EP0919614A1 - Procédé de production des compositions détergentes à haute densité - Google Patents
Procédé de production des compositions détergentes à haute densité Download PDFInfo
- Publication number
- EP0919614A1 EP0919614A1 EP98121796A EP98121796A EP0919614A1 EP 0919614 A1 EP0919614 A1 EP 0919614A1 EP 98121796 A EP98121796 A EP 98121796A EP 98121796 A EP98121796 A EP 98121796A EP 0919614 A1 EP0919614 A1 EP 0919614A1
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- European Patent Office
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
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- 150000004985 diamines Chemical class 0.000 description 1
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- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical class O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical class CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
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- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
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- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
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- 150000007530 organic bases Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
Definitions
- the present invention relates to a method for producing detergents and cleaning agents with high bulk density, in the powdered with a first process stage Starting materials are presented and mixed with liquid components and that mixture obtained in a further process step at a defined Froude number is compressed and rounded at the same time.
- European patent 486 592 describes a process for the production of compacted Granules that can be used in detergents and cleaning agents are disclosed in which a homogeneous premix of solid, common ingredients of washing and Detergents with the addition of a plasticizer and / or lubricant under pressure above Hole shapes with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar extruded and the strand after exiting the Hole shape by means of a cutting device to the predetermined granule dimension is cut. Extrudates are obtained by this process.
- washing powder particles with a high bulk density in which washing powder particles with a bulk density of 500 to 1000 g / l are mixed in a mixer with application of shear forces by contact of the particles with one another.
- the mixer used has a rotating container.
- the washing powder particles are mixed under the influence of shear forces caused by the contact of the particles with one another for 5 to 120 minutes in the mixing container at a Froude number of 0.2 to 0.7 and a volume-based filling rate of 15 to 50%.
- European patent 0 469 016 describes a method for producing Powder mixed products in a mixer with with mixing tools and cylindrical Wall disclosed, wherein at least one of the powdered starting products with at least one liquid is mixed by adding the liquid to that in the mixer rotating powdered product essentially tangential and in Direction of rotation is sprayed.
- the mixer becomes at a Froude number between 1 and 10 operated so that the powdered starting product in the form of a cloud in located inside the mixer and the liquid in the powdery mixed material is sprayed into the room.
- the present invention was based on the object of a method for producing powder detergents or compounds available for this purpose put that in grain morphology, breadth of the grain spectrum and bulk density of the means Extrusion obtained resembles powders, but an improved dissolving behavior and compared the conventionally obtained products have higher bulk densities, but a comparable one until should have better dissolving behavior.
- the method according to the invention enables granular or spherical washing and Produce detergent particles, which by comparison with the conventional Roll granulation etc. produced an increased level of detergents and cleaning agents Have bulk density that comes close to the bulk density of granules, but not like extrudates that show solubility problems.
- the washing and Detergent particles are characterized by a certain surface morphology out. From a macroscopic point of view, the particles almost become spherical while they are microscopic have a certain porosity, due to the good solubility the particle is conditioned.
- the second stage of the process does not, as in others Manufacturing process, obtained homogeneous particles. Rather, they remain original used particles in their composition essentially constant. It takes place an even distribution of the components in the mixture, but it will not get homogeneous mass.
- the powdery starting materials can be individual substances or compounds.
- One possible embodiment uses compounds of different compositions, for example from spray drying or from others Manufacturing processes can originate in a first process step with each other mixed.
- the second stage of the process there may be other sensitive ones
- Substances or compounds containing sensitive substances are added and according to the invention, the total mixture is at a Froude number of 20 to 80 condensed.
- Macroscopically, particles with a uniform particle size and Get external shape, but have a different composition can. Such enables the recipes of washing and Split detergents into compounds and then in a common one Process step to pearl.
- powdery starting materials are presented and mixed together.
- Preferred powdery starting materials are Anionic surfactants, zeolite, silicate, soda and especially peroxy bleaching agents such as perborate.
- Granular precursors for example spray-dried or granulated ones, can also be used Surfactant compounds are used. Also preferred are foam inhibitors that are bound to a granular carrier substance, with the other powdery Starting materials mixed in the first stage of the process.
- temperature-sensitive detergent and cleaning agent components such as. Bleach and enzymes added in compound form become.
- the individual components namely the Mixture from the first stage of the process and further components added condensed and rounded at the same time.
- the temperature sensitive components have the same morphological structure as that temperature-insensitive components.
- the overall appearance of the Agent produced according to the invention is uniform, although the individual particles have different ingredients.
- Any mixer can be used as a mixer in the process according to the invention that have a Froude number between 20 and 80.
- the Einch-Mischer®, Marumenzer® and Spheronizer® can be called.
- the bulk density of the detergents and cleaning agents produced according to the invention high bulk density is generally between about 600 and 1,200 g / l. Particularly preferred the bulk density is between 700 and 950 g / l.
- the diameter of the invention produced detergent and detergent particles is arbitrary, the maximum of Particle size distribution should be less than 2 mm. An optimum in terms of The solubility of the particles and the appearance of the end product are at a Particle size distribution between 0.8 and 1.4 obtained.
- the processability of the particles produced in the first stage of the process can thereby improve by adding a plasticizer to the powdered raw materials is added.
- a plasticizer for example, higher boiling, optionally liquid nonionic surfactants, polyfunctional alcohols, at Flowable polyalkoxylates and room temperature or moderately elevated temperatures the like into consideration.
- Plasticizing aids can be used in an amount of 3 to 19% by weight. be used.
- surface modification agents As a means of Surface modification comes for example finely divided zeolite powders, e.g. Zeolite A and zeolite X, magnesium silicate, silicas, powdered silicone defoamers in Consideration.
- the surface modification agents can be used in an amount of up to 10% by weight, preferably from 0.5 to 3% by weight, based on the agent produced be.
- the washing and cleaning agents produced according to the invention contain in their Total composition preferably at least 10% by weight, in particular 10 to 45 % By weight of anionic and / or nonionic surfactants. From an application perspective are detergents and cleaning agents containing 15 to 35% by weight anionic and / or contain nonionic surfactants, particularly preferred.
- Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
- alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants, as will be described further below.
- alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
- sulfate-type surfactants such as the alk (en) yl sulfates, the alkali metal and, in particular, the sodium salts of the sulfuric acid semiesters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol , 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.
- sulfate-type surfactants such as the alk (en) yl sulfates, the alkali metal and, in particular, the sodium salts of the sulfuric acid semiesters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol , Cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of
- alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C.
- the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
- saturated alkyl sulfates not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
- Mixtures of saturated sulfated fatty alcohols consisting predominantly of C 16 and unsaturated sulfated fatty alcohols consisting predominantly of C 18 are particularly preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol® type (commercial product of the applicant).
- Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
- 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.
- soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
- the anionic surfactants 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, available.
- the anionic surfactants are preferably in the form of their sodium or Potassium salts, especially in the form of the sodium salts.
- the content of the washing and cleaning agents produced according to the invention with high Bulk weight is preferably 5 to 20 wt .-%, based on the total agent. you However, the content can also exceed 20% by weight and for example up to 25% by weight. be.
- Preferred anionic surfactants are fatty alkyl sulfates, alkyl benzene sulfonates, sulfosuccinates and mixtures of these, such as mixtures of fatty alk (en) yl sulfates and sulfosuccinates or fatty alkyl sulfates and fatty alk (en) ylbenzenesulfonates, especially in Combine with soap.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 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 thereof, 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 averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- the content of the ethoxylated C 12 -C 18 fatty alcohols in the finished compositions is advantageously at least 2% by weight, preferably 5 to 15% by weight, in particular 8 to 15% by weight.
- the liquid nonionic surfactants are used in a mixture with lower polyalkylene glycols which are derived from straight-chain or branched glycols having 2 to 6 carbon atoms and / or the highly ethoxylated fatty alcohols with more than 12 EO, in particular 20 to 80 EO. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
- Preferred lower polyalkylene glycols are polyethylene glycols or polypropylene glycols which have a relative molecular mass between 200 and 12,000, in particular between 200 and 4,000, for example up to 2,000.
- the weight ratio of liquid nonionic surfactant to lower polyalkylene glycol and / or highly ethoxylated fatty alcohol in these mixtures is preferably 10 1 to 1: 2, in particular 5: 1 to 1: 1.5 and is advantageously in some cases 1.5: 1 to 1: 1.5, for example 1: 1.
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- 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 alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as are described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
- nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than the had of it.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
- the polyhydroxy fatty acid amides are 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 (II) in which 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 alkyl radical or an aryl radical having 2 to 8 carbon atoms and 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, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
- 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 alkyl radical or an
- [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-A-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.
- the content of free that means not - bound water - lies in that for detergents and cleaning agents high bulk density known frame, it can for example up to 20 wt .-% be. However, preferred granules contain no more than 10% by weight of free, unbound water.
- Suitable inorganic builder substances are, for example, phosphates, preferably Tripolyphosphates, but also orthophosphates and pyrophosphates, as well as zeolite and crystalline Layered silicates.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) and zeolite A are particularly preferred.
- zeolite X and mixtures of A, X and / or P are also suitable.
- the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
- the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1.yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
- Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used in sodium salts, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, and mixtures of these.
- Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.
- Suitable polymeric polycarboxylates are, for example, the sodium salts of Polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 800 to 150,000 (based on acid).
- Suitable copolymers Polycarboxylates are especially those of acrylic acid with methacrylic acid and Acrylic acid or methacrylic acid with maleic acid.
- Have proven to be particularly suitable Copolymers of acrylic acid with maleic acid have proven to be 50 to 90% by weight of acrylic acid and contain 50 to 10% by weight of maleic acid.
- Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
- the content of the agents in (co) polymers Polycarboxylates is preferably 1 to 8% by weight, in particular 2 to 6% by weight.
- biodegradable polymers made from more than two different ones Monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
- polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained.
- Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
- alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
- the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 2 and 15% by weight.
- the sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
- bleaching agents that serve as bleaching agents and supply H 2 O 2 in water
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
- the bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
- Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening.
- Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of Ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- water-soluble, acidic Group-containing polyamides are suitable for this purpose.
- cellulose ethers such as carboxymethyl cellulose (sodium salt) are preferred.
- Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and Polyvinylpyrrolidone, for example in amounts of 0.1 to 5 wt .-%, based on the Means used.
- Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
- Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
- the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
- the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, Diethylenetriaminepenta-methylenephosphonate or ethylenediaminetetramethylenephosphonate used in amounts of 0.1 to 1.5 wt .-%.
- the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
- bleach activators are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably multiply acylated alkylenediamines such as N, N'-tetraacylated diamines, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, Triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid esters such as p- (alkanoyloxy) benzenesulfonate, in particular sodiumisononanoyloxybenzenesulfonate, and the p- (alkenoyloxy) benzenesulfonate, furthermore caprolactam derivatives, and carbthanoic anhydride such as carboxylic acid anhydride such as ester carbonic acid anhydride such as.
- bleach activators are acetylated mixtures of sorbitol and mannitol, as described for example in European patent application EP-A-0 525 239, and acetylated pentaerythritol.
- the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
- Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
- subtilisin type and in particular proteases obtained from Bacillus lentus are used.
- enzyme mixtures for example of protease and amylase or protease and Lipase or lipolytic enzymes or protease and cellulase or from Cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic acting enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of particular Interest.
- lipolytically active enzymes are the known ones Cutinases. Peroxidases or oxidases have also been found to be suitable in some cases proven.
- Suitable amylases include in particular ⁇ -amylases, iso-amylases, Pullulanases and pectinases.
- Cellobiohydrolases are preferably used as cellulases, Endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or Mixtures of these are used. Because the different types of cellulase are characterized by their CMCase and Avicelase activities can be distinguished by targeted mixtures of the Cellulases the desired activities can be set.
- the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
- the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19752388A DE19752388A1 (de) | 1997-11-26 | 1997-11-26 | Verfahren zur Herstellung von Wasch- und Reinigungsmitteln mit hoher Schüttdichte |
DE19752388 | 1997-11-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0919614A1 true EP0919614A1 (fr) | 1999-06-02 |
EP0919614B1 EP0919614B1 (fr) | 2003-10-01 |
Family
ID=7849872
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP98121796A Expired - Lifetime EP0919614B1 (fr) | 1997-11-26 | 1998-11-17 | Procédé de production des compositions détergentes à haute densité |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0919614B1 (fr) |
AT (1) | ATE251212T1 (fr) |
DE (2) | DE19752388A1 (fr) |
ES (1) | ES2210646T3 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002102959A1 (fr) * | 2001-06-19 | 2002-12-27 | Henkel Kommanditgesellschaft Auf Aktien | Produit de lavage et/ou produit de nettoyage pauvre en zeolithe et stable au stockage |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0327963A2 (fr) * | 1988-02-10 | 1989-08-16 | Henkel Kommanditgesellschaft auf Aktien | Procédé pour augmenter la densité de détergents séchés par vaporisation |
DE4211699A1 (de) * | 1992-04-08 | 1993-10-14 | Henkel Kgaa | Verfahren zur Erhöhung des Schüttgewichts sprühgetrockneter Waschmittel |
WO1995026394A1 (fr) * | 1994-03-28 | 1995-10-05 | Kao Corporation | Procede de production de particules detergentes a densite apparente elevee |
-
1997
- 1997-11-26 DE DE19752388A patent/DE19752388A1/de not_active Withdrawn
-
1998
- 1998-11-17 EP EP98121796A patent/EP0919614B1/fr not_active Expired - Lifetime
- 1998-11-17 AT AT98121796T patent/ATE251212T1/de not_active IP Right Cessation
- 1998-11-17 ES ES98121796T patent/ES2210646T3/es not_active Expired - Lifetime
- 1998-11-17 DE DE59809793T patent/DE59809793D1/de not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0327963A2 (fr) * | 1988-02-10 | 1989-08-16 | Henkel Kommanditgesellschaft auf Aktien | Procédé pour augmenter la densité de détergents séchés par vaporisation |
DE4211699A1 (de) * | 1992-04-08 | 1993-10-14 | Henkel Kgaa | Verfahren zur Erhöhung des Schüttgewichts sprühgetrockneter Waschmittel |
WO1995026394A1 (fr) * | 1994-03-28 | 1995-10-05 | Kao Corporation | Procede de production de particules detergentes a densite apparente elevee |
US5795856A (en) * | 1994-03-28 | 1998-08-18 | Kao Corporation | Method for producing detergent particles having high bulk density |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002102959A1 (fr) * | 2001-06-19 | 2002-12-27 | Henkel Kommanditgesellschaft Auf Aktien | Produit de lavage et/ou produit de nettoyage pauvre en zeolithe et stable au stockage |
Also Published As
Publication number | Publication date |
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EP0919614B1 (fr) | 2003-10-01 |
ES2210646T3 (es) | 2004-07-01 |
DE19752388A1 (de) | 1999-05-27 |
ATE251212T1 (de) | 2003-10-15 |
DE59809793D1 (de) | 2003-11-06 |
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