EP1205537B1 - Builder composition - Google Patents

Builder composition Download PDF

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Publication number
EP1205537B1
EP1205537B1 EP01126163A EP01126163A EP1205537B1 EP 1205537 B1 EP1205537 B1 EP 1205537B1 EP 01126163 A EP01126163 A EP 01126163A EP 01126163 A EP01126163 A EP 01126163A EP 1205537 B1 EP1205537 B1 EP 1205537B1
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EP
European Patent Office
Prior art keywords
weight
builder composition
builder
optionally
bis
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.)
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EP01126163A
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German (de)
French (fr)
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EP1205537A2 (en
EP1205537A3 (en
Inventor
Harald Dr. Bauer
Josef Di. Holz
Günther Dr. Schimmel
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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Publication of EP1205537A3 publication Critical patent/EP1205537A3/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/042Acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/361Phosphonates, phosphinates or phosphonites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/364Organic compounds containing phosphorus containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378(Co)polymerised monomers containing sulfur, e.g. sulfonate

Definitions

  • the object of the present invention was to provide a builder composition which exhibits improved release residue behavior.
  • EP 0 650 926 describes the granulation of crystalline layered sodium disilicate by roll compacting with the addition of curing agents such as water, silica sol, silica gel, surfactants, water glass, maleic acid-acrylic acid polymers and other copolymers.
  • curing agents such as water, silica sol, silica gel, surfactants, water glass, maleic acid-acrylic acid polymers and other copolymers. The aim is to produce a granulate resistant to mechanical abrasion.
  • EP 0 849 355 describes a powdered detergent and cleaner component, characterized in that it contains a reaction product of an alkaline silicate and an acidic polycarboxylate.
  • the document describes a preparation process which is characterized in that an acidic polycarboxylate solution is applied to an alkaline silicate, preferably using a solid-state mixer and a jet device. Layered silicates which have been treated with an acidic polycarboxylate are also described in DE 199 42 796.
  • US 5,540,855 describes a particulate composition consisting of crystalline layered silicate and a solid water-ionizable material selected from the group of organic acids wherein the mixing ratio of silicate to acid is about 3.5: 1 and the content of unbound moisture is less than 5% by weight ,
  • the bringing into contact of the components a), b) and c) can be carried out by all methods which ensure sufficient contact of the components with each other. Mention here only mixing, spraying and spraying techniques.
  • the water b) and / or the acid component c) can also be brought into contact with the crystalline layered sodium silicate a) in the gaseous or vaporous state.
  • the components a), b) and c) are brought into contact with each other by mixing.
  • Suitable mixers are, for example, Lödige mixers, plowshare mixers, Eyrich mixers and Schugi mixers.
  • the mixing times are preferably 0.5 s to 60 min, more preferably 2 s to 30 min.
  • the acidic component c) and the water b) are first mixed and then the resulting mixture is mixed with the crystalline layered sodium silicate a).
  • the acidic component c) is first mixed with the crystalline layered sodium silicate a) and then the water b) is mixed.
  • first of all the water b) is mixed with the crystalline layered sodium silicate a) and then the acidic component c) is mixed in again.
  • the acid component c) is mixed with a portion of the water b), then with the crystalline layered sodium silicate a) is mixed and finally the remainder of the water b) is mixed.
  • the addition of the water b) and the acidic component c) to the crystalline layered sodium silicate a) can be carried out at ambient temperature, but also at elevated temperature. Preference is given to temperatures from 0 to 400 ° C., more preferably from 10 to 200 ° C.
  • the heat can be introduced by external heating. Optionally, all components or even individual can be preheated.
  • the molar ratio d) of the crystalline layered sodium silicate a) to the total amount of H + releasable of the acidic component c) is preferably 5: 1 to 550: 1, more preferably 15: 1 to 150: 1.
  • the molar ratio e) of the water b) to the total amount of deliverable H + of the acidic component c) is preferably 4: 1 to 110: 1, more preferably 6: 1 to 85: 1.
  • the sodium silicates a) are preferably those having x values of 2, 3 or 4. Particular preference is given to sodium disilicates Na 2 Si 2 O 5 .yH 2 O with x being equal to 2.
  • the sodium silicates a) may also be used to trade mixtures.
  • Crystalline layered sodium disilicate is composed of varying percentages of the polymorphic phases alpha, beta, delta and epsilon. Commercial products may also contain amorphous portions.
  • Preferred crystalline layered sodium silicates a) contain 0 to 40 wt .-% alpha-sodium disilicate, 0 to 40 wt .-% beta-sodium disilicate, 40 to 100 wt .-% delta-sodium disilicate and 0 to 40 wt .-% amorphous shares.
  • Particularly preferred crystalline layered sodium silicates a) contain 7 to 21% by weight of alpha-sodium disilicate, 0 to 12% by weight of beta-sodium disilicate and 65 to 95% by weight of delta-sodium disilicate.
  • crystalline layered sodium silicates a) with a content of 80 to 100% by weight of beta-sodium disilicate can also be used.
  • alpha-sodium disilicate corresponds to the Na-SKS-5 described in EP-B-0 164 514, characterized by the X-ray diffraction data given there, which are assigned to the alpha-Na 2 Si 2 O 5 whose X-ray diffraction diagrams are in the Joint Committee of Powder Diffraction standards are registered with the numbers 18-1241, 22-1397, 22-1397A, 19-1233, 19-1234 and 19-1237.
  • beta-sodium disilicate corresponds to the Na-SKS-7 described in EP-B-0 164 514, characterized by the X-ray diffraction data given there, which are assigned to the beta-Na 2 Si 2 O 5 whose X-ray diffraction diagrams are available from the Joint Committee of Powder Diffraction standards are registered with the numbers 24-1123 and 29-1261.
  • delta-sodium disilicate corresponds to the Na-SKS-6 described in EP-B-0 164 514, characterized by the X-ray diffraction data given there, which are assigned to the delta-Na 2 Si 2 O 5 whose X-ray diffraction diagrams are available from the Joint Committee of Powder Diffraction standards with the number 22-1396 are registered.
  • the crystalline layered sodium silicates a) contain additional cationic and / or anionic constituents.
  • the cationic constituents are preferably alkali metal ions and / or alkaline earth metal cations and / or Fe, W, Mo, Ta, Pb, Al. Zn, Ti, V, Cr, Mn, Co and / or Ni.
  • the anionic constituents are preferably sulfates, fluorides, chlorides, bromides, iodides, carbonates, bicarbonates, nitrates, hydrated oxides, phosphates and / or borates.
  • the crystalline layered sodium silicates based on the total content of SiO 2 , contain up to 10 mol% boron. In a further preferred embodiment, the crystalline layered sodium silicates, based on the total content of SiO 2 , contain up to 20 mol% % Phosphorus.
  • the crystalline layered sodium silicate is used as a powder having an average particle size of 0.1 to 4000 .mu.m, more preferably 10 to 500 .mu.m, particularly preferably 20 to 200 .mu.m.
  • the composition obtained is further treated mechanically and thermally.
  • the resulting composition is compacted, then ground and subsequently optionally grain-fractionated.
  • the compaction step leads to a further improvement in the dissolution residue behavior.
  • the compacting is preferably a roll compacting, a press granulation or a briquetting, particularly preferably a roll compaction.
  • the temperature of the material during the compaction is preferably between 10 and 200 ° C, wherein the desired temperature can be controlled by external heating / cooling or adjusts itself by the released frictional heat.
  • the pressing pressure is preferably between 2 and 200 kN / cm roll width, more preferably between 10 and 100 kN / cm roll width.
  • Suitable roll compactors are, for example, those of Hosokawa-Bepex and Alexanderwerk.
  • the slugs produced during roll compaction are comminuted with mills of the relevant type and optionally grain-fractionated.
  • the compaction can be carried out discontinuously in batch mode or continuously.
  • the Subkom is fed back into the Kompaktor in Kreislauffahrweise and the coarse grain is returned to the mill.
  • the heat treatment of the builder composition leads to a further improvement in the dissolution residue behavior.
  • the heat treatment may be carried out directly after bringing components a), b) and c) into contact, or it may take place after compaction. Multiple heat treatments at different process stages are also within the meaning of the invention.
  • the heat treatment is carried out at temperatures between 30 and 400 ° C, more preferably between 40 and 150 ° C.
  • the duration of the heat treatment is 0.5 to 1000 minutes, more preferably 2 to 120 minutes.
  • Suitable apparatus for the heat treatment are, for example, fluidized beds, belt and tunnel ovens, air conveyors and storage containers.
  • Particularly preferred is a method in which after contacting the components a), b) and c) first heat-treated, then compacted, then ground and then optionally grain-fractionated.
  • the builder composition according to the invention is used as granules having an average particle size of 200 to 2000 .mu.m, preferably 400 to 900 .mu.m.
  • the builder composition of the invention as a ground granules having an average particle size of 0.1 to 300 .mu.m, preferably 10 to 200 .mu.m.
  • the builder compositions of the invention are preferably characterized in that the Lcaptivatelessnessstand a 0.25% aqueous solution, at 20 ° C and after stirring for 20 minutes, less than or equal to 50%, preferably less than or equal to 30%.
  • the invention also provides detergents and cleaners containing at least one of the builder compositions according to the invention.
  • the detergents are preferably heavy-duty detergents, compact heavy duty detergents, compact color detergents, heavy duty bulk detergents, special detergents, e.g. Stain salts, bleach boosters, curtain washes, wool detergents, kit detergents and commercial laundry detergents.
  • the cleaning agents are preferably machine-wash and machine-dishwashing detergents.
  • silicates are in demand because of their good dirt dispersion, their high alkalinity and their protective effect on the glass.
  • glass damage is meant both the formation of layered deposits on glasses as well as the erosion of the glass surface - both leads to the known undesirable turbidity of glasses.
  • Special detergents and cleaners contain from 1 to 50% by weight.
  • the co-builders are preferably crystalline aluminosilicates, mono-, oligo- or polymeric or copolymeric carboxylic acids, alkali metal carbonates, alkali metal orthophosphates, alkali metal polyphosphates and alkali polyphosphates, crystalline phyllosilicates, crystalline alkali metal silicates without layer structure and / or X-ray amorphous alkali metal silicates.
  • the bleach systems are preferably active chlorine carriers and / or organic or inorganic active oxygen carriers, bleach activators (e.g., TAED), bleach catalysts, discoloration-removing enzymes, perborates, and / or percarbonates.
  • bleach activators e.g., TAED
  • bleach catalysts e.g., discoloration-removing enzymes, perborates, and / or percarbonates.
  • the surface-active substances are preferably anionic, cationic, nonionic and / or zwitterionic surfactants.
  • alkyl alkoxylates As nonionic surfactants, alkyl alkoxylates, gluconamides and / or alkylpolyglycosides are particularly preferred.
  • alkyl alkoxylates are preferably ethoxylated alcohols, preferably primary alcohols, preferably having 8 to 22 C atoms and preferably 1 to 80 EO units per mole of alcohol used, wherein the alcohol radical is linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture, as is usually the case in Oxoalkoholresten.
  • Preferred ethoxylated alcohols include, for example, C 11 alcohols having 3, 5, 7, 8 and 11 EO units, (C 12 -C 15 ) alcohols having 3, 6, 7, 8, 10 and 13 EO units, (C 14 -C 15 ) -alcohols having 4, 7 and 8 EO units, (C 16 -C 18 ) -alcohols having 8, 11, 15, 20, 25, 50 and 80 EO units and mixtures thereof.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • fatty alcohol EO / PO adducts for example the ®Genapol types 3970, 2909 and 2822 from Clariant GmbH.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula R 2 -CO-N (R 3 ) -Z, in which R 2 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and Z is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • Alkylglycosides of the general formula RO (G) x are preferably used, where R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G is a glycose unit with 5 or 6 carbon atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is preferably a number between 1 and 10, more preferably x is between 1.2 and 1.4.
  • alkoxylated preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or preferably those as described in the international patent application WO Are used.
  • Suitable anionic surfactants of the sulfonate type are preferably the known (C 9 -C 13 ) -alkylbenzenesulfonates, alpha-olefinsulfonates and alkanesulfonates. Also suitable are esters of sulfo fatty acids or the disalts of the alpha-sulfo fatty acids. Other suitable anionic surfactants are sulfated Fettklareglycerinester which mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by 1 mole of monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 Mole of glycerol can be obtained.
  • Suitable alkyl sulfates are, in particular, the sulfuric acid monoesters of (C 12 -C 18 ) fatty alcohols, such as lauryl, myristyl, cetyl or stearyl alcohol, and the fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which additionally contain portions of unsaturated alcohols, eg Oleyl alcohol, may contain.
  • anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular those derived from natural fatty acids, such as coconut, palm kernel or tallow fatty acids, derived soap germs.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the pH regulators are preferably soda, citric acid, sodium citrate and / or bicarbonate.
  • detergents and cleaners may optionally contain enzymes, e.g. Protease, amylase, lipase and cellulase.
  • the invention also relates to components for detergent modular systems which preferably contain from 60 to 100% by weight of the builder composition according to the invention.
  • the invention furthermore relates to water softeners which comprise at least one of the builder compositions according to the invention.
  • Water softeners exert a performance-enhancing effect on the washing result and a protective effect with regard to the washing machine, especially in regions with high water hardness.
  • the builder composition according to the invention can also be used expressly as a component for the preparation of compounds for detergents and cleaners, water softeners and detergent building block systems.
  • compounds it is possible to achieve special effects.
  • liquid components are incorporated into powdered or tablet-shaped detergents and cleaners.
  • coloring or sprinkling of detergents and cleaners is possible.
  • special disintegration effects better dispersion of difficultly dispersible components or the porosity of tablets can be achieved thereby.
  • surfactants c) the compounds listed above are preferably used.
  • the detergents, cleaners, water softeners and modular components can be used, for example, in powder form, granule form, gel form, liquid form or tablet form.
  • the respective composition is pressed by means of a tablet press into the appropriate shape, wherein the shape may be varied (eg cylindrical, cuboid, elliptical, annular, etc).
  • the ratio of radius to height between 0.2 to 5 be.
  • the pressing pressure can be between 12 and 0.3 kN / cm 2 .
  • the pressing pressure is essentially independent of the geometric shape of the tablet.
  • Pressing pressures of 0.7 to 14.2 kN / cm 2 are preferred for the tableting of machine-dishwashing detergents, particular preference being given to pressures of 2.8 to 10 kN / cm 2 .
  • the division into different compartments serves a certain separation of otherwise incompatible ingredients.
  • any desired proportions of the formulation are pressed successively onto one another in several steps, resulting in several layers.
  • a layer thickness ratio of the two layers is particularly preferably from 1:10 to 10: 1.
  • Other applications include tablets with inserted spherical compartments.
  • the different layers and compartments of the tablets can also be colored differently.
  • phase composition of the crystalline layered sodium disilicates used A crushed solid sample is measured in a Philips PW1710 X-ray powder diffractometer (CuK alpha 2 radiation, wavelength 1.54439 angstroms, acceleration voltage 35 kV, heating current 28 mA, monochromator, scanning rate 3 degrees 2 theta per minute). The measured intensities are evaluated as follows: substance characteristic peak (d value in angstroms) Alpha phase 3.29 +/- 0.07, typically 3.31 Beta phase 2.97 +/- 0.06 Delta phase 3.97 +/- 0.08
  • the crystalline proportions in percent by weight are calculated from the intensities I a , I b and I d -measured in pulses-of the alpha, beta and delta phases according to the following formulas:
  • Alpha content: A [%] 100 * I a / (I a + I b + I d )
  • B [%] 1.41 * 100 * I b / (I a + I d )
  • Delta content: D [%] 100-A - D
  • AM X-ray amorphous content
  • the starting material is conveyed between the compactor rolls by means of a plug screw (setting level 5). This happens so fast that a pressing pressure of 10 to 100 kN / cm roll length is created.
  • the roller revolution is set to levels 3 to 7, the nip is 0.1 mm.
  • the resulting slugs (length about 50mm, thickness about 2 to 5 mm, width about 10 to 15 mm) are in a hammer mill (type UPZ, Fa. Alpine) with a Siebloch millmesser of 5mm at a speed of 600 to 1400 rpm Broken.
  • the inserts are used with the desired sieves.
  • the mesh size of the sieves decreases from top to bottom.
  • 50 g of the powder to be tested are placed on the widest sieve. Due to the oscillating motion of the screening machine, the powder material is conveyed through the various screens. The residues on the sieves will be balanced and mathematically based on the material weight. From the values, the d 50 value can be calculated.
  • the optical brighteners are mixed in a quarter of the amount of the molten alkyl ethoxylate and mixed in a household Multimixer (Braun) with half of the soda or bicarbonate or phosphate amount.
  • a ploughshare mixer from Lödige, the residual soda and the total amounts of builder composition according to the invention, phosphate, zeolite, bicarbonate, citric acid or polymer are mixed for 15 minutes at 300 rpm. Thereafter, half of the remaining alkyl ethoxylate is sprayed on in 5 minutes. Thereafter, the builder composition of the present invention is added and mixed for 10 minutes. Then the remaining second half of the alkyl ethoxylate is sprayed on for a further 5 minutes.
  • alkanesulfonate, polyvinylpyrrolidone, alkylbenzenesulfonate, soap, antifoaming agent, phosphonate or compound with optical brightener are added and admixed for 10 minutes at 300 rpm.
  • the tumble mixer the mixture from the Lödige mixer is mixed with percarbonate, perborate, TAED or enzymes under low shear and mixed for 5 minutes.
  • the detergent formulations are mixed and pressed with a tablet press from Matra in the appropriate form.
  • the pressing pressure can be between 12 and 0.3 kN / cm 2 .
  • the pellets have a height of about 18 mm and a diameter of 41 mm.
  • the dissolution residue is determined from a commercially available crystalline layered sodium disilicate powder (SKS-6 powder, Clariant GmbH). The measured values are summarized in Table 1.
  • the X-ray powder diffractometry gives the following phase composition: alpha-disilicate 19.1% by weight, beta-disilicate 9.4% by weight and delta-disilicate 71.5% by weight.
  • crystalline layered sodium disilicate powder from Example 2 is mixed with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to a total of 18 kg of powder mixture in four batches. From the powder mixture, the dissolution residue is determined. In comparison with the untreated powder from Example 2, an improved dissolution residue behavior results (see Table 1 and compare Example 2).
  • Example 3 Of the mixture of Example 3 8 kg are processed in a roll compactor at a pressing pressure of 32 kN / cm roll length. It will be about 3 kg of good grain obtained, from which the solvent residue is determined. The additional compaction leads to an improved solvent residue behavior (see Table 1 and see Example 3).
  • Example 3 From the mixture of Example 3, 10 kg are heat treated in a drying oven at 75 ° C for 1 h. The warm storage improves the dissolution residue behavior (see Table 1 and see Example 3).
  • Example 5 The material of Example 5 is processed in a roll compactor at a press pressure of 32 kN / cm roll length. About 5 kg of good grain are obtained, from which the residue is determined (see Table 1). The Lenderschreibs is compared with the examples 1, 2, 3, 4 and 5 improved. X-ray powder diffractometry shows that the polymorph disilicate phases did not change: alpha disilicate 19.3%, beta disilicate 9.9%, delta disilicate 70.8%.
  • Example 6 From the material of Example 6 4 kg are ground for about 45 minutes with a ball mill U 280A0 Fa. Welte, the metal-lined inside and the drum rotates at about 50 rev / min, milled. As grinding media 44 kg porcelain balls are used. The grinding improves the dissolution residue behavior compared with the granules from Example 6 (see Table 1 and see Example 6).
  • crystalline layered sodium disilicate powder from Example 2 is mixed in two batches with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to give 9 kg of powder mixture.
  • the mixture is heat treated in a drying oven for 1 hour at 85 ° C and then processed in a roll compactor at a pressing pressure of 32 kN / cm roll length. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1).
  • the lower water to acid ratio compared to Example 6 causes a deteriorated Lée Wegstands .
  • crystalline layered sodium disilicate powder from Example 2 is mixed in two batches with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to give 9 kg of powder mixture.
  • the mixture is heat treated in a drying oven for 1 hour at 85 ° C and then processed in a roll compactor at a pressing pressure of 32 kN / cm roll length. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1). Despite the lower amount of acid / water used, the dissolution residue behavior is similar to that in Example 6.
  • crystalline layered sodium disilicate powder from Example 2 is mixed with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to form 9 kg of powder mixture in two batches.
  • the mixture is heat treated in a drying oven for 1 hour at 85 ° C and then processed in a roll compactor at a pressing pressure of 32 kN / cm roll length. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1).
  • the dissolution residue behavior is similar to that in Example 6.
  • crystalline layered sodium disilicate powder from Example 2 is mixed in two batches with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to give 9 kg of powder mixture.
  • the mixture is heat-treated in a drying oven for 10 minutes at 100 ° C and then processed in a roll compactor at a pressing pressure of 32 kN / cm roll length. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1). Despite the changed conditions in the heat treatment, the dissolution residue behavior is similar to that in Example 6.
  • crystalline layered sodium disilicate powder from Example 2 is mixed in two batches with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to give 9 kg of powder mixture.
  • the mixture is heat treated in a drying oven for 1 h at 85 ° C and then processed in a roll compactor at a pressure of 100 kN / cm roll width. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1). Despite the changed pressing pressure, the dissolution residue behavior is similar to that in Example 6.
  • Another dissolution residue is determined from another commercially available crystalline layered sodium disilicate powder (SKS-6 powder, Clariant GmbH). The measured values are summarized in Table 1. X-ray powder diffraction gives the proportions of the polymorphic disilicate phases: alpha-disilicate 9.8% by weight, beta-disilicate 1.7% by weight and delta-disilicate 88.5% by weight. Comparing the phase compositions and solvent residues of Examples 13 and 2, it can be seen that a higher delta phase content leads to a more favorable effect. The effect obtained by increasing the delta phase content is comparable to that achieved by simply mixing crystalline layered sodium disilicate powder with water and sulfuric acid (see Examples 2 and 3).
  • crystalline layered sodium disilicate powder from example 13 is mixed with a solution of 96% strength sulfuric acid and water in the proportions given in table 1 to give 9 kg of powder mixture in two batches.
  • the mixture is heat-treated in a drying oven for 1 hour at 85 ° C and then processed in a roll compactor at a pressure of 32 kN / cm roll width. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1).
  • the dissolution residue is more favorable than in Example 13.
  • X-ray powder diffractometry shows that the phase distribution of the Sodium disilicate has not changed: alpha-disilicate 10.6%, beta-disilicate 0%, delta-disilicate 89.4%.
  • the solution residue is determined from a pulverulent detergent and cleaner component prepared according to EP 0 849 355 (see Table 1).
  • crystalline layered sodium disilicate powder from Example 13 is mixed with a solution of sodium hydrogensulfate and water in the proportions given in Table 1 to form 9 kg of powder mixture in two batches.
  • the mixture is heat treated in a drying oven for 1 hour at 80 ° C and then processed in a roll compactor at a pressure of 50 kN / cm roll width. About 4 kg of good grain are obtained, from which the residue is determined (see Table 1).
  • the dissolution residue behavior is significantly better than in Comparative Example 13.
  • test detergents having the compositions indicated in Table 2 are prepared.
  • machine-dishwashing detergents are prepared with the compositions according to Table 3.
  • a machine dishwashing detergent gel having the composition shown in Table 4 is prepared by mixing together in a disperser (Ultraturrax, Messrs. Hanke and Kunkel) water glass, phosphate, soda, sodium hydroxide, phosphonate, polymer, alkanesulfonate, phosphoric acid esters.
  • a disperser Ultraturrax, Messrs. Hanke and Kunkel
  • the builder composition according to the invention according to Example 6 and sodium hypochlorite are finally mixed in.

Description

Der Zwang zum Energiesparen bei Wasch- und Reinigungsprozessen, z.B. beim maschinellen Waschen von Textilien und Spülen von Geschirr, erfordert eine immer stärkere Senkung des Wasserverbrauchs. Wasch- und Reinigungsmittel, die auf wasserunlöslichen Buildersystemen wie Zeolith oder teillöslichen Systemen wie kristallinem schichtförmigem Natriumdisilicat basieren, stoßen damit zusehends an die Grenze ihrer Leistungsfähigkeit. Als negative Folge der Senkung des Wasserverbrauchs beobachtet man z.B. beim Waschen von Textilien - insbesondere bei dunkel gefärbten Textilien - weiße Rückstände auf den Geweben, die von nicht aufgelöstem oder schlecht dispergiertem Builder stammen.The compulsion to save energy in washing and cleaning processes, e.g. Machine washing of textiles and dishwashing requires ever greater reductions in water consumption. Detergents based on water-insoluble builder systems, such as zeolite or partially soluble systems, such as crystalline layered sodium disilicate, are rapidly reaching their limits. As a negative consequence of the reduction in water consumption, e.g. when washing textiles - especially in dark colored textiles - white residues on the tissues derived from undissolved or poorly dispersed builder.

Aufgabe der vorliegenden Erfindung war es, eine Builder-Zusammensetzung bereitzustellen, die ein verbessertes Löserückstandsverhalten zeigt.The object of the present invention was to provide a builder composition which exhibits improved release residue behavior.

EP 0 650 926 beschreibt die Granulierung von kristallinem schichtförmigem Natriumdisilicat durch Rollkompaktierung unter Zugabe von Härtungsmitteln wie Wasser, Kieselsol, Kieselgel, Tenside, Wasserglas, Maleinsäure-Acrylsäure-Polymere und anderen Copolymeren. Ziel ist die Herstellung eines gegen mechanischen Abrieb resistenten Granulates.EP 0 650 926 describes the granulation of crystalline layered sodium disilicate by roll compacting with the addition of curing agents such as water, silica sol, silica gel, surfactants, water glass, maleic acid-acrylic acid polymers and other copolymers. The aim is to produce a granulate resistant to mechanical abrasion.

EP 0 849 355 beschreibt eine pulverförmige Wasch- und Reinigungsmittel-Komponente, dadurch gekennzeichnet, dass sie ein Reaktionsprodukt aus einem alkalischem Silikat und einem sauren Polycarboxylat enthält. Die Schrift beschreibt ein Herstellverfahren, das dadurch gekennzeichnet ist, dass man auf ein alkalisches Silicat eine saure Polycarboxylatlösung aufbringt, wobei bevorzugt mit einem Feststoffmischer und einer Aufdüsevorrichtung gearbeitet wird. Schichtsilikate, die mit einem sauren Polycarboxylat behandelt sind, werden auch in DE 199 42 796 beschrieben.EP 0 849 355 describes a powdered detergent and cleaner component, characterized in that it contains a reaction product of an alkaline silicate and an acidic polycarboxylate. The document describes a preparation process which is characterized in that an acidic polycarboxylate solution is applied to an alkaline silicate, preferably using a solid-state mixer and a jet device. Layered silicates which have been treated with an acidic polycarboxylate are also described in DE 199 42 796.

Aus EP 578 986 ist die Behandlung von kristallinen Schichtsilikaten mit verschiedenen Säuren, u.a. auch mit Schwefelsäure beschrieben. In den Vergleichsbeispielen von US 5 776 893 ist die Hydrolyse von delta-Na-disilikat mit Salzsäure beschrieben. In beiden Fällen fehlt jeder Hinweis auf eine thermische Nachbehandlung.From EP 578 986 the treatment of crystalline sheet silicates with various acids, i.a. also described with sulfuric acid. The comparative examples of US Pat. No. 5,776,893 describe the hydrolysis of delta-Na-disilicate with hydrochloric acid. In both cases, there is no indication of thermal post-treatment.

US 5,540,855 beschreibt eine teilchenförmige Zusammensetzung bestehend aus kristallinem Schichtsilicat und einem festen in Wasser ionisierbaren Material ausgewählt aus der Gruppe der organischen Säuren, wobei das Mischungsverhältnis von Silicat zu Säure etwa 3.5:1 und der Gehalt an nichtgebundener Feuchte weniger als 5 Gew.-% beträgt.US 5,540,855 describes a particulate composition consisting of crystalline layered silicate and a solid water-ionizable material selected from the group of organic acids wherein the mixing ratio of silicate to acid is about 3.5: 1 and the content of unbound moisture is less than 5% by weight ,

Überraschenderweise wurde nun gefunden, dass Builder-Zusammensetzungen auf Basis von kristallinem schichtförmigem Natriumsilicat, die dadurch erhältlich sind, dass man kristallines schichtförmiges Natriumsilicat mit Wasser und einer sauren, H'-abgebenden Komponente in einem bestimmten Verhältnis miteinander in Kontakt bringt, wobei die so erhaltenen Builder-Zusammensetzungen vorteilhafterweise anschließend thermisch und gegebenenfalls mechanisch nachbehandelt werden, ein verbessertes Löserückstandsverhalten zeigen.Surprisingly, it has now been found that crystalline layered sodium silicate based builder compositions obtainable by contacting crystalline layered sodium silicate with water and an acidic H 'releasing component in a particular ratio with each other, wherein the thus obtained Builder compositions are advantageously subsequently thermally and optionally post-treated mechanically, show improved Löserückstandsverhalten.

Gegenstand der Erfindung ist demnach eine Builder-Zusammensetzung erhältlich durch miteinander in Kontakt bringen, von

  • a) kristallinem schichtförmigem Natriumsilikat der Formel NaMSixO2x+1·yH2O, wobei M Natrium oder Wasserstoff, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 bedeuten,
  • b) Wasser und
  • c) Natriumhydrogensulfat oder Schwefelsäure als saure H+-abgebende Komponente, wobei das
  • d) molare Verhältnis vom kristallinen schichtförmigen Natriumsilikat a) zur Gesamtmenge der abgebbaren H+ der sauren Komponente c) 4: 1 bis 1000 : 1 beträgt, das
  • e) molare Verhältnis vom Wasser b) zur Gesamtmenge der abgebbaren H+ der sauren Komponente c) 3 : 1 bis 1000 : 1 beträgt und
  • f) das so behandelte Natriumsilikat einer Wärmebehandlung bei 30 bis 400°C während einer Zeit von 0,5 bis 1000 min unterwirft und
  • g) das so erhaltene Natriumsilikat kompaktiert und mahlt, wobei die Kompaktierung und Hahlung entweder von oder nach der Wärmebehandlung durch geführt wird.
The subject of the invention is therefore a builder composition obtainable by bringing them into contact, of
  • a) crystalline layered sodium silicate of the formula NaMSi × O 2 × + 1 × yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20,
  • b) water and
  • c) Sodium hydrogen sulfate or sulfuric acid as the acidic H + -lending component, wherein the
  • d) molar ratio of the crystalline layered sodium silicate a) to the total amount of deliverable H + of the acid component c) is 4: 1 to 1000: 1, the
  • e) molar ratio of water b) to the total amount of deliverable H + of the acidic component c) is 3: 1 to 1000: 1, and
  • f) subjecting the thus treated sodium silicate to a heat treatment at 30 to 400 ° C for a time of 0.5 to 1000 min and
  • g) the resulting sodium silicate compacted and ground, wherein the compaction and Hahlung either from or after the heat treatment is performed by.

Das in Kontakt bringen der Komponenten a), b) und c) kann durch alle Verfahren erfolgen, die einen ausreichenden Kontakt der Komponenten untereinander gewährleisten. Erwähnt seien hier nur Misch-, Spritz- und Sprühtechniken.The bringing into contact of the components a), b) and c) can be carried out by all methods which ensure sufficient contact of the components with each other. Mention here only mixing, spraying and spraying techniques.

Das Wasser b) und/oder die saure Komponente c) können auch im gas- bzw. dampfförmigen Zustand mit dem kristallinen schichtförmigen Natriumsilicat a) in Kontakt gebracht werden.The water b) and / or the acid component c) can also be brought into contact with the crystalline layered sodium silicate a) in the gaseous or vaporous state.

Vorteilhafterweise werden die Komponenten a), b) und c) durch mischen miteinander in Kontakt gebracht.
Geeignete Mischer sind z.B. Lödige-Mischer, Pflugscharmischer, Eyrich-Mischer und Schugi-Mischer.
Bevorzugt betragen die Mischzeiten 0.5 s bis 60 min, besonders bevorzugt 2 s bis 30 min.
Advantageously, the components a), b) and c) are brought into contact with each other by mixing.
Suitable mixers are, for example, Lödige mixers, plowshare mixers, Eyrich mixers and Schugi mixers.
The mixing times are preferably 0.5 s to 60 min, more preferably 2 s to 30 min.

Beim Mischen sind alle Mischvarianten denkbar, die eine ausreichende Durchmischung der Komponenten a), b) und c) gewährleisten.
Bei einer bevorzugten Ausführungsform werden zuerst die saure Komponente c) und das Wasser b) vermischt und anschließend wird die so erhaltene Mischung mit dem kristallinen schichtförmigen Natriumsilicat a) vermischt.
In einer weiteren Ausführungsform wird zunächst die saure Komponente c) mit dem kristallinen schichtförmigen Natriumsilicat a) vermischt und anschließend wird das Wasser b) nachgemischt.
In einer weiteren Ausführungsform wird zunächst das Wasser b) mit dem kristallinen schichtförmigen Natriumsilicat a) vermischt und anschließend wird die saure Komponente c) nachgemischt.
Ebenfalls möglich ist eine Ausführungsform bei der die saure Komponente c) mit einem Teil des Wassers b) vermischt wird, danach mit dem kristallinen schichtförmigen Natriumsilicat a) vermischt wird und schließlich der Rest des Wassers b) nachgemischt wird.
When mixing all mixed variants are conceivable that ensure adequate mixing of the components a), b) and c).
In a preferred embodiment, the acidic component c) and the water b) are first mixed and then the resulting mixture is mixed with the crystalline layered sodium silicate a).
In a further embodiment, the acidic component c) is first mixed with the crystalline layered sodium silicate a) and then the water b) is mixed.
In a further embodiment, first of all the water b) is mixed with the crystalline layered sodium silicate a) and then the acidic component c) is mixed in again.
Also possible is an embodiment in which the acid component c) is mixed with a portion of the water b), then with the crystalline layered sodium silicate a) is mixed and finally the remainder of the water b) is mixed.

Die Zugabe vom Wasser b) und der sauren Komponente c) zum kristallinen schichtförmigen Natriumsilicat a) kann bei Umgebungstemperatur erfolgen, jedoch auch bei erhöhter Temperatur. Bevorzugt sind Temperaturen von 0 bis 400°C, besonders bevorzugt von 10 bis 200°C. Die Wärme kann durch externe Heizung eingebracht werden. Gegebenenfalls können alle Komponenten oder auch nur einzelne vorgeheizt werden.The addition of the water b) and the acidic component c) to the crystalline layered sodium silicate a) can be carried out at ambient temperature, but also at elevated temperature. Preference is given to temperatures from 0 to 400 ° C., more preferably from 10 to 200 ° C. The heat can be introduced by external heating. Optionally, all components or even individual can be preheated.

Die Einhaltung der unter den Punkten d) und e) genannten molaren Verhältnisse ist von wesentlicher Bedeutung für die Erfindung.
Das molare Verhältnis d) vom kristallinen schichtförmigen Natriumsilikat a) zur Gesamtmenge der abgebbaren H+ der sauren Komponente c) beträgt bevorzugt 5:1 bis 550 :1, besonders bevorzugt 15:1 bis 150:1.
Das molare Verhältnis e) vom Wasser b) zur Gesamtmenge der abgebbaren H+ der sauren Komponente c) beträgt bevorzugt 4:1 bis 110:1, besonders bevorzugt 6:1 bis 85:1.
Compliance with the molar ratios mentioned under points d) and e) is of essential importance for the invention.
The molar ratio d) of the crystalline layered sodium silicate a) to the total amount of H + releasable of the acidic component c) is preferably 5: 1 to 550: 1, more preferably 15: 1 to 150: 1.
The molar ratio e) of the water b) to the total amount of deliverable H + of the acidic component c) is preferably 4: 1 to 110: 1, more preferably 6: 1 to 85: 1.

Bevorzugt handelt es sich bei den Natriumsilikaten a) um solche mit x-Werten von 2, 3 oder 4. Besonders bevorzugt sind Natriumdisilikate Na2Si2O5*yH2O mit x gleich 2. Bei den Natriumsilikaten a) kann es sich auch um Mischungen handeln.The sodium silicates a) are preferably those having x values of 2, 3 or 4. Particular preference is given to sodium disilicates Na 2 Si 2 O 5 .yH 2 O with x being equal to 2. The sodium silicates a) may also be used to trade mixtures.

Kristallines schichtförmiges Natriumdisilikat setzt sich aus wechselnden prozentualen Anteilen der polymorphen Phasen alpha, beta, delta und epsilon zusammen. In kommerziellen Produkten können auch amorphe Anteile enthalten sein.Crystalline layered sodium disilicate is composed of varying percentages of the polymorphic phases alpha, beta, delta and epsilon. Commercial products may also contain amorphous portions.

Bevorzugte kristalline schichtförmige Natriumsilikate a) enthalten 0 bis 40 Gew.-% alpha-Natriumdisilikat, 0 bis 40 Gew.-% beta-Natriumdisilikat, 40 bis 100 Gew.-% delta- Natriumdisilikat und 0 bis 40 Gew.-% amorphe Anteile.
Besonders bevorzugte kristalline schichtförmige Natriumsilikate a) enthalten 7 bis 21 Gew.-% alpha-Natriumdisilikat, 0 bis 12 Gew.-% beta-Natriumdisilikat und 65 bis 95 Gew.-% delta-Natriumdisilikat.
Insbesondere bevorzugt sind kristalline schichtförmige Natriumsilicate a) mit einem Gehalt von 80 bis 100 Gew.-% delta-Natriumdisilicat.
Preferred crystalline layered sodium silicates a) contain 0 to 40 wt .-% alpha-sodium disilicate, 0 to 40 wt .-% beta-sodium disilicate, 40 to 100 wt .-% delta-sodium disilicate and 0 to 40 wt .-% amorphous shares.
Particularly preferred crystalline layered sodium silicates a) contain 7 to 21% by weight of alpha-sodium disilicate, 0 to 12% by weight of beta-sodium disilicate and 65 to 95% by weight of delta-sodium disilicate.
Particularly preferred are crystalline layered sodium silicates a) having a content of 80 to 100 wt .-% delta-sodium disilicate.

In einer weiteren Ausführungsform können auch kristalline schichtförmige Natriumsilicate a) mit einem Gehalt von 80 bis 100 Gew.-% beta-Natriumdisilicat verwendet werden.In a further embodiment, crystalline layered sodium silicates a) with a content of 80 to 100% by weight of beta-sodium disilicate can also be used.

Das vorgenannte alpha-Natriumdisilikat entspricht dem in der EP-B-0 164 514 beschriebenen Na-SKS-5, charakterisiert durch die dort wiedergegebenen Röntgenbeugungsdaten, die dem alpha-Na2Si2O5 zugeordnet werden, dessen Röntgenbeugungsdiagramme beim Joint Commitee of Powder Diffraction Standards mit den Nummern 18-1241, 22-1397, 22-1397A, 19-1233, 19-1234 und 19-1237 registriert sind.
Das vorgenannte beta-Natriumdisilikat entspricht dem in der EP-B-0 164 514 beschriebenen Na-SKS-7, charakterisiert durch die dort wiedergegebenen Röntgenbeugungsdaten, die dem beta-Na2Si2O5 zugeordnet werden, dessen Röntgenbeugungsdiagramme beim Joint Commitee of Powder Diffraction Standards mit den Nummern 24-1123 und 29-1261 registriert sind.
Das vorgenannte delta-Natriumdisilikat entspricht dem in der EP-B-0 164 514 beschriebenen Na-SKS-6, charakterisiert durch die dort wiedergegebenen Röntgenbeugungsdaten, die dem delta-Na2Si2O5 zugeordnet werden, dessen Röntgenbeugungsdiagramme beim Joint Commitee of Powder Diffraction Standards mit der Nummer 22-1396 registriert sind.
The abovementioned alpha-sodium disilicate corresponds to the Na-SKS-5 described in EP-B-0 164 514, characterized by the X-ray diffraction data given there, which are assigned to the alpha-Na 2 Si 2 O 5 whose X-ray diffraction diagrams are in the Joint Committee of Powder Diffraction standards are registered with the numbers 18-1241, 22-1397, 22-1397A, 19-1233, 19-1234 and 19-1237.
The abovementioned beta-sodium disilicate corresponds to the Na-SKS-7 described in EP-B-0 164 514, characterized by the X-ray diffraction data given there, which are assigned to the beta-Na 2 Si 2 O 5 whose X-ray diffraction diagrams are available from the Joint Committee of Powder Diffraction standards are registered with the numbers 24-1123 and 29-1261.
The abovementioned delta-sodium disilicate corresponds to the Na-SKS-6 described in EP-B-0 164 514, characterized by the X-ray diffraction data given there, which are assigned to the delta-Na 2 Si 2 O 5 whose X-ray diffraction diagrams are available from the Joint Committee of Powder Diffraction standards with the number 22-1396 are registered.

In einer besonderen Ausführungsform enthalten die kristallinen schichtförmigen Natriumsilikate a) zusätzliche kationische und/oder anionische Bestandteile.
Bei den kationischen Bestandteilen handelt es sich bevorzugt um Alkalimetallionen und/oder Erdalkalimetallkationen und/oder Fe, W, Mo, Ta, Pb, Al. Zn, Ti, V, Cr, Mn, Co und/oder Ni.
Bei den anionischen Bestandteilen handelt es sich bevorzugt um Sulfate, Fluoride, Chloride, Bromide, lodide, Carbonate, Hydrogencarbonate, Nitrate, Oxidhydrate, Phosphate und/oder Borate.
In einer besonderen Ausführungsform enthalten die kristallinen schichtförmigen Natriumsilicate, bezogen auf den Gesamtgehalt an SiO2, bis zu 10 Mol-% Bor. in einer weiteren bevorzugten Ausführungsform enthalten die kristallinen schichtförmigen Natriumsilicate, bezogen auf den Gesamtgehalt an SiO2, bis zu 20 Mol-% Phosphor.
In a particular embodiment, the crystalline layered sodium silicates a) contain additional cationic and / or anionic constituents.
The cationic constituents are preferably alkali metal ions and / or alkaline earth metal cations and / or Fe, W, Mo, Ta, Pb, Al. Zn, Ti, V, Cr, Mn, Co and / or Ni.
The anionic constituents are preferably sulfates, fluorides, chlorides, bromides, iodides, carbonates, bicarbonates, nitrates, hydrated oxides, phosphates and / or borates.
In a particular embodiment, the crystalline layered sodium silicates, based on the total content of SiO 2 , contain up to 10 mol% boron. In a further preferred embodiment, the crystalline layered sodium silicates, based on the total content of SiO 2 , contain up to 20 mol% % Phosphorus.

Bevorzugt wird das kristalline schichtförmige Natriumsilicat als Pulver mit einer mittleren Teilchengröße von 0,1 bis 4000 µm, besonders bevorzugt 10 bis 500 µm, insbesondere bevorzugt 20 bis 200 µm, eingesetzt.Preferably, the crystalline layered sodium silicate is used as a powder having an average particle size of 0.1 to 4000 .mu.m, more preferably 10 to 500 .mu.m, particularly preferably 20 to 200 .mu.m.

Nach dem in Kontakt bringen der Komponenten a), b) und c) wird die erhaltene Zusammensetzung noch mechanisch und thermisch weiterbehandelt.After bringing the components a), b) and c) into contact, the composition obtained is further treated mechanically and thermally.

Nach dem in Kontakt bringen der Komponenten a), b) und c) wird die erhaltene Zusammensetzung kompaktiert, danach gemahlen und anschließend gegebenenfalls kornfraktioniert. Überraschenderweise führt der Kompaktierungsschritt zu einer weiteren Verbesserung des Löserückstandsverhaltens.
Bei der Kompaktierung handelt es sich bevorzugt um eine Rollkompaktierung, eine Pressgranulierung oder eine Brikettierung, besonders bevorzugt eine Rolikompaktierung.
Die Temperatur des Materials während der Kompaktierung beträgt bevorzugt zwischen 10 und 200°C, wobei die gewünschte Temperatur durch externe Heizung/Kühlung gesteuert werden kann oder sich durch die freiwerdende Reibungswärme von allein einstellt.
After bringing the components a), b) and c) into contact, the resulting composition is compacted, then ground and subsequently optionally grain-fractionated. Surprisingly, the compaction step leads to a further improvement in the dissolution residue behavior.
The compacting is preferably a roll compacting, a press granulation or a briquetting, particularly preferably a roll compaction.
The temperature of the material during the compaction is preferably between 10 and 200 ° C, wherein the desired temperature can be controlled by external heating / cooling or adjusts itself by the released frictional heat.

Bei der Rollkompaktierung beträgt der Pressdruck bevorzugt zwischen 2 und 200 kN/cm Walzenbreite, besonders bevorzugt zwischen 10 und 100 kN/cm Walzenbreite.
Als Rollkompaktoren eignen sich z.B. solche der Firmen Hosokawa-Bepex und Alexanderwerk.
Die bei der Rollkompaktierung entstehenden Schülpen werden mit Mühlen einschlägigen Typs zerkleinert und gegebenenfalls kornfraktioniert.
In roll compaction, the pressing pressure is preferably between 2 and 200 kN / cm roll width, more preferably between 10 and 100 kN / cm roll width.
Suitable roll compactors are, for example, those of Hosokawa-Bepex and Alexanderwerk.
The slugs produced during roll compaction are comminuted with mills of the relevant type and optionally grain-fractionated.

Die Kompaktierung kann diskontinuierlich in Batch-Fahrweise erfolgen oder auch kontinuierlich. Bei kontinuierlichem Betrieb wird in Kreislauffahrweise das Unterkom in den Kompaktor zurückgespeist und das Grobkorn wird in die Mühle zurückgeführt.The compaction can be carried out discontinuously in batch mode or continuously. In continuous operation, the Subkom is fed back into the Kompaktor in Kreislauffahrweise and the coarse grain is returned to the mill.

Bei der Kompaktierung können gegebenenfalls bis zu 10 Gew.-% Kompaktierhilfsmittel, bevorzugt Wasser, Wasserglas, Polyethylenglykole, nichtionische Tenside, anionische Tenside, Polycarboxylatcopolymere, modifizierte und/oder unmodifizierte Cellulosen, Bentonite, Hectorite, Saponite und/oder andere Waschmittelinhaltsstoffe, zugesetzt werden.In the compaction optionally up to 10 wt .-% Kompaktierhilfsmittel, preferably water, water glass, polyethylene glycols, nonionic surfactants, anionic surfactants, Polycarboxylatcopolymere, modified and / or unmodified celluloses, bentonites, hectorites, saponites and / or other Detergent ingredients added.

Die Wärmebehandlung der Builder-Zusammensetzung führt zu einer weiteren Verbesserung des Löserückstandsverhaltens.
Die Wärmebehandlung kann direkt nach dem in Kontakt bringen der Komponenten a), b) und c) erfolgen oder aber sie kann nach dem Kompaktieren erfolgen. Mehrfache Wärmebehandlungen auf verschiedenen Verfahrensstufen sind auch im Sinne der Erfindung.
Die Wärmebehandlung erfolgt bei Temperaturen zwischen 30 und 400°C, besonders bevorzugt zwischen 40 und 150°C.
Die Dauer der Wärmebehandlung beträgt 0,5 bis 1000 min, besonders bevorzugt 2 bis 120 min.
Geeignete Apparate für die Wärmebehandlung sind z.B. Wirbelbetten, Band- und Tunnelöfen, Flugförderungen und Lagerbehälter.
The heat treatment of the builder composition leads to a further improvement in the dissolution residue behavior.
The heat treatment may be carried out directly after bringing components a), b) and c) into contact, or it may take place after compaction. Multiple heat treatments at different process stages are also within the meaning of the invention.
The heat treatment is carried out at temperatures between 30 and 400 ° C, more preferably between 40 and 150 ° C.
The duration of the heat treatment is 0.5 to 1000 minutes, more preferably 2 to 120 minutes.
Suitable apparatus for the heat treatment are, for example, fluidized beds, belt and tunnel ovens, air conveyors and storage containers.

Besonders bevorzugt ist ein Verfahren, bei dem nach dem in Kontakt bringen der Komponenten a), b) und c) zuerst wärmebehandelt, dann kompaktiert, dann gemahlen und anschließend gegebenenfalls kornfraktioniert wird.Particularly preferred is a method in which after contacting the components a), b) and c) first heat-treated, then compacted, then ground and then optionally grain-fractionated.

Weiterhin besonders bevorzugt ist ein Verfahren bei dem nach dem in Kontakt bringen der Komponenten a), b) und c) zuerst kompaktiert, dann gemahlen, dann gegebenenfalls kornfraktioniert und anschließend wärmebehandelt wird.Also particularly preferred is a process in which after contacting the components a), b) and c) first compacted, then ground, then optionally grain-fractionated and then heat-treated.

Die erfindungsgemäße Builder-Zusammensetzung wird als Granulat mit einer mittleren Teilchengröße von 200 bis 2000 µm, bevorzugt 400 bis 900 µm, eingesetzt.The builder composition according to the invention is used as granules having an average particle size of 200 to 2000 .mu.m, preferably 400 to 900 .mu.m.

Ebenfalls bevorzugt ist die Verwendung der erfindungsgemäßen Builder-Zusammensetzung als gemahlenes Granulat mit einer mittleren Teilchengröße von 0,1 bis 300 µm, bevorzugt 10 bis 200 µm.Also preferred is the use of the builder composition of the invention as a ground granules having an average particle size of 0.1 to 300 .mu.m, preferably 10 to 200 .mu.m.

Weiterhin sind die erfindungsgemäßen Builder-Zusammensetzungen bevorzugt dadurch gekennzeichnet, dass der Löserückstand einer 0,25 %igen wässrigen Lösung, bei 20°C und nach 20 Minuten Rühren, kleiner oder gleich 50 %, bevorzugt kleiner oder gleich 30 %, ist.Furthermore, the builder compositions of the invention are preferably characterized in that the Löserückstand a 0.25% aqueous solution, at 20 ° C and after stirring for 20 minutes, less than or equal to 50%, preferably less than or equal to 30%.

Gegenstand der Erfindung sind auch Wasch- und Reinigungsmittel enthaltend mindestens eine der erfindungsgemäßen Builder-Zusammensetzungen.The invention also provides detergents and cleaners containing at least one of the builder compositions according to the invention.

Bei den Waschmitteln handelt es sich bevorzugt um Vollwaschmittel, Compact-Vollwaschmittel, Compact-Colorwaschmittel, Vollwaschmittel geringer Schüttdichte, Spezialwaschmittel, wie z.B. Fleckensalze, Bleichbooster, Gardinenwaschmittel, Wollwaschmittel, Baukasten-Waschrnittel und gewerbliche Waschmittel.The detergents are preferably heavy-duty detergents, compact heavy duty detergents, compact color detergents, heavy duty bulk detergents, special detergents, e.g. Stain salts, bleach boosters, curtain washes, wool detergents, kit detergents and commercial laundry detergents.

Bei den Reinigungsmitteln handelt es sich bevorzugt um Maschinengeschirreiniger und Maschinengeschirrspülmittel. Hier sind Silikate vor allem wegen ihrer guten Schmutzdispergierung, ihrer hohen Alkalität und wegen ihrer Schutzwirkung für das Glas gefragt. Unter Glasschädigung versteht man dabei sowohl die Bildung von schichtförmigen Ablagerungen auf Gläsern als auch die Erosion der Glasoberfläche - beides führt zu den bekannten unerwünschten Trübungen von Gläsern.The cleaning agents are preferably machine-wash and machine-dishwashing detergents. Here, silicates are in demand because of their good dirt dispersion, their high alkalinity and their protective effect on the glass. By glass damage is meant both the formation of layered deposits on glasses as well as the erosion of the glass surface - both leads to the known undesirable turbidity of glasses.

Bevorzugte Wasch- und Reinigungsmittel enthalten

  • a) 0.5 bis 99 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung
  • b) optional 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Cobuilder
  • c) optional 1 bis 50 Gew.-%, bevorzugt 2 bis 30 Gew.-%, grenzflächenaktive Stoffe
  • d) optional 1 bis 70 Gew.-%, bevorzugt 5 bis 50 Gew.-%. Bleichsysteme
  • e) optional 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, pH-Regulatoren
  • f) ad 100 Gew.-% weitere übliche Inhaltsstoffe.
Preferred washing and cleaning agents included
  • a) 0.5 to 99 wt .-% of the builder composition according to the invention
  • b) optionally 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, co-builder
  • c) optionally 1 to 50 wt .-%, preferably 2 to 30 wt .-%, surfactants
  • d) optionally 1 to 70 wt .-%, preferably 5 to 50 wt .-%. bleaching systems
  • e) optionally 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, pH regulators
  • f) ad 100 wt .-% further customary ingredients.

Besonders bevorzugte Wasch- und Reinigungsmittel enthalten

  • a) 0,5 bis 99 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung
  • b) 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Cobuilder
  • c) optional 1 bis 50 Gew.-%, bevorzugt 2 bis 30 Gew.-%, grenzflächenaktive Stoffe,
  • d) optional 1 bis 70 Gew.-%, bevorzugt 5 bis 50 Gew.-%. Bleichsysteme
  • e) optional 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, pH-Regulatoren
  • f) ad 100 Gew.-% weitere übliche Inhaltsstoffe.
Particularly preferred detergents and cleaners contain
  • a) 0.5 to 99 wt .-% of the builder composition according to the invention
  • b) 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, co-builder
  • c) optionally 1 to 50% by weight, preferably 2 to 30% by weight, surface-active substances,
  • d) optionally 1 to 70 wt .-%, preferably 5 to 50 wt .-%. bleaching systems
  • e) optionally 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, pH regulators
  • f) ad 100 wt .-% further customary ingredients.

Weiterhin besonders bevorzugte Wasch- und Reinigungsmittel enthalten

  • a) 0,5 bis 99 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung
  • c) 1 bis 50 Gew.-%, bevorzugt 2 bis 30 Gew.-%, grenzflächenaktive Stoffe
  • b) optional 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Cobuilder
  • d) optional 1 bis 70 Gew.-%, bevorzugt 5 bis 50 Gew.-%. Bleichsysteme
  • e) optional 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, pH-Regulatoren
  • f) ad 100 Gew.-% weitere übliche Inhaltsstoffe.
Furthermore, particularly preferred washing and cleaning agents
  • a) 0.5 to 99 wt .-% of the builder composition according to the invention
  • c) 1 to 50 wt .-%, preferably 2 to 30 wt .-%, surfactants
  • b) optionally 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, co-builder
  • d) optionally 1 to 70 wt .-%, preferably 5 to 50 wt .-%. bleaching systems
  • e) optionally 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, pH regulators
  • f) ad 100 wt .-% further customary ingredients.

Weiterhin besonders bevorzugte Wasch- und Reinigungsmittel enthalten

  • a) 0,5 bis 99 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung
  • d) 1 bis 70 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Bleichsysteme
  • b) optional 0,5 bis 80 Gew.%, bevorzugt 5 bis 50 Gew.%, Cobuilder
  • c) optional 1 bis 50 Gew.%, bevorzugt 2 bis 30 Gew.-%, grenzflächenaktive Stoffe
  • e) optional 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, pH-Regulatoren
  • f) ad 100 Gew.-% weitere übliche Inhaltsstoffe.
Furthermore, particularly preferred washing and cleaning agents
  • a) 0.5 to 99 wt .-% of the builder composition according to the invention
  • d) 1 to 70 wt .-%, preferably 5 to 50 wt .-%, bleaching systems
  • b) optionally 0.5 to 80 wt.%, Preferably 5 to 50 wt.%, Cobuilder
  • c) optionally 1 to 50% by weight, preferably 2 to 30% by weight, surface-active substances
  • e) optionally 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, pH regulators
  • f) ad 100 wt .-% further customary ingredients.

Weiterhin besonders bevorzugte Wasch- und Reinigungsmittel enthalten

  • a) 0,5 bis 99 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung
  • e) 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, pH-Regulatoren
  • b) optional 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Cobuilder
  • c) optional 1 bis 50 Gew.-%, bevorzugt 2 bis 30 Gew.-%, grenzflächenaktive Stoffe,
  • d) optional 1 bis 70 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Bleichsysteme
  • f) ad 100 Gew.-% weitere übliche Inhaltsstoffe.
Furthermore, particularly preferred washing and cleaning agents
  • a) 0.5 to 99 wt .-% of the builder composition according to the invention
  • e) 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, pH regulators
  • b) optionally 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, co-builder
  • c) optionally 1 to 50% by weight, preferably 2 to 30% by weight, surface-active substances,
  • d) optionally 1 to 70 wt .-%, preferably 5 to 50 wt .-%, bleaching systems
  • f) ad 100 wt .-% further customary ingredients.

Weiterhin besonders bevorzugte Wasch- und Reinigungsmittel enthalten

  • a) 0,5 bis 99 Gew.% der erfindungsgemäßen Builder-Zusammensetzung
  • b) 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Cobuilder
  • c) 1 bis 50 Gew.-%, bevorzugt 2 bis 30 Gew.-%, grenzflächenaktive Stoffe,
  • d) optional 1 bis 70 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Bleichsysteme
  • e) optional 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, pH-Regulatoren
  • f) ad 100 Gew.-% weitere übliche Inhaltsstoffe.
Furthermore, particularly preferred washing and cleaning agents
  • a) 0.5 to 99 wt.% Of the builder composition according to the invention
  • b) 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, co-builder
  • c) 1 to 50% by weight, preferably 2 to 30% by weight, surface-active substances,
  • d) optionally 1 to 70 wt .-%, preferably 5 to 50 wt .-%, bleaching systems
  • e) optionally 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, pH regulators
  • f) ad 100 wt .-% further customary ingredients.

Weiterhin besonders bevorzugte Wasch- und Reinigungsmittel enthalten

  • a) 0,5 bis 99 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung
  • b) 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.%, Cobuilder
  • c) 1 bis 50 Gew.-%, bevorzugt 2 bis 30 Gew.-%, grenzflächenaktive Stoffe,
  • d) 1 bis 70 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Bleichsysteme
  • e) optional 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, pH-Regulatoren
  • f) ad 100 Gew.-% weitere übliche Inhaltsstoffe.
Furthermore, particularly preferred washing and cleaning agents
  • a) 0.5 to 99 wt .-% of the builder composition according to the invention
  • b) 0.5 to 80 wt .-%, preferably 5 to 50 wt.%, Cobuilder
  • c) 1 to 50% by weight, preferably 2 to 30% by weight, surface-active substances,
  • d) 1 to 70 wt .-%, preferably 5 to 50 wt .-%, bleaching systems
  • e) optionally 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, pH regulators
  • f) ad 100 wt .-% further customary ingredients.

Weiterhin besonders bevorzugte Wasch- und Reinigungsmittel enthalten

  • a) 0,5 bis 99 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung
  • b) 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Cobuilder
  • c) 1 bis 50 Gew.-%, bevorzugt 2 bis 30 Gew.-%, grenzflächenaktive Stoffe,
  • d) 1 bis 70 Gew.-%, bevorzugt 5 bis 50 Gew.-%, Bleichsysteme
  • e) 0,5 bis 80 Gew.-%, bevorzugt 5 bis 50 Gew.-%, pH-Regulatoren
  • f) ad 100 Gew.-% weitere übliche Inhaltsstoffe.
Furthermore, particularly preferred washing and cleaning agents
  • a) 0.5 to 99 wt .-% of the builder composition according to the invention
  • b) 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, co-builder
  • c) 1 to 50% by weight, preferably 2 to 30% by weight, surface-active substances,
  • d) 1 to 70 wt .-%, preferably 5 to 50 wt .-%, bleaching systems
  • e) 0.5 to 80 wt .-%, preferably 5 to 50 wt .-%, pH regulators
  • f) ad 100 wt .-% further customary ingredients.

Spezielle Wasch- und Reinigungsmittel enthalten 1 bis 50 Gew.-%. z.B. Vollwaschmittel, Colorwaschmittel, Wasserenthärter und Fleckensalze, oder 60 bis 100 Gew.-%, z.B. Baukasten-Waschmittelsysteme, der erfindungsgemäßen Builder-Zusammensetzung.Special detergents and cleaners contain from 1 to 50% by weight. For example, heavy duty detergents, color detergents, water softeners and stain salts, or 60 to 100% by weight, for example modular detergent systems, of the builder composition according to the invention.

Andere spezielle Wasch- und Reinigungsmittel, z.B. Maschinengeschirreiniger, enthalten 1 bis 30 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung.Other special detergents and cleaners, e.g. Machine dishwashing detergent, containing 1 to 30 wt .-% of the builder composition according to the invention.

Bei den Cobuildern handelt es sich bevorzugt um kristalline Aluminosilikate, mono-, oligo- oder polymere oder copolymere Carbonsäuren, Alkalicarbonate, Alkaliortho-, Alkalipyro- und Alkalipolyphosphate, kristalline Schichtsilikate, kristalline Alkalisilikate ohne Schichtstruktur und/oder röntgenamorphe Alkalisilikate.The co-builders are preferably crystalline aluminosilicates, mono-, oligo- or polymeric or copolymeric carboxylic acids, alkali metal carbonates, alkali metal orthophosphates, alkali metal polyphosphates and alkali polyphosphates, crystalline phyllosilicates, crystalline alkali metal silicates without layer structure and / or X-ray amorphous alkali metal silicates.

Bei den Bleichsystemen handelt es sich bevorzugt um Aktivchlorträger und/oder organische oder anorganische Aktivsauerstoffträger, Bleichaktivatoren (z.B. TAED), Bleichkatalysatoren, Enzyme zur Entfernung von Verfärbungen, Perborate und/oder Percarbonate.The bleach systems are preferably active chlorine carriers and / or organic or inorganic active oxygen carriers, bleach activators (e.g., TAED), bleach catalysts, discoloration-removing enzymes, perborates, and / or percarbonates.

Bei den grenzflächenaktiven Substanzen handelt es sich bevorzugt um anionische, kationische, nicht-ionische und/oder zwitterionische Tenside.The surface-active substances are preferably anionic, cationic, nonionic and / or zwitterionic surfactants.

Als nichtionische Tenside sind Alkylalkoxylate, Gluconamide und/oder Alkylpolyglycoside besonders bevorzugt.As nonionic surfactants, alkyl alkoxylates, gluconamides and / or alkylpolyglycosides are particularly preferred.

Unter den Alkylalkoxylaten werden bevorzugt ethoxylierte Alkohole, bevorzugt primäre Alkohole, mit bevorzugt 8 bis 22 C Atomen und bevorzugt 1 bis 80 EO-Einheiten pro Mol Alkohol, eingesetzt, wobei der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt ist oder lineare und methylverzweigte Reste im Gemisch enthält, so wie dies üblicherweise in Oxoalkoholresten der Fall ist. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C11-Alkohole mit 3, 5, 7,8 und 11 EO-Einheiten, (C12-C15)-Alkohole mit 3, 6, 7, 8, 10 und 13 EO-Einheiten, (C14-C15)-Alkohole mit 4, 7 und 8 EO-Einheiten, (C16-C18)-Alkohole mit 8, 11, 15, 20, 25, 50 und 80 EO-Einheiten und Mischungen derselben. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Zusätzlich zu diesen können auch Fettalkohol-EO/PO-Addukte eingesetzt werden, wie z.B. die ®Genapol-Typen 3970, 2909 und 2822 der Fa. Clariant GmbH.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel R2-CO-N(R3)-Z, in der R2CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R3 für Wasserstoff, einen Alkyl oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und Z für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.
Bevorzugt werden Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt, wobei R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten, aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, bedeutet und G für eine Glykoseeinheit mit 5 oder 6 Kohlenstoffatomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist bevorzugt eine Zahl zwischen 1 und 10, besonders bevorzugt liegt x zwischen 1,2 und 1,4.
Among the alkyl alkoxylates are preferably ethoxylated alcohols, preferably primary alcohols, preferably having 8 to 22 C atoms and preferably 1 to 80 EO units per mole of alcohol used, wherein the alcohol radical is linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture, as is usually the case in Oxoalkoholresten. Preferred ethoxylated alcohols include, for example, C 11 alcohols having 3, 5, 7, 8 and 11 EO units, (C 12 -C 15 ) alcohols having 3, 6, 7, 8, 10 and 13 EO units, (C 14 -C 15 ) -alcohols having 4, 7 and 8 EO units, (C 16 -C 18 ) -alcohols having 8, 11, 15, 20, 25, 50 and 80 EO units and mixtures thereof. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. In addition to these It is also possible to use fatty alcohol EO / PO adducts, for example the ®Genapol types 3970, 2909 and 2822 from Clariant GmbH.
Further suitable surfactants are polyhydroxy fatty acid amides of the formula R 2 -CO-N (R 3 ) -Z, in which R 2 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and Z is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
Alkylglycosides of the general formula RO (G) x are preferably used, where R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G is a glycose unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is preferably a number between 1 and 10, more preferably x is between 1.2 and 1.4.

Bevorzugt werden alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder vorzugsweise solche wie sie nach dem in der internationalen Patentanmeldung WO-90/13533 beschriebenen Verfahren hergestellt werden, eingesetzt.Preference is given to alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or preferably those as described in the international patent application WO Are used.

Als anionische Tenside vom Sulfonat-Typ kommen vorzugsweise die bekannten (C9-C13)-Alkylbenzolsulfonate, alpha-Olefinsulfonate und Alkansulfonate in Betracht. Geeignet sind auch Ester von Sulfofettsäuren bzw. die Disalze der alpha-Sulfofettsäuren. Weitere geeignete anionische Tenside sind sulfierte Fettsäureglycerinester, welche Mono-, Di- und Triester sowie deren Gemische darstellen, wie sie bei der Herstellung durch Veresterung durch 1 Mol Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Als Alkylsulfate eignen sich insbesondere die Schwefelsäuremonoester der (C12-C18)-Fettalkohole, wie Lauryl-, Myristyl-, Cetyl-oder Stearylalkohol und die aus Kokosöl, Palm- und Palmkernöl gewonnenen Fettalkoholgemische, die zusätzlich noch Anteile an ungesättigten Alkoholen, z.B. Oleylalkohol, enthalten können.Suitable anionic surfactants of the sulfonate type are preferably the known (C 9 -C 13 ) -alkylbenzenesulfonates, alpha-olefinsulfonates and alkanesulfonates. Also suitable are esters of sulfo fatty acids or the disalts of the alpha-sulfo fatty acids. Other suitable anionic surfactants are sulfated Fettsäureglycerinester which mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by 1 mole of monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 Mole of glycerol can be obtained. Suitable alkyl sulfates are, in particular, the sulfuric acid monoesters of (C 12 -C 18 ) fatty alcohols, such as lauryl, myristyl, cetyl or stearyl alcohol, and the fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which additionally contain portions of unsaturated alcohols, eg Oleyl alcohol, may contain.

Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierten Erucasäure und Behensäure, sowie insbesondere solche aus natürlichen Fettsäuren, wie z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengernische. Die anionischen Tenside können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze, sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze, vor.
Bei den pH-Regulatoren handelt es sich bevorzugt um Soda, Zitronensäure, Natriumcitrat und/oder Bicarbonat.
As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular those derived from natural fatty acids, such as coconut, palm kernel or tallow fatty acids, derived soap germs. The anionic surfactants can be present in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
The pH regulators are preferably soda, citric acid, sodium citrate and / or bicarbonate.

Schließlich können die Wasch- und Reinigungsmittel gegebenenfalls noch Enzyme, wie z.B. Protease, Amylase, Lipase und Cellulase, enthalten.Finally, the detergents and cleaners may optionally contain enzymes, e.g. Protease, amylase, lipase and cellulase.

Gegenstand der Erfindung sind auch Komponenten für Waschmittel-Baukastensysteme, die bevorzugt 60 bis 100 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung enthalten.The invention also relates to components for detergent modular systems which preferably contain from 60 to 100% by weight of the builder composition according to the invention.

Gegenstand der Erfindung sind weiterhin Wasserenthärter, die mindestens eine der erfindungsgemäßen Builder-Zusammensetzungen enthalten. Wasserenthärter üben vor allem in Regionen mit hoher Wasserhärte einen leistungssteigemden Effekt auf das Waschergebnis und einen Schutzeffekt hinsichtlich der Waschmaschine aus.The invention furthermore relates to water softeners which comprise at least one of the builder compositions according to the invention. Water softeners exert a performance-enhancing effect on the washing result and a protective effect with regard to the washing machine, especially in regions with high water hardness.

Bevorzugte Wasserenthärter enthalten

  • a) 0,5 bis 99 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung
  • b) optional 0,5 bis 80 Gew.-% Cobuilder
  • c) optional 0 bis 15 Gew.-% grenzflächenaktive Substanzen
  • d) optional 0,5 bis 80 Gew.-% pH-Regulatoren
Preferred water softeners included
  • a) 0.5 to 99 wt .-% of the builder composition according to the invention
  • b) optionally 0.5 to 80 wt .-% cobuilder
  • c) optionally 0 to 15 wt .-% surfactants
  • d) optionally from 0.5 to 80% by weight of pH regulators

Als Komponenten a), b), c) und d) werden bevorzugt die weiter oben aufgeführten Verbindungen eingesetzt.As components a), b), c) and d), the compounds listed above are preferably used.

Die erfindungsgemäße Builder-Zusammensetzung kann ausdrücklich auch als Komponente zur Herstellung von Compounds für Wasch- und Reinigungsmittel, Wasserenthärter und Waschmittel-Baukastensysteme verwendet werden. Mit Compounds ist es möglich, spezielle Effekte zu erzielen. So können z.B. flüssige Komponenten in pulver- oder tablettenförmige Wasch- und Reinigungsmittel eingearbeitet werden. Außerdem ist so das Einfärben oder Sprenkeln von Wasch-und Reinigungsmitteln möglich. Ebenso lassen sich dadurch spezielle Desintegrationseffekte, bessere Dispergierung von schwer dispergierbaren Komponenten oder die Porosität von Tabletten erzielen.The builder composition according to the invention can also be used expressly as a component for the preparation of compounds for detergents and cleaners, water softeners and detergent building block systems. With compounds it is possible to achieve special effects. Thus, e.g. liquid components are incorporated into powdered or tablet-shaped detergents and cleaners. In addition, so the coloring or sprinkling of detergents and cleaners is possible. Likewise, special disintegration effects, better dispersion of difficultly dispersible components or the porosity of tablets can be achieved thereby.

Die Compounds enthalten bevorzugt

  • a) 70 bis 99,5 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung, bevorzugt als Pulver mit mittleren Teilchengrößen von 1 bis 500 µm, besonders bevorzugt 20 bis 100 µm, oder in einer anderen Ausführungsform bevorzugt als Granulat mit einer mittleren Teilchengröße von 200 bis 2000 µm, bevorzugt 300 bis 900 µm, und
  • b) 0,5 bis 30 Gew.-% anionische, kationische, nichtionische und/oder zwitterionische Tenside.
The compounds contain preferred
  • a) 70 to 99.5 wt .-% of the builder composition according to the invention, preferably as a powder having average particle sizes of 1 to 500 .mu.m, more preferably 20 to 100 .mu.m, or in another embodiment preferably as granules having an average particle size of 200 to 2000 microns, preferably 300 to 900 microns, and
  • b) from 0.5 to 30% by weight of anionic, cationic, nonionic and / or zwitterionic surfactants.

Als Tenside c) werden bevorzugt die weiter oben aufgeführten Verbindungen eingesetzt.As surfactants c) the compounds listed above are preferably used.

Andere bevorzugte Compounds enthalten

  • a) 50 bis 99 Gew.-% der erfindungsgemäßen Builder-Zusammensetzung,
  • b) 0,01 bis 10 Gew.-% Farbstoff
  • c) ad 100 Gew.-% weitere übliche Inhaltsstoffe.
Other preferred compounds included
  • a) 50 to 99% by weight of the builder composition according to the invention,
  • b) 0.01 to 10 wt .-% dye
  • c) ad 100 wt .-% further customary ingredients.

Die Wasch-, Reinigungsmittel, Wasserenthärter und Baukasten-Komponenten können z.B. in Pulverform, Granulatform, Gelform, Flüssigform oder Tablettenform eingesetzt werden.
Zur Herstellung der Tabletten wird die jeweilige Zusammensetzung mittels einer Tablettenpresse in die entsprechende Form gepresst, wobei die Form vielgestaltig sein kann (z.B. zylinderförmig, quaderförmig, ellipsenförmig, ringförmig etc). Im Falle der Zylinderform kann das Verhältnis von Radius zu Höhe zwischen 0,2 bis 5 betragen. Der Pressdruck kann zwischen 12 und 0,3 kN/cm2 betragen. Der Pressdruck ist im wesentlichen unabhängig von der geometrischen Form der Tablette.
Für die Tablettierung von Maschinengeschirrreinigern sind Pressdrücke von 0,7 bis 14,2 kN/cm2 bevorzugt, besonders bevorzugt sind Drücke von 2,8 bis 10 kN/cm2. Bevorzugt ist auch die mehrstufige Verpressung zu komplexeren Formen. Die Aufteilung in verschiedene Kompartimente dient einer gewissen Trennung von ansonsten miteinander unverträglichen Inhaltsstoffen. Für Mehrschichttabletten werden beliebige Anteile der Formulierung in mehreren Schritten nacheinander aufeinander gepresst, so dass sich mehrere Schichten ergeben. Im Falle einer Zweischichttablette ist dabei besonders bevorzugt ein Schichtdickenverhältnis der beiden Schichten von 1 : 10 bis 10 : 1. Andere Anwendungsformen sind z.B. Tabletten mit eingefügten kugelförmigen Kompartimenten. Die unterschiedlichen Schichten und Kompartimente der Tabletten können auch unterschiedlich eingefärbt sein.
The detergents, cleaners, water softeners and modular components can be used, for example, in powder form, granule form, gel form, liquid form or tablet form.
To produce the tablets, the respective composition is pressed by means of a tablet press into the appropriate shape, wherein the shape may be varied (eg cylindrical, cuboid, elliptical, annular, etc). In the case of the cylindrical shape, the ratio of radius to height between 0.2 to 5 be. The pressing pressure can be between 12 and 0.3 kN / cm 2 . The pressing pressure is essentially independent of the geometric shape of the tablet.
Pressing pressures of 0.7 to 14.2 kN / cm 2 are preferred for the tableting of machine-dishwashing detergents, particular preference being given to pressures of 2.8 to 10 kN / cm 2 . Preference is also the multi-stage compression to more complex forms. The division into different compartments serves a certain separation of otherwise incompatible ingredients. For multilayer tablets, any desired proportions of the formulation are pressed successively onto one another in several steps, resulting in several layers. In the case of a two-layer tablet, a layer thickness ratio of the two layers is particularly preferably from 1:10 to 10: 1. Other applications include tablets with inserted spherical compartments. The different layers and compartments of the tablets can also be colored differently.

Die nachfolgenden Beispiele dienen der Erläuterung der Erfindung ohne sie jedoch einzuschränken.The following examples serve to illustrate the invention without, however, restricting it.

Bestimmung der Phasenzusammensetzung der eingesetzten kristallinen schichtförmigen Natriumdisilicate:
Eine gemörserte Feststoffprobe wird in einem Röntgenpulverdiffraktometer Philips PW1710 vermessen (CuK alpha 2-Strahlung, Wellenlänge 1,54439 Angström, Beschleunigungsspannung 35kV, Heizstrom 28 mA, Monochromator, Scangeschwindigkeit 3 Grad 2 theta pro Minute). Die gemessenen Intensitäten werden wie folgt ausgewertet: Substanz charakteristischer Peak (d-Wert in Angström) Alpha-Phase 3,29 +/- 0,07, typisch 3,31 Beta-Phase 2,97 +/- 0,06 Delta-Phase 3,97 +/- 0,08
Determination of the phase composition of the crystalline layered sodium disilicates used:
A crushed solid sample is measured in a Philips PW1710 X-ray powder diffractometer (CuK alpha 2 radiation, wavelength 1.54439 angstroms, acceleration voltage 35 kV, heating current 28 mA, monochromator, scanning rate 3 degrees 2 theta per minute). The measured intensities are evaluated as follows: substance characteristic peak (d value in angstroms) Alpha phase 3.29 +/- 0.07, typically 3.31 Beta phase 2.97 +/- 0.06 Delta phase 3.97 +/- 0.08

Die kristallinen Anteile in Gewichtsprozent errechnen sich aus den Intensitäten la, lb und ld - gemessen in Impulsen - der alpha, beta und delta Phase nach folgenden Formeln:

        Alpha-Gehalt: A [%] = 100*Ia/(Ia+Ib+Id)

        Beta-Gehalt: B [%] = 1,41*100*Ib/(Ia+Id)

        Delta-Gehalt: D [%] = 100- A - D
The crystalline proportions in percent by weight are calculated from the intensities I a , I b and I d -measured in pulses-of the alpha, beta and delta phases according to the following formulas:

Alpha content: A [%] = 100 * I a / (I a + I b + I d )

Beta content: B [%] = 1.41 * 100 * I b / (I a + I d )

Delta content: D [%] = 100-A - D

Zur Bestimmung des röntgenamorphen Anteils (AM) wird der Untergrund (Impulse) des Röntgenpeaks bei einem d-Wert von 2,65 Angström bestimmt (Iam) und mit folgender empirischen Formel in den Prozentgehalt umgerechnet: AM [%] = (Iam-70)*100/450To determine the X-ray amorphous content (AM), the background (impulses) of the X-ray peak at a d value of 2.65 angstroms is determined (I am ) and converted into the percentage by the following empirical formula: AM [%] = (I am - 70) * 100/450

Sollen in einer Analyse neben den kristallinen Anteilen auch röntgenamorphe Anteile genannt werden, so werden die Gehalte A, B, C um AM korrigiert.If in an analysis not only the crystalline parts but also X-ray amorphous parts are mentioned, the contents A, B, C are corrected by AM.

Kompaktieren und Mahlen der Builder-Zusammensetzungen:Compacting and milling the builder compositions:

In einem Rollkompaktor (Firma Hosokawa-Bepex) wird das Ausgangsmaterial mit Hilfe einer Stopfschnecke zwischen die Kompaktorwalzen befördert (Einstellung Stufe 5). Dies geschieht so schnell, dass ein Pressdruck von 10 bis 100 kN/cm Walzenlänge entsteht. Die Walzenumdrehung wird auf Stufe 3 bis 7 gestellt, der Walzenspalt beträgt 0,1 mm. Die entstehenden Schülpen (Länge ca. 50mm, Dicke ca. 2 bis 5 mm, Breite ca. 10 bis 15 mm) werden in einer Hammermühle (Typ UPZ, Fa. Alpine) mit einem Sieblochdurchmesser von 5mm bei einer Umdrehungszahl von 600 bis 1400 Upm gebrochen. Vom gebrochenen pulverförmigen Produkt werden Überkom (Sieb mit Lochdurchmesser 1000 µm) und Unterkorn (Sieb mit Lochdurchmesser 300 µm) abgetrennt. Das Überkorn wird einem weiteren Mahlschritt unterworfen und nochmals gesiebt. Die beiden Fraktionen mit Teilchengröße zwischen 300 µm und 1000 µm werden vereinigt.In a roll compactor (Hosokawa-Bepex company), the starting material is conveyed between the compactor rolls by means of a plug screw (setting level 5). This happens so fast that a pressing pressure of 10 to 100 kN / cm roll length is created. The roller revolution is set to levels 3 to 7, the nip is 0.1 mm. The resulting slugs (length about 50mm, thickness about 2 to 5 mm, width about 10 to 15 mm) are in a hammer mill (type UPZ, Fa. Alpine) with a Sieblochdurchmesser of 5mm at a speed of 600 to 1400 rpm Broken. From the crushed powdery product Überkom (sieve with hole diameter 1000 microns) and undersize (sieve with hole diameter 300 microns) are separated. The oversize is subjected to another grinding step and sieved again. The two fractions with particle size between 300 microns and 1000 microns are combined.

Bestimmung der Kornverteilung der Builder-Zusammensetzungen durch Siebanalyse:Determination of the particle size distribution of the builder compositions by sieve analysis:

In eine Siebmaschine der Fa. Retsch werden die Einsätze mit den gewünschten Sieben eingesetzt. Dabei nimmt die Maschenweite der Siebe von oben nach unten ab. 50 g des zu untersuchenden Pulvers werden auf das weiteste Sieb aufgegeben. Durch die Schwingbewegung der Siebmaschine wird das Pulvermaterial durch die verschiedenen Siebe befördert. Die Rückstände auf den Sieben werden ausgewogen und rechnerisch auf die Materialeinwaage bezogen. Aus den Werten kann der d50-Wert berechnet werden.In a screening machine from the company Retsch the inserts are used with the desired sieves. The mesh size of the sieves decreases from top to bottom. 50 g of the powder to be tested are placed on the widest sieve. Due to the oscillating motion of the screening machine, the powder material is conveyed through the various screens. The residues on the sieves will be balanced and mathematically based on the material weight. From the values, the d 50 value can be calculated.

Herstellung der Testwaschmittel:Preparation of the test detergents:

Die optischen Aufheller werden in einem Viertel der Menge des geschmolzenen Alkylethoxylates angerührt und in einem Haushalts-Multimixer (Fa. Braun) mit der Hälfte der Soda- bzw. Bicarbonat- bzw. Phosphat-Menge gemischt. In einem Pflugscharmischer der Fa. Lödige werden die Rest-Soda und die Gesamtmengen an erfindungsgemäßer Builder-Zusammensetzung, Phosphat, Zeolith, Bicarbonat, Zitronensäure bzw. Polymer 15 Minuten bei 300 U/min gemischt. Danach wird die Hälfte des verbliebenen Alkylethoxylates in 5 Minuten aufgesprüht. Danach wird die erfindungsgemäße Builder-Zusammensetzung zugegeben und 10 Minuten gemischt. Dann wird die restliche zweite Hälfte des Alkylethoxylates in weiteren 5 Minuten aufgesprüht. Schließlich werden Alkansulfonat, Polyvinylpyrrolidon, Alkylbenzolsulfonat, Seife, Antischaummittel, Phosphonat bzw. Compound mit optischem Aufheller zugegeben und 10 Minuten bei 300 U/min nachgemischt. Im Taumelmischer wird die Mischung aus dem Lödige-Mischer unter geringer Scherbelastung mit Percarbonat, Perborat, TAED bzw. Enzymen versetzt und 5 Minuten vermischt.The optical brighteners are mixed in a quarter of the amount of the molten alkyl ethoxylate and mixed in a household Multimixer (Braun) with half of the soda or bicarbonate or phosphate amount. In a ploughshare mixer from Lödige, the residual soda and the total amounts of builder composition according to the invention, phosphate, zeolite, bicarbonate, citric acid or polymer are mixed for 15 minutes at 300 rpm. Thereafter, half of the remaining alkyl ethoxylate is sprayed on in 5 minutes. Thereafter, the builder composition of the present invention is added and mixed for 10 minutes. Then the remaining second half of the alkyl ethoxylate is sprayed on for a further 5 minutes. Finally, alkanesulfonate, polyvinylpyrrolidone, alkylbenzenesulfonate, soap, antifoaming agent, phosphonate or compound with optical brightener are added and admixed for 10 minutes at 300 rpm. In the tumble mixer, the mixture from the Lödige mixer is mixed with percarbonate, perborate, TAED or enzymes under low shear and mixed for 5 minutes.

Tablettierung von Waschmitteln:Tabletting of detergents:

Zur Tablettierung werden die Waschmittelformulierungen gemischt und mit einer Tablettenpresse der Fa. Matra in die entsprechende Form gepresst. Der Pressdruck kann zwischen 12 und 0,3 kN/cm2 betragen. Die Presslinge haben eine Höhe von ca. 18 mm und einen Durchmesser von 41 mm.For tableting, the detergent formulations are mixed and pressed with a tablet press from Matra in the appropriate form. The pressing pressure can be between 12 and 0.3 kN / cm 2 . The pellets have a height of about 18 mm and a diameter of 41 mm.

Herstellung der Maschinengeschirreiniger:Manufacture of machine dishes:

In einem Pflugscharmischer der Fa. Lödige werden die festen Komponenten, außer Enzyme, Bleiche und Parfüm, vorgelegt und gut gemischt. Dann wird das Alkylethoxylat aufgesprüht. Enzyme, Parfüm und Bleichsystem werden zum Schluss untergemischt.In a ploughshare mixer Fa. Lödige the solid components, except enzymes, bleach and perfume, submitted and mixed well. Then the alkyl ethoxylate is sprayed on. Enzymes, perfume and bleach system are finally mixed in.

Durchführung der Löserückstandstests:Execution of the solvent residue tests:

800 ml Leitungswasser (Wasserhärte 20 Grad deutscher Härte, Molverhältnis Ca:Mg = ca. 4: 1) werden auf 20°C temperiert. 2 g der Testsubstanz werden zugegeben und 20 min mit einem Magnetrührer gerührt. Mit dem leichten Vakuum einer Wasserstrahlpumpe wird die Dispersion in einem Büchner-Trichter (Durchmesser ca. 95 mm, Typ WFK 10A von wfk-Testgewebe GmbH, Christenfeld 10, 41379 Brueggen, Deutschland) durch ein Baumwollgewebe gesaugt. Das Sieb wird bei 80 bis 100°C 1 Stunde im Umlufttrockenschrank getrocknet. Die Gewichtszunahme wird auf die Einwaage bezogen, auf Prozente normiert und als Löserückstand (KRT in %) bezeichnet.800 ml of tap water (water hardness 20 degrees German hardness, molar ratio Ca: Mg = approx. 4: 1) are heated to 20 ° C. 2 g of the test substance are added and stirred for 20 minutes with a magnetic stirrer. With the light vacuum of a water jet pump, the dispersion is drawn through a cotton fabric in a Büchner funnel (diameter approx. 95 mm, type WFK 10A from wfk-Testgewebe GmbH, Christenfeld 10, 41379 Brueggen, Germany). The sieve is dried at 80 to 100 ° C for 1 hour in a convection oven. The weight increase is based on the initial weight, normalized to percentages and referred to as the solvent residue (KRT in%).

Beispiel 1 (Vergleich):Example 1 (comparison):

Von einem kommerziell erhältlichen kristallinen schichtförmigen Natriumdisilikat-Granulat (SKS-6 Granulat, Clariant GmbH) werden der Löserückstand, die Schüttdichte und der mittlere Teilchendurchmesser d50 bestimmt. Die Messwerte sind in Tabelle 1 zusammengefasst.From a commercially available crystalline layered sodium disilicate granules (SKS-6 granules, Clariant GmbH), the dissolution residue, the bulk density and the average particle diameter d 50 are determined. The measured values are summarized in Table 1.

Beispiel 2 (Vergleich):Example 2 (comparison):

Von einem kommerziell erhältlichen kristallinen schichtförmigen Natriumdisilikat-Pulver (SKS-6 Pulver, Clariant GmbH) wird der Löserückstand bestimmt. Die Messwerte sind in Tabelle 1 zusammengefasst. Die Röntgenpulverdiffraktometrie ergibt folgende Phasenzusammensetzung: Alpha-Disilicat 19,1 Gew.-%, Beta-Disilicat 9,4 Gew.-% und Delta-Disilicat 71,5 Gew.-%.The dissolution residue is determined from a commercially available crystalline layered sodium disilicate powder (SKS-6 powder, Clariant GmbH). The measured values are summarized in Table 1. The X-ray powder diffractometry gives the following phase composition: alpha-disilicate 19.1% by weight, beta-disilicate 9.4% by weight and delta-disilicate 71.5% by weight.

Beispiel 3 (Vergleich):Example 3 (comparison):

In einem Pflugscharmischer der Firma Lödige wird in vier Ansätzen kristallines schichtförmiges Natriumdisilicat-Pulver aus Beispiel 2 mit einer Lösung aus 96 %-iger Schwefelsäure und Wasser in den in Tabelle 1 angegebenen Mengenverhältnissen zu insgesamt 18 kg Pulvergemisch vermischt. Von der Pulvermischung wird der Löserückstand bestimmt. Im Vergleich mit dem unbehandelten Pulver aus Beispiel 2 ergibt sich ein verbessertes Löserückstandsverhalten (s.h. Tabelle 1 und vgl. Beispiel 2).In a ploughshare mixer from Lödige, crystalline layered sodium disilicate powder from Example 2 is mixed with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to a total of 18 kg of powder mixture in four batches. From the powder mixture, the dissolution residue is determined. In comparison with the untreated powder from Example 2, an improved dissolution residue behavior results (see Table 1 and compare Example 2).

Beispiel 4 (Vergleich):Example 4 (comparison):

Von der Mischung aus Beispiel 3 werden 8 kg in einem Rollkompaktor bei einem Pressdruck von 32 kN/cm Walzenlänge verarbeitet. Es werden ca. 3 kg Gutkorn erhalten, wovon der Löserückstand bestimmt wird. Die zusätzliche Kompaktierung bewirkt ein verbessertes Löserückstandverhalten (s.h. Tabelle1 und vgl. Beispiel 3).Of the mixture of Example 3 8 kg are processed in a roll compactor at a pressing pressure of 32 kN / cm roll length. It will be about 3 kg of good grain obtained, from which the solvent residue is determined. The additional compaction leads to an improved solvent residue behavior (see Table 1 and see Example 3).

Beispiel 5 (Vergleich):Example 5 (comparison):

Von der Mischung aus Beispiel 3 werden 10 kg in einem Trockenschrank 1 h bei 75°C wärmebehandelt. Durch die Warmlagerung wird das Löserückstandsverhalten verbessert (s.h. Tabelle 1 und vgl. Beispiel 3).From the mixture of Example 3, 10 kg are heat treated in a drying oven at 75 ° C for 1 h. The warm storage improves the dissolution residue behavior (see Table 1 and see Example 3).

Beispiel 6:Example 6:

Das Material aus Beispiel 5 wird in einem Rollkompaktor bei einem Pressdruck von 32 kN/cm Walzenlänge verarbeitet. Es werden ca. 5 kg Gutkorn erhalten wovon der Löserückstand bestimmt wird (s.h. Tabelle 1). Das Löserückstandsverhalten ist gegenüber den Beispielen 1, 2, 3, 4 und 5 verbessert. Anhand der Röntgenpulverdiffraktometrie ist zu erkennen, dass sich die Anteile der polymorphen Disilicat-Phasen nicht verändert haben: Alpha-Disilicat 19,3%, Beta-Disilicat 9,9%, Delta-Disilicat 70,8%.The material of Example 5 is processed in a roll compactor at a press pressure of 32 kN / cm roll length. About 5 kg of good grain are obtained, from which the residue is determined (see Table 1). The Löserückstandsverhalten is compared with the examples 1, 2, 3, 4 and 5 improved. X-ray powder diffractometry shows that the polymorph disilicate phases did not change: alpha disilicate 19.3%, beta disilicate 9.9%, delta disilicate 70.8%.

Beispiel 7:Example 7:

Von dem Material aus Beispiel 6 werden 4 kg ca. 45 min mit einer Kugelmühle U 280A0 der Fa. Welte, die innen metallausgekleidet ist und deren Trommel sich mit ca. 50 U/min dreht, gemahlen. Als Mahlkörper werden 44 kg Porzellankugeln eingesetzt. Durch die Mahlung wird das Löserückstandsverhalten gegenüber dem Granulat aus Beispiel 6 verbessert (s.h. Tabelle 1 und vgl. Beispiel 6).From the material of Example 6 4 kg are ground for about 45 minutes with a ball mill U 280A0 Fa. Welte, the metal-lined inside and the drum rotates at about 50 rev / min, milled. As grinding media 44 kg porcelain balls are used. The grinding improves the dissolution residue behavior compared with the granules from Example 6 (see Table 1 and see Example 6).

Beispiel 8 (Vergleich):Example 8 (comparison):

In einem Pflugscharmischer der Firma Lödige wird in zwei Ansätzen kristallines schichtförmiges Natriumdisilicat-Pulver aus Beispiel 2 mit einer Lösung aus 96 %iger Schwefelsäure und Wasser in den in Tabelle 1 angegebenen Mengenverhältnissen zu 9 kg Pulvergemisch vermischt. Die Mischung wird in einem Trockenschrank 1 Stunde bei 85°C wärmebehandelt und danach in einem Rollkompaktor bei einem Pressdruck von 32 kN/cm Walzenlänge verarbeitet. Es werden ca. 4 kg Gutkorn erhalten, wovon der Löserückstand bestimmt wird (siehe Tabelle 1). Das gegenüber Beispiel 6 niedrigere Wasser-zu-Säure-Verhältnis bewirkt ein verschlechtertes Löserückstandsverhalten.In a ploughshare mixer from Lödige, crystalline layered sodium disilicate powder from Example 2 is mixed in two batches with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to give 9 kg of powder mixture. The mixture is heat treated in a drying oven for 1 hour at 85 ° C and then processed in a roll compactor at a pressing pressure of 32 kN / cm roll length. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1). The lower water to acid ratio compared to Example 6 causes a deteriorated Löserückstandsverhalten.

Beispiel 9:Example 9:

In einem Pflugscharmischer der Firma Lödige wird in zwei Ansätzen kristallines schichtförmiges Natriumdisilicat-Pulver aus Beispiel 2 mit einer Lösung aus 96 %iger Schwefelsäure und Wasser in den in Tabelle 1 angegebenen Mengenverhältnissen zu 9 kg Pulvergemisch vermischt. Die Mischung wird in einem Trockenschrank 1 Stunde bei 85°C wärmebehandelt und danach in einem Rollkompaktor bei einem Pressdruck von 32 kN/cm Walzenlänge verarbeitet. Es werden ca. 4 kg Gutkorn erhalten, wovon der Löserückstand bestimmt wird (siehe Tabelle 1). Trotz der geringeren Säure/Wasser-Einsatzmenge ist das Löserückstandsverhalten ähnlich gut wie in Beispiel 6.In a ploughshare mixer from Lödige, crystalline layered sodium disilicate powder from Example 2 is mixed in two batches with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to give 9 kg of powder mixture. The mixture is heat treated in a drying oven for 1 hour at 85 ° C and then processed in a roll compactor at a pressing pressure of 32 kN / cm roll length. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1). Despite the lower amount of acid / water used, the dissolution residue behavior is similar to that in Example 6.

Beispiel 10:Example 10:

In einem Pflugscharmischer der Firma Lödige wird in zwei Ansätzen kristallines schichtförmiges Natriumdisilicat-Pulver aus Beispiel 2 mit einer Lösung aus 96 %-iger Schwefelsäure und Wasser in den in Tabelle 1 angegebenen Mengenverhältnissen zu 9 kg Pulvergemisch vermischt. Die Mischung wird in einem Trockenschrank 1 Stunde bei 85°C wärmebehandelt und danach in einem Rollkompaktor bei einem Pressdruck von 32 kN/cm Walzenlänge verarbeitet. Es werden ca. 4 kg Gutkorn erhalten, wovon der Löserückstand bestimmt wird (siehe Tabelle 1). Trotz der hohen Säure/Wasser-Einsatzmenge ist das Löserückstandsverhalten ähnlich gut wie in Beispiel 6.In a ploughshare mixer from Lödige, crystalline layered sodium disilicate powder from Example 2 is mixed with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to form 9 kg of powder mixture in two batches. The mixture is heat treated in a drying oven for 1 hour at 85 ° C and then processed in a roll compactor at a pressing pressure of 32 kN / cm roll length. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1). Despite the high amount of acid / water used, the dissolution residue behavior is similar to that in Example 6.

Beispiel 11:Example 11:

In einem Pflugscharmischer der Firma Lödige wird in zwei Ansätzen kristallines schichtförmiges Natriumdisilicat-Pulver aus Beispiel 2 mit einer Lösung aus 96 %iger Schwefelsäure und Wasser in den in Tabelle 1 angegebenen Mengenverhältnissen zu 9 kg Pulvergemisch vermischt. Die Mischung wird in einem Trockenschrank 10 min bei 100°C wärmebehandelt und danach in einem Rollkompaktor bei einem Pressdruck von 32 kN/cm Walzenlänge verarbeitet. Es werden ca. 4 kg Gutkorn erhalten, wovon der Löserückstand bestimmt wird (siehe Tabelle 1). Trotz der geänderten Bedingungen bei der Wärmebehandlung ist das Löserückstandsverhalten ähnlich gut wie in Beispiel 6.In a ploughshare mixer from Lödige, crystalline layered sodium disilicate powder from Example 2 is mixed in two batches with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to give 9 kg of powder mixture. The mixture is heat-treated in a drying oven for 10 minutes at 100 ° C and then processed in a roll compactor at a pressing pressure of 32 kN / cm roll length. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1). Despite the changed conditions in the heat treatment, the dissolution residue behavior is similar to that in Example 6.

Beispiel 12:Example 12:

In einem Pflugscharmischer der Firma Lödige wird in zwei Ansätzen kristallines schichtförmiges Natriumdisilicat-Pulver aus Beispiel 2 mit einer Lösung aus 96 %iger Schwefelsäure und Wasser in den in Tabelle 1 angegebenen Mengenverhältnissen zu 9 kg Pulvergemisch vermischt. Die Mischung wird in einem Trockenschrank 1h bei 85°C wärmebehandelt und danach in einem Rollkompaktor bei einem Pressdruck von 100 kN/cm Walzenbreite verarbeitet. Es werden ca. 4 kg Gutkorn erhalten, wovon der Löserückstand bestimmt wird (siehe Tabelle 1). Trotz des geänderten Pressdruckes ist das Löserückstandsverhalten ähnlich gut wie in Beispiel 6.In a ploughshare mixer from Lödige, crystalline layered sodium disilicate powder from Example 2 is mixed in two batches with a solution of 96% strength sulfuric acid and water in the proportions given in Table 1 to give 9 kg of powder mixture. The mixture is heat treated in a drying oven for 1 h at 85 ° C and then processed in a roll compactor at a pressure of 100 kN / cm roll width. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1). Despite the changed pressing pressure, the dissolution residue behavior is similar to that in Example 6.

Beispiel 13 (Vergleich)Example 13 (comparison)

Von einem weiteren kommerziell erhältlichen kristallinen schichtförmigen Natriumdisilicat-Pulver (SKS-6 Pulver, Clariant GmbH) wird der Löserückstand bestimmt. Die Messwerte sind in Tabelle 1 zusammengefasst. Die Röntgenpulverdiffraktometrie ergibt die Anteile der polymorphen Disilicat-Phasen: Alpha-Disilicat 9,8 Gew.-%, Beta-Disilicat 1,7 Gew.-% und Delta-Disilicat 88,5 Gew.-%. Vergleicht man die Phasenzusammensetzungen und Löserückstände der Beispiele 13 und 2, so zeigt sich, dass ein höherer delta-Phasen-Gehalt zu einem günstigeren Effekt führt. Der Effekt, den man durch Erhöhen des delta-Phasenanteils erzielt, ist etwa mit dem zu vergleichen, den man durch einfaches Vermischen von kristallinem schichtförmigen Natriumdisilicat-Pulver mit Wasser und Schwefelsäure erzielt (vgl. Beispiele 2 und 3).Another dissolution residue is determined from another commercially available crystalline layered sodium disilicate powder (SKS-6 powder, Clariant GmbH). The measured values are summarized in Table 1. X-ray powder diffraction gives the proportions of the polymorphic disilicate phases: alpha-disilicate 9.8% by weight, beta-disilicate 1.7% by weight and delta-disilicate 88.5% by weight. Comparing the phase compositions and solvent residues of Examples 13 and 2, it can be seen that a higher delta phase content leads to a more favorable effect. The effect obtained by increasing the delta phase content is comparable to that achieved by simply mixing crystalline layered sodium disilicate powder with water and sulfuric acid (see Examples 2 and 3).

Beispiel 14:Example 14:

In einem Pflugscharmischer der Firma Lödige wird in zwei Ansätzen kristallines schichtförmiges Natriumdisilicat-Pulver aus Beispiel 13 mit einer Lösung aus 96 %iger Schwefelsäure und Wasser in den in Tabelle 1 angegebenen Mengenverhältnissen zu 9 kg Pulvergemisch vermischt. Die Mischung wird in einem Trockenschrank 1 Stunde bei 85°C wärmebehandelt und danach in einem Rollkompaktor bei einem Pressdruck von 32 kN/cm Walzenbreite verarbeitet. Es werden ca. 4 kg Gutkorn erhalten, wovon der Löserückstand bestimmt wird (siehe Tabelle 1). Der Löserückstand ist günstiger als bei Beispiel 13. Die Röntgenpulverdiffraktometrie zeigt, dass sich die Phasenverteilung des Natriumdisilicates nicht verändert hat: Alpha-Disilicat 10,6 %, Beta-Disilicat 0 %, Delta-Disilicat 89,4 %.In a ploughshare mixer from Lödige, crystalline layered sodium disilicate powder from example 13 is mixed with a solution of 96% strength sulfuric acid and water in the proportions given in table 1 to give 9 kg of powder mixture in two batches. The mixture is heat-treated in a drying oven for 1 hour at 85 ° C and then processed in a roll compactor at a pressure of 32 kN / cm roll width. Approximately 4 kg of good grain are obtained, from which the residue is determined (see Table 1). The dissolution residue is more favorable than in Example 13. X-ray powder diffractometry shows that the phase distribution of the Sodium disilicate has not changed: alpha-disilicate 10.6%, beta-disilicate 0%, delta-disilicate 89.4%.

Beispiel 15 (Vergleich):Example 15 (comparison):

Von einer nach EP 0 849 355 hergestellten pulverförmigen Wasch- und Reinigungsmittel-Komponente wird der Löserückstand bestimmt (s.h. Tabelle 1).The solution residue is determined from a pulverulent detergent and cleaner component prepared according to EP 0 849 355 (see Table 1).

Beispiel 16:Example 16:

In einem Pflugscharmischer der Firma Lödige wird in zwei Ansätzen kristallines schichtförmiges Natriumdisilicat-Pulver aus Beispiel 13 mit einer Lösung aus Natriumhydrogensulfat und Wasser in den in Tabelle 1 angegebenen Mengenverhältnissen zu 9 kg Pulvergemisch vermischt. Die Mischung wird in einem Trockenschrank 1 Stunde bei 80°C wärmebehandelt und danach in einem Rollkompaktor bei einem Pressdruck von 50 kN/cm Walzenbreite verarbeitet. Es werden ca. 4 kg Gutkorn erhalten wovon der Löserückstand bestimmt wird (siehe Tabelle 1). Das Löserückstandsverhalten ist wesentlich besser als bei Vergleichsbeispiel 13.In a ploughshare mixer from Lödige, crystalline layered sodium disilicate powder from Example 13 is mixed with a solution of sodium hydrogensulfate and water in the proportions given in Table 1 to form 9 kg of powder mixture in two batches. The mixture is heat treated in a drying oven for 1 hour at 80 ° C and then processed in a roll compactor at a pressure of 50 kN / cm roll width. About 4 kg of good grain are obtained, from which the residue is determined (see Table 1). The dissolution residue behavior is significantly better than in Comparative Example 13.

Beispiele 17 bis 21 und 24 bis 27:Examples 17 to 21 and 24 to 27:

Entsprechend der allgemeinen Vorschrift "Herstellung der Testwaschmittel" werden Test-Waschmittel mit den in Tabelle 2 angegebenen Zusammensetzungen hergestellt.According to the general procedure "preparation of the test detergents", test detergents having the compositions indicated in Table 2 are prepared.

Beispiel 22:Example 22:

Im Pflugscharmischer der Fa. Lödige wird eine Wasserenthärter-Formulierung entsprechend Tabelle 2 hergestellt, wobei die festen Komponenten 15 Minuten bei 300 U/min gemischt werden. Das Alkylethoxylat wird geschmolzen und unter Mischen aufgesprüht.In Lödige's ploughshare mixer, a water softener formulation according to Table 2 is prepared, the solid components being mixed for 15 minutes at 300 rpm. The alkyl ethoxylate is melted and sprayed on with mixing.

Beispiel 23:Example 23:

Nach der allgemeinen Vorschrift "Herstellung der Testwaschmittel" und "Tablettierung von Waschmitteln" werden Waschmittel-Tabletten mit Zusammensetzungen entsprechend Tabelle 2 hergestellt.According to the general instructions "preparation of the test detergents" and "tabletting of detergents" detergent tablets are prepared with compositions according to Table 2.

Beispiel 28:Example 28:

Im Pflugscharmischer der Fa. Lödige wird eine Fleckensalz-Formulierung entsprechend Tabelle 2 hergestellt, wobei die festen Komponenten 15 Minuten bei 300 U/min gemischt werden. Das Alkansulfonat wird geschmolzen und unter Mischen aufgesprüht.In Lödige's ploughshare mixer, a stain-salt formulation according to Table 2 is prepared, with the solid components being mixed for 15 minutes at 300 rpm. The alkanesulfonate is melted and sprayed on with mixing.

Beispiele 29 bis 30:Examples 29 to 30:

Nach der allgemeinen Vorschrift "Herstellung der Maschinengeschirreiniger" werden Maschinengeschirreiniger mit den Zusammensetzungen entsprechend Tabelle 3 hergestellt.According to the general regulation "Manufacture of machine-harness cleaners", machine-dishwashing detergents are prepared with the compositions according to Table 3.

Beispiel 31:Example 31:

Ein Maschinengeschirreinigergel mit der in Tabelle 4 angegebenen Zusammensetzung wird so hergestellt, dass man in einem Dispergator (Ultraturrax, Fa. Hanke und Kunkel) Wasserglas, Phosphat, Soda, Natriumhydroxid, Phosphonat, Polymer, Alkansulfonat, Phosphorsäureester miteinander vermischt. Die erfindungsgemäße Builder-Zusammensetzung gemäß Beispiel 6 und Natriumhypochlorit werden zum Schluss untergemischt.A machine dishwashing detergent gel having the composition shown in Table 4 is prepared by mixing together in a disperser (Ultraturrax, Messrs. Hanke and Kunkel) water glass, phosphate, soda, sodium hydroxide, phosphonate, polymer, alkanesulfonate, phosphoric acid esters. The builder composition according to the invention according to Example 6 and sodium hypochlorite are finally mixed in.

Verwendete Chemikalien:Used chemicals:

AE 1AE 1 ®Genapol 3070, Fa. Clariant GmbH® Genapol 3070, Clariant GmbH AE 2AE 2 ®Genapol 2822, Fa. Clariant GmbH® Genapol 2822, Clariant GmbH Alkansulfonatalkanesulfonate ®Hostapur SAS 60, Fa. Clariant GmbH®Hostapur SAS 60, Clariant GmbH Alkylbenzolsulfonatalkylbenzenesulfonate ®Marlon ARL, Fa. Hüls®Marlon ARL, Fa. Huls Antischaumantifoam ®11 Plv ASP3, Fa. Wacker® 11 Plv ASP3, from Wacker Zitronensäurecitric acid Fa. JungbunzlauerFa. Jungbunzlauer CMCCMC ®Tylose 2000, Fa. Clariant GmbH® Tylose 2000, Clariant GmbH Enzym 1Enzyme 1 ®Termamyl 60T, Fa. Solvay Enzymes®Termamyl 60T, from Solvay Enzymes Enzym 2Enzyme 2 ®Termamyl 120T, Fa. Solvay Enzymes®Termamyl 120T, from Solvay Enzymes Enzym 3Enzyme 3 ®Savinase 6.0 TW, Fa. Solvay Enzymes® Savinase 6.0 TW, from Solvay Enzymes Natriumacetat thSodium acetate th Fa. Merck KGaAMerck KGaA Natriumbicarbonatsodium bicarbonate Fa. SolvaySolvay Natriumchloridsodium chloride Fa. Merck KGaAMerck KGaA Natriumcitrat thSodium citrate th Fa. JungbunzlauerFa. Jungbunzlauer Natriumhydroxidsodium hydroxide Microprills 100 %, Fa. Riedel-de HaenMicroprills 100%, Riedel-de Haen Natriumhypochloritsodium hypochlorite Fa. Celanese GmbHFa. Celanese GmbH Natriummetasilicat phSodium metasilicate ph Fa. vanBaerleFa. Van Baerle Natriumperborat mhSodium perborate mh Fa. DegussaDegussa Natriumperborat thSodium perborate th Fa. DegussaDegussa Natriumpercarbonatsodium ®Oxyper C, Fa. Solvay Interox®Oxyper C, from Solvay Interox Natriumphosphat 1Sodium phosphate 1 Natriumtripolyphosphat, Fa. Thermphos Intl.Sodium tripolyphosphate, Fa. Thermphos Intl. Natriumphosphat 2Sodium phosphate 2 ®Makrophos 1018, Fa. BK Giulini® Macrophos 1018, BK Giulini Natriumphosphat 3Sodium phosphate 3 ®Thermphos NW grob, Fa. Thermphos Intl.®Thermphos NW coarse, Fa. Thermphos Intl. Natriumsulfatsodium sulphate Fa. SolvaySolvay 45,5 % Aktivsubstanz, Modul 2,0, Fa. Clariant45.5% active ingredient, module 2.0, Clariant NatriumwasserglasSodium silicate France SAFrance SA Opt. AufhellerOpt. Brightener ®Tinopal CBS-X, Fa. Ciba®Tinopal CBS-X, Ciba ParfümPerfume Zitronenparfüm 78122D, Fa OrissaLemon Perfume 78122D, Fa Orissa Phosphonat 1Phosphonate 1 ®Dequest 2041, Fa. Monsanto®Dequest 2041, Monsanto Phosphonat 2Phosphonate 2 ®Dequest 200, Fa. Monsanto®Dequest 200, from Monsanto Polycarboxylat 1Polycarboxylate 1 ®Sokalan CP5 Pulver, Fa. BASF® Sokalan CP5 powder, BASF Polycarboxylat 2Polycarboxylate 2 ®Sokalan CP45, Fa. BASF® Sokalan CP45, BASF Polycarboxylat 3Polycarboxylate 3 ®Sokalan CP5 flüssig, Fa. BASF® Sokalan CP5 liquid, BASF Polyvinylpyrrolidonpolyvinylpyrrolidone ®Sokalan HP50, Fa. BASF® Sokalan HP50, BASF SeifeSoap ®Liga Grundseife HM11E®Liga basic soap HM11E Sodasoda Schwersoda, Fa. Matthes&WeberSchwersoda, Fa. Matthes & Weber Soil release polymerSoil release polymer ®SRC 1, Fa. Clariant GmbH® SRC 1, Clariant GmbH TAED 1TAED 1 ®Peractive AN, Fa. Clariant GmbH®Peractive AN, Clariant GmbH TAED 2TAED 2 ®Peractive AC White, Fa. Clariant GmbH®Peractive AC White, Clariant GmbH Zeolith AZeolite A ®Wessalith P, Fa. Degussa®Wessalith P, Degussa

Figure imgb0001
Figure imgb0001
Figure imgb0002
Figure imgb0002
Figure imgb0003
Figure imgb0003
Tabelle 3Table 3 BeispieleExamples 2929 3030 Schichtsilicat aus Bsp. 6Phyllosilicate from Ex. 6 (Gew.-%)(Wt .-%) 55 -- Schichtsilicat aus Bsp. 14Phyllosilicate from Ex. 14 (Gew.-%)(Wt .-%) -- 5,25.2 Schichtsilicat aus Bsp. 16Phyllosilicate from Ex. 16 (Gew.-%)(Wt .-%) -- -- Phosphat 2Phosphate 2 (Gew.-%)(Wt .-%) -- 4747 Natriummetasilicat phSodium metasilicate ph (Gew.-%)(Wt .-%) -- -- Sodasoda (Gew.-%)(Wt .-%) 32,732.7 27,527.5 Natriumhydroxidsodium hydroxide (Gew.-%)(Wt .-%) -- -- Natriumcitrat thSodium citrate th (Gew.-%)(Wt .-%) 35,035.0 -- Natriumpercarbonatsodium (Gew.-%)(Wt .-%) 1010 -- Natriumperborat mhSodium perborate mh (Gew.-%)(Wt .-%) -- 1010 NaDCCNaDCC (Gew.-%)(Wt .-%) -- -- Polycarboxylat 2Polycarboxylate 2 (Gew.-%)(Wt .-%) 7,57.5 3,53.5 TAED 2TAED 2 (Gew.-%)(Wt .-%) 55 22 Enzym 2Enzyme 2 (Gew.-%)(Wt .-%) 1,51.5 1,51.5 Enzym 3Enzyme 3 (Gew.-%)(Wt .-%) 1,51.5 1,51.5 AE 2AE 2 (Gew.-%)(Wt .-%) 1,51.5 1,51.5 ParfümPerfume (Gew.-%)(Wt .-%) 0,30.3 0,30.3 Dosierungdosage -- 20 g20 g 20g20g Tabelle 4Table 4 Beispielexample 3131 Phosphat 3Phosphate 3 (Gew.-%)(Wt .-%) 2525 Schichtsilicat aus Bsp. 6Phyllosilicate from Ex. 6 (Gew.-%)(Wt .-%) 55 Sodasoda (Gew.-%)(Wt .-%) 11 Natriumhydroxidsodium hydroxide (Gew.-%)(Wt .-%) 11 Phosphonat 2Phosphonate 2 (Gew.-%)(Wt .-%) 0,50.5 Polycarboxylat 3Polycarboxylate 3 (Gew.-%)(Wt .-%) 22 Alkansulfonatalkanesulfonate (Gew.-%)(Wt .-%) 1.51.5 Wasserglaswater glass (Gew.-%)(Wt .-%) 3535 Natriumhypochloritsodium hypochlorite (Gew.-%)(Wt .-%) 99 Wasserwater (Gew.-%)(Wt .-%) 2020 Dosierungdosage (g)(G) 4040

Claims (21)

  1. A builder composition obtainable by bringing into contact with one another
    a) crystalline sheetlike sodium silicate of the formula NaMSixO2x+1·yH2O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20,
    b) water and
    c) sodium hydrogensulfate or sulfuric acid as acidic, H+-releasing component, where the
    d) molar ratio of the crystalline sheetlike sodium silicate a) to the total amount of the releasable H+ of the acid component c) is 4 : 1 to 1 000 : 1, the
    e) molar ratio of the water b) to the total amount of the releasable H+ of the acidic component c) is 3 : 1 to 1 000 : 1 and
    f) subjecting the sodium silicate treated in this way to a heat treatment at 30 to 400°C over a period of from 0.5 to 1000 min and
    g) Compacting and grinding the sodium silicate obtained in this way, the compaction and grinding being carried out either before or after the heat treatment.
  2. The builder composition as claimed in claim 1, wherein the crystalline sheetlike sodium silicate a) comprises 0 to 40% by weight of alpha-sodium disilicate, 0 to 40% by weight of beta-sodium disilicate, 40 to 100% by weight of delta-sodium disilicate and 0 to 40% by weight of amorphous fractions.
  3. The builder composition as claimed in claim 2, wherein the crystalline sheetlike sodium silicate a) comprises 80 to 100% by weight of delta-sodium disilicate.
  4. A builder composition as claimed in at least one of claims 1 to 3, wherein the crystalline sheetlike sodium silicate a) comprises additional cationic and/or anionic constituents.
  5. The builder composition as claimed in at least one of claims 1 to 4, wherein the crystalline sheetlike sodium silicate a) is used as a powder having an average particle size of from 0.1 to 4 000 µm.
  6. The builder composition as claimed in one of claims 1 - 5, wherein, after the components a), b) and c) have been brought into contact, the mixture is firstly heat-treated, then compacted, then ground and is then optionally fractionated according to size.
  7. The builder composition as claimed in one of claims 1-5, wherein, after the components a), b) and c) have been brought into contact, the mixture is first compacted, then ground, then optionally fractionated according to size and is then heat-treated.
  8. The builder composition as claimed in at least one of claims 1-7, wherein the compaction is roll compaction.
  9. The builder composition as claimed in at least one of claims 1 to 8, wherein, during the compaction, up to 10% by weight of compacting auxiliaries, preferably water, water glass, polyethylene glycol, nonionic surfactants, anionic surfactants, polycarboxylate copolymers, modified, and/or unmodified celluloses, bentonite, hectonites and/or saponites.
  10. The builder composition as claimed in at least one of claims 1 to 9, which is granules having an average particle size of from 200 to 2 000 µm.
  11. The builder composition as claimed in at least one of claims 1 to 10, which is ground granules having an average particle size of from 0.1 to 300 µm.
  12. The builder composition as claimed in at least one of claims 1 to 11, wherein the dissolution residue of a 0.25% strength aqueous solution at 20°C and after stirring for 20 minutes is less than or equal to 50%.
  13. A laundry detergent or cleaner comprising at least one builder composition as claimed in at least one of claims 1 to 12.
  14. The cleaner as claimed in claim 13, which is a machine dishwashing detergent.
  15. The laundry detergent or cleaner as claimed in claim 13 and/or 14,which comprises:
    a) 0.5 to 98% by weight of the builder composition
    b) optionally 0.5 to 80% by weight of cobuilders
    c) optionally 1 to 50% by weight of interface-active substances
    d) optionally 0.5 to 80% by weight of pH regulators
    e) optionally 1 to 70% by weight of bleaches
    f) ad 100% by weight of further customary ingredients.
  16. A component of a laundry detergent modular system which comprises 60 to 100% by weight of a builder composition as claimed in at least one of claims 1 to 12.
  17. A water softener comprising at least one builder composition as claimed in at least one of claims 1 to 12.
  18. The water softener as claimed in claim 17, which comprises
    a) 0.5 to 99% by weight of the builder composition
    b) optionally 0.5 to 80% by weight of cobuilders
    c) optionally 0 to 10% by weight of interface-active substances and
    d) optionally 0.5 to 80% by weight of pH regulators.
  19. A laundry detergent or cleaner, water softener or component of a laundry detergent modular system which comprises at least one builder composition as claimed in at least one of claims 1 to 12 in the form of a compound of composition
    a) 70 to 99.5% by weight of the builder composition and
    b) 0.5 to 30% by weight of anionic, cationic, nonionic and/or zwitterionic surfactant.
  20. A laundry detergent or cleaner, water softener or component of a laundry detergent modular system, which comprises at least one builder composition as claimed in at least one of claims 1 to 12 in the form of a compound of composition
    a) 50 to 99% by weight of the builder composition.
    b) 0.01 to 10% by weight of dye and
    c) ad 100% by weight of further customary ingredients.
  21. The composition or component as claimed in at least one of claims 13 to 20, which is in tablet form.
EP01126163A 2000-11-14 2001-11-03 Builder composition Expired - Lifetime EP1205537B1 (en)

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DE10056346A DE10056346A1 (en) 2000-11-14 2000-11-14 Builders for use in detergents, washing agents and water-softeners show reduced amounts of residue on dissolving and are based on crystalline layered sodium silicates
DE10056346 2000-11-14

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US7109157B2 (en) * 2003-02-27 2006-09-19 Lawnie Taylor Methods and equipment for removing stains from fabrics using a composition comprising hydroxide and hypochlorite
DE102004063801A1 (en) * 2004-12-30 2006-07-13 Henkel Kgaa Preparation of ascorbic acid granulates, used for preparing particulate shaped washing/cleaning agents, comprises granulation of ascorbic acid, a water-soluble polymer, as bonding agents, and optionally an inorganic carrier material
ES2639442T3 (en) * 2009-01-28 2017-10-26 The Procter And Gamble Company Composition for washing clothes in a multi-compartment bag
JP2014522896A (en) * 2011-07-12 2014-09-08 クラリアント・インターナシヨナル・リミテツド Use of a combination of secondary paraffin sulfonate and amylase to enhance the cleaning capacity of a liquid laundry detergent
JP2014523469A (en) * 2011-07-12 2014-09-11 クラリアント・インターナシヨナル・リミテツド Use of secondary paraffin sulphonate to enhance the cleaning ability of the enzyme
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JP7414835B2 (en) 2019-02-19 2024-01-16 ユニリーバー・アイピー・ホールディングス・ベスローテン・ヴェンノーツハップ Extruded soap bar with high water content

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