV, Halle (BE / LU).
- the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
- the moldings can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
- the spatial shape of another embodiment of the shaped bodies is adapted in its dimensions to the metering chamber of commercially available dishwashers, so that the shaped bodies can be metered directly into the dispenser chamber without a metering aid, from where they are released during the cleaning process.
- the detergent tablets can also be used without problems using dosing aids.
- the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
- ⁇ - ⁇ Dt
- ⁇ diametral fracture stress (DFS) in Pa
- P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break
- D is the molded body diameter in meters
- t the height of the molded body.
- the method can also be expanded to the effect that multilayer molded articles are produced in a manner known per se by preparing two or more premixes which are pressed onto one another.
- the premix which has been filled in first is slightly pre-pressed in order to obtain a smooth upper surface which runs parallel to the mold body bottom, and after the second premix is filled in, it is finally pressed to give the finished mold body.
- a further preliminary treatment is carried out after each premix addition, before the molded body is finally pressed after addition of the last premix.
- the bleach activator in a form in particulate form according to the invention, it is also possible without problems to incorporate the bleach and the bleach activator into the same layer and to incorporate other sensitive constituents, in particular enzymes, into a separate second layer of the molded body.
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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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 (de) | 2000-08-04 | 2001-06-15 | Teilchenförmig konfektionierte acetonitril-derivate als bleichaktivatoren in festen waschmitteln |
Publications (2)
Publication Number | Publication Date |
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EP1305384A1 true EP1305384A1 (de) | 2003-05-02 |
EP1305384B1 EP1305384B1 (de) | 2007-08-01 |
Family
ID=7651836
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP01938265A Expired - Lifetime EP1305384B1 (de) | 2000-08-04 | 2001-06-15 | Teilchenförmig konfektionierte acetonitril-derivate als bleichaktivatoren in festen waschmitteln |
Country Status (7)
Country | Link |
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US (1) | US20040067862A1 (de) |
EP (1) | EP1305384B1 (de) |
AT (1) | ATE368723T1 (de) |
AU (1) | AU2001263963A1 (de) |
DE (2) | DE10038845A1 (de) |
ES (1) | ES2288513T3 (de) |
WO (1) | WO2002012425A1 (de) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
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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 (de) * | 2003-02-10 | 2004-08-19 | Henkel Kommanditgesellschaft Auf Aktien | Bleichmittelhaltige wasch- oder reinigungsmittel mit wasserlöslichem buildersystem und schmutzablösevermögendem cellulosederivat |
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 (de) * | 2003-02-10 | 2007-05-30 | Henkel Kommanditgesellschaft auf Aktien | Verstärkung der reinigungsleistung von waschmitteln durch cellulosederivat und hygroskopisches polymer |
WO2004069976A2 (de) * | 2003-02-10 | 2004-08-19 | Henkel Kommanditgesellschaft Auf Aktien | Verwendung von cellulosederivaten als schaumregulatoren |
DE10351321A1 (de) * | 2003-02-10 | 2004-08-26 | Henkel Kgaa | Verstärkung der Reinigungsleistung von Waschmitteln durch eine Kombination von Cellulosderivaten |
WO2005116179A1 (de) * | 2004-05-17 | 2005-12-08 | Henkel Kommanditgesellschaft Auf Aktien | Waschmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem übergangsmetallkomplex |
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) |
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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 |
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GB9022724D0 (en) * | 1990-10-19 | 1990-12-05 | Unilever Plc | Detergent compositions |
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-
2000
- 2000-08-04 DE DE10038845A patent/DE10038845A1/de not_active Ceased
-
2001
- 2001-06-15 DE DE50112796T patent/DE50112796D1/de not_active Expired - Fee Related
- 2001-06-15 AT AT01938265T patent/ATE368723T1/de not_active IP Right Cessation
- 2001-06-15 WO PCT/EP2001/006810 patent/WO2002012425A1/de active IP Right Grant
- 2001-06-15 ES ES01938265T patent/ES2288513T3/es not_active Expired - Lifetime
- 2001-06-15 EP EP01938265A patent/EP1305384B1/de not_active Expired - Lifetime
- 2001-06-15 US US10/470,281 patent/US20040067862A1/en not_active Abandoned
- 2001-06-15 AU AU2001263963A patent/AU2001263963A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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DE10038845A1 (de) | 2002-02-21 |
ATE368723T1 (de) | 2007-08-15 |
EP1305384B1 (de) | 2007-08-01 |
WO2002012425A1 (de) | 2002-02-14 |
ES2288513T3 (es) | 2008-01-16 |
US20040067862A1 (en) | 2004-04-08 |
DE50112796D1 (de) | 2007-09-13 |
AU2001263963A1 (en) | 2002-02-18 |
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