EP1456340B9 - Verfahren zur herstellung builderhaltiger tensidgranulate - Google Patents

Verfahren zur herstellung builderhaltiger tensidgranulate Download PDF

Info

Publication number
EP1456340B9
EP1456340B9 EP02795170A EP02795170A EP1456340B9 EP 1456340 B9 EP1456340 B9 EP 1456340B9 EP 02795170 A EP02795170 A EP 02795170A EP 02795170 A EP02795170 A EP 02795170A EP 1456340 B9 EP1456340 B9 EP 1456340B9
Authority
EP
European Patent Office
Prior art keywords
acid
acids
weight
builder
anionic surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02795170A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1456340A1 (de
EP1456340B1 (de
Inventor
Wilfried Rähse
Bernhard Orlich
Henriette Weber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1456340A1 publication Critical patent/EP1456340A1/de
Application granted granted Critical
Publication of EP1456340B1 publication Critical patent/EP1456340B1/de
Publication of EP1456340B9 publication Critical patent/EP1456340B9/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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

Definitions

  • the present invention relates to a process for the preparation of builder-containing surfactant granules and to special surfactant granules or compounds.
  • anionic surfactants fall in the course of the manufacturing process in their acid form and must be converted with suitable neutralizing agents in their alkali or alkaline earth metal salts.
  • This neutralization step can be carried out with solutions of alkali metal hydroxides or else with solid alkaline substances, in particular sodium carbonate.
  • the surfactant salts are obtained in the form of aqueous formulations, wherein water contents in the range of about 10 to 80 wt .-% and in particular in the range of about 35 to 60 wt .-% are adjustable.
  • products of this type have paste-like to cuttable properties, the flowability and pumpability of such pastes being restricted or even lost even in the range of about 50% by weight of active substance, so that further processing of such pastes, in particular during their incorporation in Solid mixtures, for example, in solid detergents and cleaning agents, considerable problems arise.
  • anionic detergent surfactants in a dry, in particular free-flowing form.
  • FAS fatty alcohol sulfates
  • anionic oleochemical surfactant compounds are the known sulfofatty acid methyl esters (fatty acid methyl ester sulfonates, MES) to be mentioned by ⁇ -sulfonation of methyl esters of fatty acids of vegetable or animal origin having predominantly 10 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts, in particular the corresponding alkali metal salts, getting produced.
  • MES fatty acid methyl ester sulfonates
  • EP-A-0 678 573 Procter & Gamble
  • EP-A-0 678 573 a process for the preparation of free-flowing surfactant granules having bulk densities above 600 g / l, in which anionic surfactant acids are reacted with an excess of neutralizing agent to form a paste containing at least 40% by weight of surfactant and this paste is mixed with one or more powders. , of which at least one must be spray-dried and contains the anionic polymer and cationic surfactant, is mixed, whereby the resulting granules can be optionally dried.
  • this document reduces the proportion of spray-dried granules in the detergents and cleaners, but does not completely avoid the spray-drying.
  • EP-A-0 438 320 discloses a batch process for the preparation of surfactant granules having bulk densities above 650 g / l. This is a solution of an alkaline inorganic substance in water with the possible addition of other solids with the Anionentensidklare and granulated in a high speed mixer / granulator with a liquid binder. Although neutralization and granulation are carried out in the same apparatus, but in separate process steps, so that the process can only be operated batchwise.
  • EP-A-0 402 112 is a continuous neutralization / granulation process for the production of FAS and / or ABS granules from the acid is known in which neutralized the ABS acid with at least 62% NaOH and then with the addition of excipients, for Example, ethoxylated alcohols or alkylphenols or a above 48.9 ° C melting polyethylene glycol having a molecular weight between 4000 and 50,000 granulated.
  • EP-A-0 508 543 (Procter & Gamble) refers to a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40 wt% surfactant paste, which is subsequently conditioned and granulated, with direct cooling with dry ice or liquid nitrogen.
  • surfactant mixtures which are subsequently sprayed onto solid absorbents and provide detergent compositions or components therefor are also disclosed in U.S. Pat EP 265,203 (Unilever).
  • the liquid surfactant mixtures disclosed in this document contain sodium or potassium salts of alkylbenzenesulfonic acids or alkylsulfuric acids in amounts of up to 80% by weight, ethoxylated nonionic surfactants in amounts of up to 80% by weight and at most 10% by weight of water.
  • the surfactant mixtures to be sprayed contain between 40 and 92% by weight of a surfactant mixture and more than 8 to at most 60% by weight of water.
  • the surfactant mixture is in turn at least 50% of polyalkoxylated nonionic surfactants and ionic surfactants.
  • a process for producing a liquid surfactant mixture from the three components anionic surfactant, nonionic surfactant and water is described in US Pat EP 507 402 (Unilever).
  • the surfactant blends disclosed herein, which are said to contain little water, are prepared by combining equimolar amounts of neutralizing agent and anionic surfactant acid in the presence of nonionic surfactant.
  • German patent application DE-A-42 32 874 discloses a process for the preparation of washing and cleaning-active Anionentensidgranulate by neutralization of anionic surfactants in their acid form.
  • the neutralizing agent there are disclosed solid powdery substances, especially sodium carbonate, which reacts with the anionic surfactant acids to form anionic surfactant, carbon dioxide and water.
  • the granules obtained have surfactant contents of about 30% by weight and bulk densities of less than 550 g / l.
  • EP 642 576 (Henkel KGaA) describes a two-stage granulation in two successive mixers / granulators, wherein in a first, low-speed granulator 40-100 wt .-%, based on the total amount of the ingredients used, the solid and liquid components vorgranuliert and in a second, insectourigen granulator, the progranulate is optionally mixed with the remaining ingredients and transferred into a granule.
  • EP 772 674 (Henkel KGaA) describes a process for the preparation of surfactant granules by spray drying, in which anionic surfactant (s) and highly concentrated alkaline solutions are treated separately with a gaseous medium and mixed in a multi-fluid nozzle, neutralized and spray-dried by spraying into a hot gas stream. The finely divided surfactant particles thus obtained are then agglomerated in a mixer to form granules having bulk densities above 400 g / l.
  • German patent application DE-A-43 14 885 discloses a process for preparing washing and cleaning-active anionic surfactant granules by neutralizing the acid form of anionic surfactants with a basic compound, wherein the hydrolysis-sensitive acid form of a hydrolysis-sensitive anionic surfactant is reacted with the neutralizing agent without releasing water.
  • the neutralizing agent used is sodium carbonate, which reacts in this process to form sodium bicarbonate.
  • the process to be provided should also allow the direct and economically attractive processing of the acid forms of detergent raw materials, but to the greatest possible extent avoid the disadvantage of energy-consuming evaporation of water.
  • the bulk densities of the builder- and surfactant-containing granules to be produced should be variable within wide limits, and it was a particular object of the present invention to be able to achieve the low bulk densities of conventional spray-drying products by means of a non-tower method.
  • the solubilities of the process end products should also be equal or superior to the end products of the processes known from the prior art.
  • the present invention relates to a process for preparing builder-containing surfactant granules by neutralization of mixtures of anionic surfactant acids and builders acids with solid neutralizing agents, in which the acids mentioned contact the solid neutralizing agent (s) wherein the weight ratio of builder acid (s) to anionic surfactant acid (s) in the acid mixture to be neutralized is 1: 500 to 50: 1 and the builder acid (s) are / is suspended in the anionic surfactant acid (s); Builder acid (s) have a particle size below 200 microns.
  • anionic surfactant acid (s) and builder acid (s) prior to neutralization i. before contacting with the solid neutralizing agent (s) mixed together.
  • This acidic mixture is then neutralized with solid neutralizing agents.
  • the acid mixture contains at least about 0.2% by weight and at most about 98% by weight of builder acid (s), corresponding to a mass ratio of builder acids to anionic surfactant acids in the acid mixture of from 1: 500 to 50: 1.
  • Builder acids are preferably used in a narrower weight ratio to anionic surfactant acids, wherein it is particularly preferred that the acid mixture contains more anionic surfactant than builder acids.
  • Preferred processes according to the invention are characterized in that the weight ratio of builder acid (s) to anionic acid (s) in the acid mixture to be neutralized is 1: 400 to 1:10, preferably 1: 250 to 1:15, particularly preferably 1: 100 to 1: 20 and especially 1:75 to 1:25.
  • the acidic mixture preferably contains at least about 0.25 wt .-% and at most about 90 wt .-% builder acid (s), preferably at least about 0.4 wt .-% and at most about 67 wt .-% Builder acid (s), more preferably at least about 1 wt .-% and at most about 80 wt .-% builder acid (s) and in particular at least about 1.3 wt .-% and at most about 4 wt .-% builder acid (n).
  • Preferred amounts of builder acid (s) in the acid mixture to be neutralized are, for example, 1.5% by weight, 1.75% by weight, 2% by weight, 2.25% by weight, 2.5% by weight. -%, 2.75 wt .-%, 3 wt .-%, 3.25 wt .-%, 3.5 wt .-% and 3.75 wt .-%, each based on the mass of the mixture to be neutralized ,
  • Preferred anionic surfactants in acid form are one or more substances from the group of carboxylic acids, sulfuric acid half esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids.
  • the compounds mentioned should have longer-chain hydrocarbon radicals, ie have at least 6 carbon atoms in the alkyl or alkenyl radical.
  • the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
  • Preferred processes according to the invention are characterized in that one or more substances from the group of the carboxylic acids, the sulfuric monoesters and the sulfonic acids, preferably from the group of the fatty acids, the fatty alkyl sulfuric acids and the alkylaryl sulfonic acids, are used as anionic surfactant in acid form. These are described below.
  • Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage.
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic acid etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octa
  • Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C) 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 ' , 1 wt .-% C 18 " ), tallow fatty acid (about 3 Wt% C 14 , 26 wt% C 16 , 2 wt% C
  • Sulfuric acid semi-esters of relatively long-chain alcohols are likewise anionic surfactants in their acid form and can be used in the context of the process according to the invention.
  • Their alkali metal salts, in particular sodium salts the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to the respective alkyl sulfuric acids and subsequently neutralized.
  • the fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters.
  • the quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
  • alkyl ether sulfuric acids which can be used in the process according to the invention are the alkyl ether sulfuric acids whose salts, the alkyl ether sulfates, are characterized by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
  • Alkyl ether sulfuric acids like the alkyl sulfuric acids, are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.
  • Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form.
  • Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons.
  • n-paraffins are treated with sulfur dioxide and chlorine under UV light irradiation converted to the corresponding sulfochlorides, the alkanesulfonates on hydrolysis with alkalis directly, upon reaction with water, the alkanesulfonic provide. Since di- and Polysulfochloride and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.
  • Another process for producing alkanesulfonic acids is sulfoxidation in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation.
  • This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals.
  • the reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical.
  • the reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid.
  • this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.
  • Olefinsulfonates are produced industrially by reaction of ⁇ -olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.
  • alkyl benzene sulfonates as powerful anionic surfactants have been known since the thirties of our century. At that time, alkylbenzenes were prepared by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
  • Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins.
  • large-scale petroleum fractions are separated with molecular sieves in the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both ⁇ - and i-olefins.
  • ABSS alkylbenzenesulfonic acid
  • alkylbenzenesulfonic acids whose alkylbenzenes were prepared by the HF process, so that the C 8-16 -, preferably C 9-13 -alkyl benzene sulfonic acids used have a content of 2-phenyl isomer of less than 22% by weight. , based on the alkylbenzenesulfonic acid.
  • anionic surfactants in their acid form may be used alone or in admixture with each other in the process of the present invention.
  • the anionic surfactant in acid form before addition to the solid neutralizing agent (s) further, preferably acidic, ingredients of detergents and cleaners in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing mixture, are admixed.
  • one or more builder acids are added to the anionic surfactant acids before the neutralization in specific proportions. These acids are mixed with the anionic surfactant acids and neutralized, with their salts in the finished granules or compound builder effect, ie, have a complex effect on the hardness of the water.
  • Builder acids which can be used here are the acid forms of the builders and co-builders usually admixed in salt form, where representatives from certain classes, in particular the class of carboxylic acids are preferred.
  • Particularly preferred methods of the invention are characterized in that as builders one or more substances from the group of citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid, gluconic acid and / or nitrilotriacetic acid, aspartic acid, ethylenediamine tetraacetic acid, aminotrimethylenephosphonic, hydroxyethanediphosphonic and / or the groups of polyaspartic acids, polyacrylic and -methacrylic acids and copolymers thereof are used. These substances will be described below.
  • Citric acid (2-hydroxy-1,2,3-propanetricarboxylic acid) has a monohydrate density of 1.542 and a melting point of 100 ° C, in anhydrous form has a density of 1.665 and a melting point of 153 ° C.
  • Citric acid is very light in water with an acid taste and an acid reaction, but it is also light in alcohol but heavy in ether and insoluble in benzene and chloroform. Upon heating above 175 ° C, decomposition occurs to produce methylmaleic anhydride.
  • Citric acid is an intermediate of the citric acid cycle which is obtained from lemon juice by precipitation with lime milk as calcium citrate, which is decomposed by sulfuric acid into calcium sulfate and free citric acid. Technically, citric acid is recovered by more than 90% by aerobic fermentation.
  • Tartaric acid (2,3-dihydroxybutanedioic acid, 2,3-dihydroxysuccinic acid, tetraric acid, tartaric acid) occurs in 3 stereoisomeric forms: the L - (+) - form [so-called natural tartaric acid, (2 R, 3 R) -form], the D - (-) - Form [(2 S, 3S) -form] and the meso-form [erythraric acid].
  • Tartaric acid is a strong acid, readily soluble in water (the L-form better than the racemate), methanol, ethanol, 1-propanol, glycerol, insoluble in chloroform.
  • the L-form occurs in many plants and fruits, in free form and as potassium, calcium or magnesium salt, eg. B. in grape juice partly as free tartaric acid, partly as potassium hydrogen tartrate, which separates as tartar along with calcium tartrate after fermentation of the wine.
  • tartaric acid tartar z. B. converted with calcium chloride or calcium hydroxide in calcium tartrate.
  • tartaric acid and gypsum are liberated with sulfuric acid, tartaric acid is thus a by-product of wine production.
  • DL or meso-tartaric acid is obtained in the oxidation of fumaric acid or maleic anhydride Hydrogen peroxide, potassium permanganate, peracids, in the presence of tungstic acid on an industrial scale.
  • Succinic acid (butanedioic acid), HOOC-CH 2 -CH 2 -COOH, has a density of 1.56, a melting point of 185-187 ° C and a boiling point of 235 ° C to form the anhydride.
  • Succinic acid is very soluble in boiling water, readily soluble in alcohols and acetone, but not in benzene, carbon tetrachloride and petroleum ether.
  • the production of succinic acid is carried out by hydrogenation of maleic acid, oxidation of 1,4-butanediol, oxo synthesis of acetylene or by fermentation of glucose.
  • Malonic acid (propanedioic acid), HOOC-CH 2 -COOH, C 3 H 4 O 4, has a density of 1.619 and a melting point of 135 ° C, slightly above this temperature forms with elimination of carbon dioxide, acetic acid.
  • Malonic acid is very light in water and pyridine, soluble in alcohol and ether, not in benzene; in aqueous solution, it decomposes from about 70 ° C to acetic acid and carbon dioxide.
  • the production of malonic acid succeeds z. B. by reaction of chloroacetic acid with NaCN and subsequent hydrolysis of the resulting cyanoacetic acid.
  • Adipic acid (hexanedioic acid).
  • HOOC- (CH 2 ) 4 -COOH has a melting point of 153 ° C and a boiling point of 265 ° C (at 133 hPa) ,. It is sparingly soluble in water.
  • the technically preferred approach to adipic acid is the oxidative cleavage of cyclohexane. Adispinic acid is produced in two stages via the intermediates cyclohexanol / cyclohexanone.
  • Maleic acid [(Z) -2-butenedioic acid] has a density of 1.590, a melting point of 130-131 ° C (from alcohol and benzene), and 138-139 ° C (from water), is readily soluble in water and Alcohol, less well in acetone, ether and glacial acetic acid, practically insoluble in benzene.
  • Maleic acid is stereoisomeric with fumaric acid, in which it can be rearranged thermally or catalytically. In contrast to fumaric acid, it is not a naturally occurring compound and is generally prepared by adding water to maleic anhydride.
  • Fumaric acid [(E) - or trans-butenedioic acid, has a density of 1.625 and is moderately soluble in boiling water and alcohol, sparingly soluble in most organic acids Solvents. Fumaric acid belongs to the fruit acids and occurs in a number of plants, eg. In fumitory (Fumaria officinalis), in Icelandic moss and in fungi and lichens. In the citric acid cycle, it occurs in the dehydrogenation of succinic acid as an intermediate. Fumaric acid is stereoisomeric with maleic acid, from which it can be prepared by isomerization; The industrial production is also done by fermentation of sugar or starch.
  • Oxalic acid (ethanedioic acid, clover acid), HOOC-COOH, has a density of 1.653, a melting point of 101.5 ° C and a boiling point of 150 ° C. Oxalic acid dissolves very well in water (120 g / L) and in ethanol, but little in ether and not at all in benzene, chloroform, petroleum ether. Oxalic acid is one of the most common vegetable acids and is found mainly in the sour clover as an acidic potassium salt, in sorrel and rhubarb.
  • Oxalic acid was previously prepared by the acid hydrolysis of cyanogen, today by the oxidation of carbohydrates, glycols, olefins, acetylenes or acetaldehyde with concentrated nitric acid in the presence of catalysts or by alkali fusion of sodium formate.
  • Nitrilotriacetic acid N (CH 2 -COOH) 3
  • NTA Nitrilotriacetic acid
  • the preparation of the sodium salts of NTA is carried out by cyanomethylation of ammonia with formaldehyde and sodium cyanide and subsequent saponification of the intermediately formed intermediate tris (cyanomethyl) amine (alkaline process), which can also be obtained by reacting hexamethylenetriamine with hydrogen cyanide in sulfuric acid (acidic process).
  • the sodium salts of NTA are readily biodegradable, complexing agents (chelating agents) from the class of aminocarboxylates, which are used in some countries, such as Canada and Switzerland, as part of builder systems in detergents. In the Federal Republic of Germany and other European countries, detergents containing NTA are not marketable because of the clearly detectable, but not mediated, differences to the biodegradable complexing agent EDTA (see below).
  • Aspartic acid (2-amino succinic acid, abbreviation of the L-form is Asp or D) has a density of 1.66, melts at 270 ° C (with decomposition) and is heavy in water, insoluble in alcohols. The nonessential amino acid L-aspartic acid can be found z. B.
  • Polyaspartic acids are polypeptides of aspartic acid. Polyaspartic acid sequences are naturally found in mussel or snail shells, where they regulate shell growth. The technical product is prepared from maleic anhydride by ammonolysis and polymerization with subsequent basic hydrolysis (Bayer) and contains both ⁇ - and ⁇ -bonds. Polyaspartic acids are excellent dispersants for solids and particularly effective stabilizers for hardness in water. As an excellent sequestering agent they are suitable for removing and preventing incrustations. They are already used in ecologically high-quality detergents.
  • Ethylenediaminetetraacetic acid (ethylenedinitrilotetraacetic acid, EDTA) decomposes at 150 ° C with CO 2 loss and is sparingly soluble in water.
  • Ethylenediaminetetraacetic acid and its alkali and alkaline earth salts (called edetates), like ethylenediamine, react with many metal ions to form non-ionized chelates, which is exploited to dissolve and remove troublesome metal salt deposits;
  • Ethylenediaminetetraacetic acid is prepared from ethylenediamine and chloroacetic acid or by acidic or alkaline cyanomethylation of ethylenediamine with formaldehyde and hydrocyanic acid.
  • phosphonic acids are, in particular, hydroxyalkane or aminoalkanephosphonic acids.
  • hydroxyalkanephosphonic acids 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is of particular importance. It is preferably neutralized to the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • suitable builder acids are, for example, the polymeric polycarboxylic acids, these being, for example, the polyacrylic acid or the polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylic acids are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are in particular polyacrylic acids, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Owing to the superior solubility of their neutralized salts, the short-chain polyacrylic acids which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylic acids in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • ethylenediaminetetra methylenephosphonic acid
  • DTPMP diethylenetriamine penta
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • PBTC 2-phosphonobutane-1,2,4-tricarboxylic acid
  • HDTMP hexa methylenediaminetetra (methylenephosphonic acid)
  • DTPA diethylenetriamine pentaacetic acid
  • PDTA propylenediaminetetraacetic acid
  • MGDA methylglycine diacetic acid
  • IDS iminodisuccinic acid
  • acid-stable ingredients with the anionic surfactant acid.
  • anionic surfactant acid offer so-called small components, which otherwise would have to be added in complicated further steps, so for example optical brighteners, dyes, etc., in which case the acid stability is to be checked.
  • Nonionic surfactants are preferably added to the anionic surfactant in acid form. This addition can improve the physical properties of the anionic surfactant-containing mixture and make subsequent incorporation of nonionic surfactants into the surfactant granules or the entire detergent and cleaning agent superfluous.
  • the different representatives from the group of nonionic surfactants are described below.
  • Processes preferred according to the invention are characterized in that the mixture of builder acid (s) and anionic surfactant acid (s) contains, prior to neutralization, further ingredients of detergents or cleaners, preferably nonionic surfactant (s), preferably in amounts of from 5 to 90% by weight. %, particularly preferably from 25 to 80% by weight and in particular from 30 to 70% by weight, in each case based on the weight of the mixture to be added to the neutralizing agent.
  • Processes according to the invention are preferred in which the builder acid (s) are present suspended in the anionic surfactant acid (s) and the builder acid (s) have a particle size below 150 ⁇ m and in particular below 100 ⁇ m.
  • the temperature of the mixture to be applied as low as possible is.
  • the anionic surfactant acids have a temperature of from 15 to 70 ° C. when added to the solid bed. preferably from 20 to 60 ° C, particularly preferably from 25 to 55 ° C and in particular from 40 to 50 ° C.
  • the solid bed has the lowest possible temperature. Preference is given here to temperatures between 0 and 30 ° C., preferably between 5 and 25 ° C. and in particular between 10 and 20 ° C.
  • the process according to the invention can be carried out, for example, in all devices in which neutralization with simultaneous granulation can be carried out.
  • Examples include mixers and granulators, in particular granulators of the type Turbo dryer ® (device from Vomm, Italy).
  • mixer granules can be carried out in a variety of conventional mixing and granulating.
  • suitable mixer for example, Eirich are ® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ® Flexomix, the Fukae ® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co ., Japan), the Lödige ® FM, KM and CB mixer (trade name of Lödige Maschinenbau GmbH, Paderborn) or the Drais ® - series T or KT (trademarks of Drais-Werke GmbH, Mannheim).
  • the process according to the invention in a low-speed mixer / granulator at peripheral speeds of the tools of 2 m / s to 7 m / s.
  • the process is carried out in a high-speed mixer / granulator at peripheral speeds of 8 m / s to 35 m / s.
  • a liquid granulation assistant in the present case the anionic surfactant acid (s) with optionally contained additives
  • a liquid granulation assistant in the present case the anionic surfactant acid (s) with optionally contained additives
  • a first, low-speed mixer / granulator on a moving solid bed sodium carbonate in the process according to the invention with optional other ingredients
  • 40 to 100 wt .-%, based on the total amount of the ingredients used pre-granulated the solid and liquid components and mixed in a second, high-speed mixer / granulator, the pregranulate from the first stage optionally with the remaining solid and / or liquid components, and is transferred into a granule.
  • a granulation aid is added to a solid bed in the first mixer / granulator and the mixture is pregranulated.
  • the composition of the granulation aid and the solid bed introduced in the first mixer are selected such that from 40 to 100% by weight, preferably from 50 to 90% by weight and in particular from 60 to 80% by weight, of the solid and liquid constituents are obtained on the total amount of ingredients used, are in the "pre-granules”.
  • This "pre-granulate" is then mixed in the second mixer with other solids and granulated with the addition of further liquid components to the finished surfactant granules.
  • the said sequence of low-speed high-speed mixer can also be reversed according to the invention, so that a process according to the invention results in which the liquid granulation aid is added to a moving solid bed in a first, high-speed mixer / granulator, wherein 40 to 100 wt .-%, based pre-granulated on the total amount of the ingredients used, the solid and liquid components and in a second, low-speed mixer / granulator, the pregranulate from the first process stage optionally mixed with the remaining solid and / or liquid components and transferred into a granule.
  • a mixer is used as a high-speed mixer, which has both a mixing and a crushing device, wherein the mixing shaft at rotational speeds of 50 to 150 revolutions / minute, preferably from 60 to 80 revolutions / Minute and the shaft of the crushing device at rotational speeds of 500 to 5000 revolutions / minute, preferably from 1000 to 3000 revolutions / minute, is operated.
  • Preferred granulation processes for producing mixer granules are carried out in mixer granulators in which some mixer parts or the entire mixer are designed to be coolable, in order to be able to remove the heat released during the neutralization reaction (in particular at high throughputs and when using undiluted raw materials).
  • the mixture of anionic surfactant acid and builder acid (s) may be fed to the solid bed by pouring in a more or less intense jet, which is less preferred for reasons of reaction control and homogeneity of anionic acid and builder acid distribution in the neutralizer is.
  • spraying or atomizing the mixture can be fed to the solid bed also in the form of droplets or a fine mist.
  • Another alternative is to prepare an acidic foam which is added to the neutralizing agent (or to which the neutralizing agent is added).
  • Such a process according to the invention is preferred and characterized in that the mixture of builder acid (s) and anionic acid (s) is charged with a gaseous medium and foamed through the gaseous medium and the resulting foam is subsequently added to a solid bed introduced into a mixer ,
  • pores denotes structures of gas-filled, spherical or polyhedron-shaped cells (pores), which are delimited by liquid, semi-liquid or highly viscous cell webs.
  • the gas bubbles are spherical due to the surface-area-decreasing effect of the interfacial tension. Above the boundary of the densest sphere packing, the bubbles are deformed into polyhedral fins, which are delimited by approximately 4-600 nm thin pellicles.
  • the cell barriers connected by so-called nodal points, form a coherent framework.
  • the foam lamellae (closed-cell foam) stretch between the cell bridges. If the foam lamellae are destroyed or flow back into the cell ridges at the end of foaming, an open-celled foam is obtained.
  • Foams are thermodynamically unstable because surface energy can be obtained by reducing the surface area. The stability and thus the existence of the foams according to the invention is thus dependent on the extent to which it is possible to prevent their self-destruction.
  • the gaseous medium is blown into said liquids, or the foaming is achieved by vigorously beating, shaking, splashing or stirring the liquid in the relevant gas atmosphere. Due to the lighter and better controllable and feasible foaming is within the present invention, the foam generation by blowing the gaseous medium ("gassing") over the other variants clearly preferred.
  • the gassing takes place continuously or discontinuously via perforated plates, sintered disks, sieve inserts, venturi nozzles, inline mixers, homogenizers or other conventional systems.
  • a gaseous medium for foaming any gases or gas mixtures can be used.
  • gases used in the art are nitrogen, oxygen, noble gases and noble gas mixtures such as helium, neon, argon and mixtures thereof, carbon dioxide, etc.
  • the inventive method is preferably carried out with air as the gaseous medium.
  • the gaseous medium can also consist entirely or partially of ozone, as a result of which oxidatively destructible impurities or discolorations in the surfactant-containing flowable components to be foamed can be eliminated or microbial attack of these components can be prevented.
  • the mixture of anionic surfactant acid and builder acid (s) is preferably foamed by the gaseous medium in each case in amounts of at least 20 vol .-%, based on the amount of liquid to be foamed, is used.
  • an anionic surfactant acid / builder acid (s) mixture is to be foamed, preferably at least 200 ml of gaseous medium are used for foaming.
  • the amount of gaseous medium is significantly above this value, so that processes are preferred in which the amount of gas used for foaming one to three hundred times. preferably five to two hundred times and especially ten to one hundred times the volume of the foamable amount of the mixture of builder acid (s) and anionic surfactant acid (s) and optionally other optional ingredients.
  • air is preferably used here as the gaseous medium. But it is also possible to use other gases or gas mixtures for foaming.
  • ozone content of the foaming gas then leads to the oxidative destruction of undesired constituents in the liquids to be foamed.
  • a clear lightening can be achieved by the addition of ozone.
  • Preferred processes are characterized in that air is used as the gaseous medium.
  • the acidic foam used as granulation aid can be characterized by further physical parameters.
  • the acidic foam has a density of not more than 0.80 gcm -3 , preferably from 0.10 to 0.60 gcm -3 and in particular from 0.30 to 0.55 gcm -3 .
  • the foam has average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm.
  • the mean pore size is calculated from the sum of all pore sizes (Pore diameter), which is divided by the number of pores and can be determined for example by photographic methods.
  • the mentioned physical parameters of temperature, density and average pore size characterize the acidic foam at the time of its formation.
  • the procedure is chosen so that the acidic foam meets the above criteria even when added to the mixer.
  • process guides are possible in which the foam meets only one or two of the above criteria when added to the mixer, but are preferably both the temperature, and the density and the pore size in the above areas when the foam enters the mixer ,
  • the acid mixture of surfactant acid (s) and builder acid (s) is added as a liquid, in the form of fine droplets or as a foam on the solid bed, it is further preferred if used as a neutralizing agent for the acids sodium carbonate and the reaction so is led that this reacts to sodium bicarbonate.
  • the amounts of anionic surfactant acid (s), builder acid (s) and sodium carbonate are to be coordinated so that a certain carbonate / bicarbonate ratio is maintained in the product.
  • the solid neutralizing agents comprise sodium carbonate which reacts at least partly to sodium bicarbonate; wherein the ratio of the weight proportions of sodium carbonate to sodium bicarbonate in the process end products is preferably 2: 1 or more, the ranges being from 50: 1 to 2: 1, preferably from 40: 1 to 2.1: 1, more preferably from 35: 1 to 2.2: 1 and in particular from 30: 1 to 2.25: 1, are particularly preferred.
  • the reaction between anionic surfactant (s) and sodium carbonate is performed so that the reaction Na 2 CO 3 + 2 anionic surfactant H ⁇ 2 anionic surfactant Na + CO 2 + H 2 O is largely suppressed and in their place the reaction Na 2 CO 3 + anionic surfactant H ⁇ anionic surfactant Na + NaHCO 3 entry.
  • the sodium carbonate is used here in excess, so that unreacted sodium carbonate remains in the product, while sodium bicarbonate is additionally formed in the reaction.
  • the amount of sodium carbonate on average (based on the agent, without taking into account any water of hydration present) is in relation to the amount of sodium bicarbonate on average (based on the agent, without consideration of any water of hydration present) in relation to this preferred variant 5: 1 to 2: 1 amount.
  • per gram of NaHCO 3 contained in the agents preferably 2 to 5 grams of Na 2 CO 3 are included.
  • "at least partially” means that a certain amount of sodium carbonate must react to sodium hydrogen carbonate at all (otherwise the definition of a Na 2 CO 3 / NaHO 3 ratio would be nonsense), but on the other hand, that for the same reasons unreacted sodium carbonate present in the product.
  • the proportion of sodium carbonate, which indeed reacts, but forms no sodium bicarbonate in the reaction should be as low as possible.
  • at least 70%, preferably at least 80%, more preferably at least 90% and in particular the total amount of reacting sodium carbonate is converted to sodium bicarbonate.
  • the proportion of reacting sodium carbonate can be determined by stoichiometric calculation of the amount of anionic acid used. Alternatively, from the formation of carbon dioxide and its quantitative determination, the proportion of "incorrectly" reacting sodium carbonate can be measured.
  • the water content of the process end products is ⁇ 15% by weight, preferably ⁇ 10% by weight, particularly preferably ⁇ 5% by weight and in particular ⁇ 2.5% by weight.
  • the low-water process procedure to ensure the desired reaction to sodium bicarbonate is preferred.
  • the raw materials used should therefore be so far as dry, dried or water-poor as possible.
  • the anionic surfactant acids preferably the highest possible concentrations are to be selected according to the invention, as long as the technical process control (agitation of the anionic surfactant acid and application to the sodium carbonate) is perfectly guaranteed.
  • Another way to promote the formation of sodium bicarbonate and to avoid the formation of carbon dioxide and water is to maintain the lowest possible temperatures. This can be achieved, for example, by cooling, but also by suitable process control or the coordination of the amounts of the reactants.
  • Processes preferred according to the invention are characterized in that the reactants are used in amounts relative to one another such that in the process end products the ratio of the proportions by weight of sodium carbonate to sodium bicarbonate is 2: 1 or more. Preferably, this weight ratio is within narrower limits, so that preferred methods are characterized in that the weight ratio of sodium carbonate to sodium bicarbonate in the process end products 50: 1 to 2: 1, preferably 40: 1 to 2.1: 1, particularly preferably 35: 1 to 2.2: 1 and in particular 30: 1 to 2.25: 1.
  • Very particularly preferred process end products of the process according to the invention are the agents described above.
  • processes according to the invention are particularly preferred which are characterized in that the weight ratio of sodium carbonate to sodium bicarbonate in the process end products is 5: 1 to 2: 1, preferably 4.5: 1 to 2: 1, particularly preferably 4: 1 to 2 , 1: 1, more preferably 3.5: 1 to 2.2: 1, and especially 3.25: 1 to 2.25: 1.
  • processes according to the invention are preferred in which the content of the process by-products of sodium hydrogencarbonate 0.5 to 20 wt .-%, preferably 1 to 15 wt .-%, particularly preferably 2.5 to 12.5 wt .-% and in particular 3 to 10 wt .-%, each based on the weight of the process end products, is.
  • the process according to the invention is based on the reaction of anionic surfactant acids and builders acids with solid neutralizing agents.
  • anionic surfactant acids and builders acids with solid neutralizing agents.
  • anionic surfactant acid and builder acid and sodium carbonate are reacted with each other.
  • other substances may also be present in the reaction mixture which may or may not be involved in the reaction.
  • reactive or inert species may be admixed with either the sodium carbonate or the anionic surfactant acid (s) prior to the reaction; Alternatively, both reactants may contain other reactive or inert ingredients.
  • excipients which do not take part in the reaction may also be added to the sodium carbonate. These should then have sufficient stability against the added acids in order to avoid local decomposition and thus unwanted discoloration or other contamination of the product.
  • the temperature of the mixture being dispensed be as low as possible.
  • the anionic surfactant acids have a temperature of from 15 to 70.degree. C., preferably from 20 to 60.degree. C., particularly preferably from 25 to 55.degree. C. and in particular from 40 to 50.degree. C., when added to the solid bed , Analogously, it is also preferred that the solid bed has the lowest possible temperature. Preference is given here to temperatures between 0 and 30 ° C., preferably between 5 and 25 ° C. and in particular between 10 and 20 ° C. Overall, preference is given to processes in which the temperature during the process is kept below 100 ° C., preferably below 80 ° C., more preferably below 60 ° C. and in particular below 50 ° C.
  • the content of the process by-products of sodium hydrogencarbonate is from 0.5 to 40% by weight, preferably from 3 to 30% by weight, particularly preferably from 5 to 25 wt .-% and in particular 10 to 20 wt .-%, each based on the weight of the process end products, is.
  • the process according to the invention can be carried out in all devices in which neutralization with simultaneous granulation can be carried out.
  • Examples include mixers and granulators, in particular granulators of the type Turbo dryer ® (device from Vomm, Italy).
  • the process according to the invention can also be carried out in a fluidized bed.
  • the invention provides that the process according to the invention is carried out in a batchwise or continuously flowing fluidized bed. It is particularly preferred to carry out the process continuously in the fluidized bed.
  • the liquid anionic surfactants in their acid form or the various liquid components can be introduced simultaneously or successively via one, for example via a nozzle with a plurality of openings, or via a plurality of nozzles in the fluidized bed.
  • the nozzle or the nozzles and the spray direction of the products to be sprayed can be arranged as desired.
  • the solid carriers which are the neutralizing agent and optionally other solids, can be dusted via one or more lines simultaneously (continuous process) or sequentially (batch process), preferably pneumatically via blowing lines, wherein the neutralizing agent in the batch process as the first solid is dusted.
  • Preferably used fluidized bed apparatus have bottom plates with dimensions of at least 0.4 m.
  • fluidized bed apparatuses are preferred which have a bottom plate with a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m.
  • fluid bed apparatuses are also suitable which have a bottom plate with a diameter larger than 5 m.
  • the bottom plate is preferably a perforated bottom plate or a Conidurplatte (commercial product of the company Hein & Lehmann, Federal Republic of Germany) used.
  • the process according to the invention is preferably carried out at fluidized air velocities of between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s, for example up to 3.5 m / s.
  • the discharge of the granules from the fluidized bed is advantageously carried out by a size classification of the granules.
  • This classification can be carried out, for example, by means of a screening device or by a countercurrent air stream (classifier air), which is regulated so that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
  • the incoming air is composed of the preferably unheated classifier air and the preferably only slightly or not heated bottom air.
  • the bottom air temperature is preferably between 10 and 70 ° C, preferably between 15 and 60 ° C, more preferably between 18 and 50 ° C. Temperatures between 20 and are particularly advantageous 40 ° C.
  • the fluidizing air generally cools due to heat losses and possibly due to the heat of vaporization of the components. However, this heat loss can be compensated or even exceeded by the heat of neutralization in the process according to the invention. It is even possible that the air outlet temperature exceeds the temperature of the fluidized air about 5 cm above the bottom plate. In a particularly preferred embodiment, the temperature of the fluidized air is about 5 cm above the bottom plate 30 to 100 ° C, preferably 35 to 80 ° C and especially 40 to 70 ° C. The air outlet temperature is preferably between 20 and 100 ° C, in particular below 70 ° C and with particular advantage between 25 and 50 ° C.
  • a starting material which serves as an initial carrier for the sprayed anionic surfactants in their acid form.
  • a starting material which serves as an initial carrier for the sprayed anionic surfactants in their acid form.
  • the neutralizing agent sodium carbonate for example, ingredients of detergents and cleaners, in particular those which can also be used as solids in the process according to the invention and which have a particle size distribution which corresponds approximately to the particle size distribution of the finished granules, are suitable as starting material.
  • sodium carbonate it is preferred to use.
  • mixer granulation and fluidized bed processes can also be combined with each other.
  • the reactants can be reacted with each other in a mixer and the resulting neutralizate be fed to a "Nachreiffung" a fluidized bed apparatus.
  • the surfactant granules obtained by the process according to the invention have in preferred processes a bulk density of 300 to 1000 g / l, preferably from 350 to 800 g / l, more preferably from 400 to 700 g / l and in particular from 400 to 500 g / l and are dust-free, ie In particular, they contain no particles with a particle size below 50 microns. Otherwise, the particle size distribution of the granules corresponds to the usual particle size distribution of a washing and cleaning agent of the prior art.
  • the granules have a particle size distribution in which a maximum of 5 wt .-%, with particular advantage at most 3 wt .-% of the particles have a diameter below 0.1 mm, in particular below 0.2 mm.
  • the particle size distribution is influenced by the nozzle positioning in the fluidized bed plant.
  • the granules are characterized by their light color and by their flowability. In this case, a further measure to prevent the sticking of the granules according to the invention is not required.
  • a process step can be followed, wherein the granules for the purpose of further increasing the bulk density in a known manner with finely divided materials, such as zeolite NaA, soda, powdered. This powdering can be carried out, for example, during a rounding step.
  • preferred granules already have such a regular, in particular approximately spherical, structure that a rounding step is generally not necessary and therefore also not preferred.
  • the process end products of the process according to the invention can be added directly to detergents or cleaners; for certain applications they can also be packaged directly as detergents or cleaners and marketed.
  • the process end products of the process according to the invention can also serve as a basis for further refined compounds.
  • the final process products of the neutralization process - optionally after mixing with other solids - are granulated with the addition of liquid active substances.
  • This granulation can in turn be carried out in a variety of apparatuses, with mixer granulators being preferred for this post-treatment step.
  • methods according to the invention are preferred in which the addition of liquid active substances takes place shortly before or during the post-maturation. This can be done in a mixer with preferably short residence times of 0.1 to 5 seconds or in a fluidized bed. Prior complete neutralization is preferred, but is not mandatory.
  • liquid active substances for the subsequent Aufgranulierung the process end products of the process according to the expert granulating liquids, ie in particular water or aqueous solutions of salts, water glass, alkylpolyglycosides, carbohydrates (mono-, oligo- and polysaccharides), synthetic polymers (PEG, PVAL, Polycarboxylates), BioPolymeren, etc. serve.
  • nonionic surfactants with water, silicone oil and water, supersaturated solvents or surfactant / air mixtures.
  • soaps for example, soaps, nonionic surfactant / polymer solutions, nonionic surfactant / pigment mixtures, melts, mono-, di-, trihydric alcohols, acetone, carbon tetrachloride, solids-containing melts, water-swollen polymers (water-containing organic solvents with swollen polymer) are used as low-water or -free granulation liquids. or gaseous melts use.
  • aqueous solutions of silicates and / or polymers preferably aqueous solutions of water glasses and / or (meth) acrylic acid polymers and / or copolymers, are used as liquid active substances.
  • the granules can be dried and / or subjected to further substances.
  • process variants are preferred in which the process end products of the granulation process are agglomerated in a fluidized bed and optionally dried.
  • the process products of the process according to the invention which have been subsequently treated have a high absorption capacity for liquid substances, in particular for nonionic surfactants, without losing their excellent solubility.
  • a further preferred variant of the method according to the invention therefore provides that the granules discharged from the fluidized bed are subjected to further substances, in particular nonionic surfactants.
  • nonionic surfactants are preferably used alkoxylated, preferably ethoxylated, especially 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 is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (II) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (III)
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can 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 can be applied.
  • Low-foaming nonionic surfactants are used as preferred surfactants.
  • the compositions prepared according to the invention contain a nonionic surfactant which has a melting point above room temperature.
  • preferred agents prepared according to the invention are characterized in that they contain nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, included.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • particularly preferred agents prepared according to the invention contain ethoxylated nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 18-20 fatty alcohols and more than 12 mol, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).
  • ethoxylated nonionic surfactant consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 18-20 fatty alcohols and more than 12 mol, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred process end products of the process according to the invention with aftertreatment step are characterized in that they are ethoxylated and contain propoxylated nonionic surfactants in which the propylene oxide in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant make up.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • a further preferred aftertreated process end product according to the invention contains nonionic surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ], in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5 stand.
  • R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • agents prepared and post-treated according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • Cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, these having only minor importance and usually only in amounts below 10% by weight, in most cases even below 5% by weight, for example from 0, 01 to 2.5 wt .-%, each based on the agent used.
  • the agents prepared according to the invention and optionally post-treated can thus also contain cationic and / or amphoteric surfactants as surfactant component.
  • anionic surfactant granules prepared according to the invention can, as described above, be processed directly into detergents or cleaners by admixing other customary ingredients of detergents or cleaners. But they can also serve as a carrier base for liquid or pasty substances, in particular nonionic surfactants and are then anionic surfactant / nonionic surfactant mixed compounds, which can also be mixed into detergents or cleaners.
  • Another object of the present invention are therefore detergents or cleaning agents containing a Maschinensendecks of the method according to the invention.
  • detergents or cleaners containing these process end products usually contain further substances from the groups of builders, co-builders, bleaches, bleach activators, dyes and bleaches Perfumes, optical brighteners, enzymes, soil-release polymers, etc. These substances are described below for the sake of completeness.
  • Builders are used in detergents or cleaners especially for binding calcium and magnesium.
  • Usual builders which are preferred in the context of the invention in amounts of 22.5 to 45 wt .-%, preferably from 25 to 40 wt .-% and in particular from 27.5 to 35 wt .-%, each based on the total agent which also contains the process end products of the process according to the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates.
  • trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders from the class of alkali metal isilicates.
  • the potassium salts are preferable to the sodium salts because they often have a higher water solubility.
  • Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.
  • Washing or cleaning agents may contain as builders phosphates, preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • builders phosphates preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids in which metaphosphoric acids (HPO 3 ), and orthophosphoric H 3 PO 4 in addition can distinguish higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddric salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH 2 PO 4 , is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price in the detergent industry, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Maddrelisches salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio, and the solution is dissolved by spraying dewatered. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.
  • Preferred washing or cleaning agents contain from 20 to 50% by weight of one or more water-soluble builders, preferably citrates and / or phosphates, preferably alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • water-soluble builders preferably citrates and / or phosphates, preferably alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • the level of water-soluble builders is within narrower limits. Preference is given here to washing or cleaning agents which contain the water-soluble excipient (s) in amounts of from 22.5 to 45% by weight, preferably from 25 to 40% by weight and in particular from 27.5 to 35% by weight. %, in each case based on the total mean.
  • compositions according to the invention may contain phosphates condensed as water-softening substances. These substances form a group of - because of their production also mentioned melting or annealing phosphates - phosphates, which can be derived from acidic salts of orthophosphoric acid (phosphoric acids) by condensation.
  • the condensed phosphates can be classified into the metaphosphates [Mnn (PO 3 ) n ] and polyphosphates (M 1 n + 2 P n O 3n + 1 or M 1 n H 2 P n O 3n + 1 ).
  • Metaphosphates are obtained as by-products of Graham's salt - mistakenly referred to as sodium hexametaphosphate - by melting NaH 2 PO 4 at temperatures above 620 ° C, wherein also intermediately so-called Maddrelisches salt is formed.
  • This and Kurrolsches salt are linear polyphosphates, which are usually not one of the metaphosphates today, but also in the context of the present invention are also used with preference as water-softening substances.
  • the quenched, glassy melt is, depending on the reaction conditions, the water-soluble Graham's salt, (NaPO 3 ) 40-50 , or a glassy condensed phosphate of the composition (NaPO 3 ) 15-20 , known as Calgon.
  • the misleading term hexametaphosphate is still in use.
  • Kurrol's salt (NaPO 3 ) n with n »5000, is also produced from the 600 ° C melt of the Maddrelian salt, if it is left for a short time at about 500 ° C. It forms high polymer water-soluble fibers.
  • ingredients In addition to builders, bleaches, bleach activators, enzymes, silver protectants, dyes and fragrances, etc. are particularly preferred ingredients. In addition, further ingredients may be present, with agents being preferred which, in addition to the end products of the process according to the invention, additionally comprise one or more substances from the group of acidifying agents, chelating agents or coating-inhibiting polymers.
  • Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients.
  • solid mono-, oligo- and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid.
  • anhydrides of these acids can be used as Acidisersstoff, in particular maleic anhydride and succinic anhydride are commercially available.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • a commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.
  • chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • complex-forming polymers ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms usually with the formation of chelate complexes, can be used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of common complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and crown ethers. Leftovers with z. T. very specific. Activities towards ions of different metals.
  • Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Also natural polymers such as cellulose, starch or chitin are complexing polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
  • Dishwashing detergent in amounts above 0.1 wt .-%, preferably above 0.5 wt .-%, more preferably above 1 wt .-% and in particular above 2.5 wt .-%, each based on the weight of Dishwashing detergent, included.
  • polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA are preferred.
  • these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts.
  • alkali metal, ammonium or alkylammonium salts, in particular sodium salts are preferred.
  • Scale-inhibiting polymers can likewise be present in the agents according to the invention. These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.
  • Scale-inhibiting polymers may also have co-builder properties.
  • Organic cobuilders which can be used in the compositions which comprise the process end products according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which are obtained by partial hydrolysis of starches can be obtained.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Aminoalkanphosphonate are preferably Ethylenediaminetetramethylenephosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, eg.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the agents according to the invention may contain further customary ingredients of cleaning agents, in particular bleaching agents, bleach activators, enzymes, silver protectants, dyes and fragrances being of importance. These substances will be described below.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Detergents or cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diper
  • Chlorinating or bromine-releasing substances can also be used as bleaching agents in dishwasher detergents according to the invention.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantione compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • Bleach activators aid the action of the bleaching agents.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacethylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
  • bleach catalysts can also be present in the agents according to the invention.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
  • Bleach activators from the group of the polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred Methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt.%, Particularly 2 to 8 wt .-% and particularly preferably 2 to 6 % By weight relative to the total agent used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOSI)
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt.%, In particular of 0.0025 wt. -% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, in each case based on the total agent used. But in special cases, more bleach activator can be used.
  • Suitable enzymes in the detergents or cleaners according to the invention are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. To bleach Oxidoreductases can also be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants.
  • the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as protein
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5 wt.%, Preferably 0.5 to about 4.5 wt.%, In each case based on ready-made washing or cleaning agent.
  • Dyes and fragrances can be added to the washing or cleaning agents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to performance.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ⁇ -isomethylionone and methyl cedryl ketone, the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the fragrances can be incorporated directly into the compositions of the invention, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and provide a lingering fragrance release for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • compositions made according to the invention may (or parts thereof) be colored with suitable dyes.
  • suitable dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.
  • the detergents or cleaners according to the invention may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • cleaner formulations In addition, frequently active chlorine-containing agents that can significantly reduce the corrosion of the silver surface.
  • chlorine-free cleaner are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • Detergents according to the invention may contain as optical brighteners derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, the parts of the Morpholino a Diethanolaminooeuvre , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g.
  • the final process products of the process according to the invention can not only be admixed with particulate detergents or cleaners, but can also be used in detergent tablets. Surprisingly, the solubility of such tablets improved by the use of the process end products of the method according to the invention in comparison to the same hard and identically composed tablets, which do not include end products of the method according to the invention.
  • Another object of the present invention is therefore the use of the process end products of process according to the invention for the production of detergents, in particular detergent tablets.
  • washing and cleaning active moldings is done by applying pressure to a mixture to be pressed, which is located in the cavity of a press.
  • the mixture to be tableted is injected directly, i. pressed without previous granulation.
  • the advantages of this so-called Maistablett ist are their simple and cost-effective application, since no further process steps and consequently no other systems are needed. However, these advantages are also faced with disadvantages.
  • a powder mixture, which is to be tabletted directly have sufficient plastic deformability and have good flow properties, furthermore, it must not show any separation tendencies during storage, transport and filling of the die.
  • washing and cleaning agent tablets are based on pulverulent components ("primary particles") which are agglomerated or granulated by suitable processes to form secondary particles having a relatively high particle diameter. These granules or mixtures of different granules are then mixed with individual powdered additives and fed to the tableting. In the context of the present invention, this means that the process end products of the process according to the invention are worked up to a premix with further ingredients, which may also be present in granular form.
  • the premix Before the particulate premix is compressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This may be advantageous for the nature and physical properties of both the premix (storage, compression) and the finished detergent tablets. finely divided Abwud réellesmittel are well-known in the art, with mostly zeolites, silicates or other inorganic salts are used. Preferably, however, the premix is "powdered” with finely divided zeolite, with faujasite-type zeolites being preferred.
  • the term "faujasite type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 ( Compare Donald W.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which need not necessarily belong to the zeolite structure group 4, can be used as a powdering agent, it being advantageous if at least 50 wt .-% of the powdery powder of a zeolite of faujasite Type persist.
  • detergent tablets which consist of a particulate premix containing granular components and subsequently admixed pulverulent substances, the one or more subsequently admixed pulverulent components comprising a faujasite-type zeolite having particle sizes of less than 100 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m and makes up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be tabletted.
  • the premixes to be compressed may additionally contain one or more substances from the group of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors. These substances have been described above.
  • the production of the shaped body according to the invention is carried out first by the dry mixing of the constituents, which may be pre-granulated in whole or in part, and subsequent InformML, in particular compression to tablets, wherein conventional Method can be used.
  • the premix is compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • the premix particles are also crushed, and even higher pressures cause sintering of the premix.
  • the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tableting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down.
  • eccentric tablet presses are preferred used, in which the one or more stamps are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are 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 commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks.
  • the filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix.
  • the pressing pressure on the premix is individually adjustable via the pressing paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.
  • Concentric presses can be provided with two Drik to increase the throughput, with the production of a tablet only a semicircle must be traversed.
  • several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling.
  • suitable process control coat and point tablets can be produced in this way, which have a zwiebischalenartigen structure, wherein in the case of the point tablets, the top of the core or the Core layers is not covered and thus remains visible.
  • Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses amount to over one million moldings per hour.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.
  • Tabletting machines suitable for the purposes of the present invention are available, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Packaging Systems GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Presses AG, Berlin, and Romaco GmbH, Worms.
  • Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ).
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can be designed in each case as separate individual elements, which corresponds to the predetermined dosage amount of the washing and / or cleaning agent.
  • the formation of the portioned compacts as tablets, in cylindrical or cuboidal form may be appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
  • Commercially available hydraulic presses, eccentric presses or Rotary presses are suitable devices, in particular for producing such compacts.
  • the spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process.
  • a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.
  • Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered.
  • This principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one side thereof.
  • the various components are not pressed into a single tablet, but that moldings are obtained which have multiple layers, ie at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution.
  • the layer structure of the moldings can be carried out in a staggered manner, whereby a dissolving process of the inner layer (s) on the edges of the molded article takes place already when the outer layers have not yet completely dissolved, but it is also possible to completely cover the inner layer (s) ) are achieved by the respective outer layer (s), which leads to a prevention of premature dissolution of constituents of the inner layer (s).
  • a shaped body consists of at least three layers, ie two outer and at least one inner layer, at least in one of the inner layers containing a peroxy bleach, while the stacked shaped body, the two outer layers and the envelope-shaped body
  • outermost layers are free of peroxy bleach.
  • peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other.
  • Such multilayer moldings have the advantage that they can be used not only via a dispensing compartment or via a metering device, which is placed in the wash liquor; Rather, it is also possible in such cases, to give the molding in direct contact with the textiles in the machine without stains caused by bleach and the like to be feared.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the moldings.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
EP02795170A 2001-12-21 2002-12-12 Verfahren zur herstellung builderhaltiger tensidgranulate Expired - Lifetime EP1456340B9 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10163603A DE10163603B4 (de) 2001-12-21 2001-12-21 Verfahren zur Herstellung builderhaltiger Tensidgranulate
DE10163603 2001-12-21
PCT/EP2002/014124 WO2003054131A1 (de) 2001-12-21 2002-12-12 Verfahren zur herstellung builderhaltiger tensidgranulate

Publications (3)

Publication Number Publication Date
EP1456340A1 EP1456340A1 (de) 2004-09-15
EP1456340B1 EP1456340B1 (de) 2008-09-10
EP1456340B9 true EP1456340B9 (de) 2009-03-04

Family

ID=7710608

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02795170A Expired - Lifetime EP1456340B9 (de) 2001-12-21 2002-12-12 Verfahren zur herstellung builderhaltiger tensidgranulate

Country Status (8)

Country Link
US (1) US7186677B2 (ja)
EP (1) EP1456340B9 (ja)
JP (1) JP4416508B2 (ja)
AT (1) ATE408000T1 (ja)
AU (1) AU2002361061A1 (ja)
DE (2) DE10163603B4 (ja)
ES (1) ES2309226T3 (ja)
WO (1) WO2003054131A1 (ja)

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10258011A1 (de) * 2002-12-12 2004-07-08 Henkel Kgaa Trockenneutralisationsverfahren
DE102004011087A1 (de) * 2004-03-06 2005-09-22 Henkel Kgaa Partikel umfassend diskrete, feinpartikuläre Tensidpartikel
KR101392380B1 (ko) * 2007-02-21 2014-05-07 주식회사 엘지생활건강 산성형태의 수용성 고분자를 함유하는 분말세제 입자 및그의 제조방법
US7763576B2 (en) * 2008-01-04 2010-07-27 Ecolab Inc. Solidification matrix using a polycarboxylic acid polymer
US8338352B2 (en) * 2007-05-07 2012-12-25 Ecolab Usa Inc. Solidification matrix
US8759269B2 (en) * 2007-07-02 2014-06-24 Ecolab Usa Inc. Solidification matrix including a salt of a straight chain saturated mono-, di-, and tri- carboxylic acid
US7759300B2 (en) * 2007-07-02 2010-07-20 Ecolab Inc. Solidification matrix including a salt of a straight chain saturated mono-, di-, or tri- carboxylic acid
GB0718944D0 (en) * 2007-09-28 2007-11-07 Reckitt Benckiser Nv Detergent composition
US8198228B2 (en) * 2008-01-04 2012-06-12 Ecolab Usa Inc. Solidification matrix using an aminocarboxylate
US8772221B2 (en) 2008-01-04 2014-07-08 Ecolab Usa Inc. Solidification matrices using phosphonocarboxylic acid copolymers and phosphonopolyacrylic acid homopolymers
US8138138B2 (en) * 2008-01-04 2012-03-20 Ecolab Usa Inc. Solidification matrix using a polycarboxylic acid polymer
EP2138568A1 (en) * 2008-06-25 2009-12-30 The Procter and Gamble Company Neutralisation process for producing a laundry detergent composition comprising anionic detersive surfactant and polymeric material
ES2471456T3 (es) * 2008-10-31 2014-06-26 Henkel Ag & Co. Kgaa Detergente para el lavado a máquina de la vajilla
DE102008063801A1 (de) * 2008-12-19 2010-06-24 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
US20100197545A1 (en) * 2009-01-30 2010-08-05 Ecolab USA High alkaline detergent composition with enhanced scale control
DE102009027164A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
MX342487B (es) * 2009-07-09 2016-09-29 The Procter & Gamble Company * Composicion detergente solida para tratamiento de tela con bajo contenido de aditivo. ligeramente alcalina, que comprende acido ftalimido peroxicaproico.
US8530403B2 (en) * 2009-11-20 2013-09-10 Ecolab Usa Inc. Solidification matrix using a maleic-containing terpolymer binding agent
US20110124547A1 (en) * 2009-11-23 2011-05-26 Ecolab Inc. Solidification matrix using a sulfonated/carboxylated polymer binding agent
US8754026B2 (en) 2010-09-27 2014-06-17 Basf Se Process for producing granules comprising one or more complexing agent salts
CN103547665B (zh) * 2011-05-18 2016-04-13 花王株式会社 洗涤剂颗粒群的制造方法
CN105829516A (zh) * 2013-11-11 2016-08-03 艺康美国股份有限公司 具有强化的污垢控制和污物分散的高碱性餐具清洗洗涤剂
USD784819S1 (en) 2015-02-18 2017-04-25 Henkel Us Iv Corporation Container for a solid state detergent
US9512388B2 (en) 2015-02-18 2016-12-06 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
USD762486S1 (en) 2015-02-18 2016-08-02 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
EP3762477B1 (en) * 2018-03-08 2024-02-07 Ecolab USA Inc. Solid enzymatic detergent compositions and methods of use and manufacture
CN109517673B (zh) * 2018-11-16 2021-03-19 太原理工大学 一种加酶无磷衣物用粉末洗涤剂及其制备方法

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3425948A (en) * 1966-01-03 1969-02-04 Wyandotte Chemicals Corp Composition and process for light-weight surfactant products
CA1276852C (en) 1985-06-21 1990-11-27 Francis John Leng Liquid detergent composition
GB8625104D0 (en) 1986-10-20 1986-11-26 Unilever Plc Detergent compositions
US5108642A (en) * 1986-10-30 1992-04-28 Colgate-Palmolive Company Solid detergent cleaning composition, and method of manufacturing
CA2017922C (en) 1989-06-09 1995-07-11 Frank Joseph Mueller Formation of discrete, high active detergent granules using a continuous neutralization system
GB9001285D0 (en) 1990-01-19 1990-03-21 Unilever Plc Detergent compositions and process for preparing them
US5066425A (en) * 1990-07-16 1991-11-19 The Procter & Gamble Company Formation of high active detergent particles
CA2027518A1 (en) * 1990-10-03 1992-04-04 Richard L. Tadsen Process for preparing high density detergent compositions containing particulate ph sensitive surfactant
GB9107092D0 (en) 1991-04-04 1991-05-22 Unilever Plc Process for preparing detergent compositions
DE69221357T2 (de) 1991-04-12 1998-03-12 Procter & Gamble Chemische Strukturierung von oberflächenaktiven Pasten zwecks Herstellung hochwirksamer Tensidgranulate
GB9120657D0 (en) * 1991-09-27 1991-11-06 Unilever Plc Detergent powders and process for preparing them
ES2104884T3 (es) * 1992-02-14 1997-10-16 Procter & Gamble Procedimiento para elaborar granulos de detergente por neutralizacion de acidos sulfonicos.
DE4216629A1 (de) * 1992-05-20 1993-11-25 Henkel Kgaa Verfahren zur Herstellung aniontensidhaltiger Wasch- und Reinigungsmittel
DE4216774A1 (de) 1992-05-21 1993-11-25 Henkel Kgaa Verfahren zur kontinuierlichen Herstellung eines granularen Wasch und/oder Reinigungsmittels
ZA936554B (en) * 1992-09-08 1995-03-06 Unilever Plc Detergent composition and process for its production.
DE4232874A1 (de) * 1992-09-30 1994-03-31 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
DE4314885A1 (de) 1993-05-05 1994-11-10 Sued Chemie Ag Verfahren zur Neutralisation der Säureform von anionischen Tensiden, danach erhaltene Agglomerate und Waschmittel
EP0678573B1 (en) 1994-04-20 2000-11-29 The Procter & Gamble Company Process for the manufacture of free-flowing detergent granules
DE4425968A1 (de) 1994-07-25 1996-02-01 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
JPH09241698A (ja) * 1996-03-13 1997-09-16 Lion Corp 高嵩密度粒状洗剤組成物の製造方法
TW397862B (en) * 1996-09-06 2000-07-11 Kao Corp Detergent granules and method for producing the same, and high-bulk density detergent composition
WO1998020104A1 (en) 1996-11-06 1998-05-14 The Procter & Gamble Company Neutralization process for making agglomerate detergent granules
GB9713748D0 (en) * 1997-06-27 1997-09-03 Unilever Plc Production of detergent granulates
DE19735788A1 (de) * 1997-08-18 1999-02-25 Henkel Kgaa Verfahren zur Herstellung hochtensidhaltiger Granulate
DE19844523A1 (de) * 1998-09-29 2000-03-30 Henkel Kgaa Granulationsverfahren
DE19844522A1 (de) * 1998-09-29 2000-03-30 Henkel Kgaa Granulationsverfahren
DE19855380A1 (de) * 1998-12-01 2000-06-08 Henkel Kgaa Granulationsverfahren
GB2344597A (en) * 1998-12-08 2000-06-14 Procter & Gamble Effervescence components
DE19858859A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Granulate
BR0016209B1 (pt) * 1999-12-08 2011-12-27 processo de preparaÇço de uma composiÇço detergente em barra.

Also Published As

Publication number Publication date
US7186677B2 (en) 2007-03-06
DE10163603A1 (de) 2003-07-10
DE10163603B4 (de) 2006-05-04
JP4416508B2 (ja) 2010-02-17
JP2005534721A (ja) 2005-11-17
DE50212773D1 (de) 2008-10-23
WO2003054131A1 (de) 2003-07-03
ES2309226T3 (es) 2008-12-16
AU2002361061A1 (en) 2003-07-09
EP1456340A1 (de) 2004-09-15
ATE408000T1 (de) 2008-09-15
US20050020469A1 (en) 2005-01-27
EP1456340B1 (de) 2008-09-10

Similar Documents

Publication Publication Date Title
EP1456340B9 (de) Verfahren zur herstellung builderhaltiger tensidgranulate
EP1192241B1 (de) Verfahren zur herstellung von wasch- und reinigungsmittelformkörpern
EP1451280B1 (de) Tensidgranulate und verfahren zur herstellung von tensidgranulaten
EP1570040B1 (de) Trockenneutralisationsverfahren ii
EP1390463B1 (de) Waschmittelformkörper mit viskoelastischer phase
EP1165742B1 (de) Ein- oder mehrphasige wasch- und reinigungsmittelformkörper mit speziellen bleichaktivatoren
EP1165741B1 (de) Wasch- und reinigungsmittelformkörper mit speziellen bleichaktivatoren
DE10232304B4 (de) Neutralisation im Mischer
WO2000014196A1 (de) Waschmitteltabletten mit bindemitteln
WO2000053713A1 (de) Granulationsverfahren
EP1159392B2 (de) Wasch- und reinigungsmittelformkörper mit tensid- bleichmittel- builderkombination
WO2005123893A1 (de) Gezielte granulation durch neutralisation im compomix
WO2004053046A1 (de) Trockenneutralisationsverfahren
EP1155111B1 (de) Verfahren zur herstellung schnell zerfallender wasch- und reinigungsmittelformkörper
WO2000017305A1 (de) Wasch- und reinigungsmittelformkörper mit grobteiligen aufbereitungskomponenten
WO2001014512A1 (de) Wasch- oder reinigungsmittelformkörper
EP1112342A1 (de) Wasch- und reinigungsmittelformkörper mit speziellem tensidgranulat
WO2000022086A1 (de) Bleichaktivator-haltige wasch- und reiningungsmittelformkörper

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040611

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: RO

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 50212773

Country of ref document: DE

Date of ref document: 20081023

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2309226

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: FI

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

Effective date: 20080910

Ref country code: SI

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

Effective date: 20080910

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

Ref country code: IE

Ref legal event code: FD4D

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

Ref country code: IE

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

Effective date: 20080910

Ref country code: BG

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

Effective date: 20081210

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

Ref country code: PT

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

Effective date: 20090210

Ref country code: NL

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

Effective date: 20080910

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20081231

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: EE

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

Effective date: 20080910

Ref country code: DK

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

Effective date: 20080910

Ref country code: MC

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

Effective date: 20081231

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20090611

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

Ref country code: BE

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

Effective date: 20081231

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

Ref country code: LI

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

Effective date: 20081231

Ref country code: CH

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

Effective date: 20081231

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

Ref country code: SE

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

Effective date: 20081210

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

Ref country code: CZ

Payment date: 20091127

Year of fee payment: 8

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

Ref country code: SK

Payment date: 20091123

Year of fee payment: 8

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

Ref country code: ES

Payment date: 20100113

Year of fee payment: 8

Ref country code: FR

Payment date: 20091221

Year of fee payment: 8

Ref country code: GB

Payment date: 20091209

Year of fee payment: 8

Ref country code: IT

Payment date: 20091221

Year of fee payment: 8

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

Ref country code: AT

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

Effective date: 20081212

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

Ref country code: DE

Payment date: 20091222

Year of fee payment: 8

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

Ref country code: CY

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

Effective date: 20080910

Ref country code: LU

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

Effective date: 20081212

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

Ref country code: TR

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

Effective date: 20080910

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

Ref country code: GR

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

Effective date: 20081211

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

Ref country code: CZ

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

Effective date: 20101212

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

Effective date: 20101212

REG Reference to a national code

Ref country code: SK

Ref legal event code: MM4A

Ref document number: E 4622

Country of ref document: SK

Effective date: 20101212

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110831

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

Ref country code: FR

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

Effective date: 20110103

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

Ref country code: GB

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

Effective date: 20101212

Ref country code: DE

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

Effective date: 20110701

Ref country code: SK

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

Effective date: 20101212

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50212773

Country of ref document: DE

Effective date: 20110701

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

Ref country code: IT

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

Effective date: 20101212

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20120305

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

Ref country code: ES

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

Effective date: 20101213