EP1205537B1 - Composition d' adjuvant - Google Patents

Composition d' adjuvant 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)
English (en)
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EP1205537A2 (fr
EP1205537A3 (fr
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/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular 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.

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Claims (21)

  1. Composition d'adjuvant pouvant être obtenue en mettant en contact les uns avec les autres
    a) du phyllosilicate de sodium cristallin de formule NaMSixO2x+1*yH2O, où M représente un atome de sodium ou d'hydrogène, x représente un nombre de 1,9 à 4 et y représente un nombre de 0 à 20
    b) de l'eau et ..
    c) de l'hydrogénosulfate de sodium ou de l'acide sulfurique en tant que composant acide libérant des ions H+,
    dans laquelle
    d) le rapport molaire du phyllosilicate de sodium cristallin a) à la quantité totale des ions H+ libérables du composant acide c) est de 4:1 à 1000:1,
    e) le rapport molaire de l' eau b) à la quantité totale des ions H+ libérables du composant acide est de 3:1 à 1000:1 et
    f) en soumettant le silicate de sodium ainsi traité à un traitement thermique à une température de 30°C à 400°C pendant une durée de 0,5 à 1000 min., et
    g) en compactant et en broyant le silicate de sodium ainsi obtenu, le compactage et le broyage étant réalisés avant ou après le traitement thermique.
  2. Composition d'adjuvant selon la revendication 1, dans laquelle le phyllosilicate de sodium cristallin a) comprend 0% à 40% de disilicate de sodium alpha, 0% à 40% en poids de disilicate de sodium bêta, 40% à 100% en poids de disilicate de sodium delta et 0% à 40% en poids de fractions amorphes.
  3. Composition d'adjuvant selon la revendication 2, dans laquelle le phyllosilicate de sodium cristallin a) comprend 80% à 100% en poids de disilicate de sodium delta.
  4. Composition d'adjuvant selon au moins l'une des revendications 1 à 3, dans laquelle le phyllosilicate de sodium cristallin a) comprend des composants cationiques et/ou anioniques supplémentaires.
  5. Composition d'adjuvant selon au moins l'une des revendications 1 à 4, dans laquelle le phyllosilicate de sodium cristallin a) est utilisé sous la forme d'une poudre ayant une taille moyenne des particules de 0,1 à 4000 µm.
  6. Composition d'adjuvant selon l'une quelconque des revendications 1 à 5, dans laquelle, après la mise en contact des composants a), b) et c), le mélange est d'abord soumis à un traitement thermique puis compacté, puis broyé, et il est ensuite éventuellement fractionné selon la taille.
  7. Composition d'adjuvant selon l'une quelconque des revendications 1 à 5, dans laquelle, après la mise en contact des composants a), b) et c), le mélange est d'abord compacté, puis broyé, puis éventuellement fractionné selon la taille, et il est ensuite soumis à un traitement thermique.
  8. Composition d'adjuvant selon au moins l'une des revendications 1 à 7, dans laquelle le compactage est un compactage au rouleau.
  9. Composition d'adjuvant selon au moins l'une des revendications 1 à 8, dans laquelle, pendant le compactage, jusqu'à 10% en poids d'adjuvants de compactage, de préférence de l'eau, du verre soluble, du polyéthylèneglycol, des tensio-actifs non ioniques, des tensio-actifs anioniques, des copolymères de polycarboxylate, des celluloses modifiées et/ou non modifiées, des bentonites, des hectorites et/ou des saponites sont présents.
  10. Composition d'adjuvant selon au moins l'une des revendications 1 à 9, qui est sous forme de granulés ayant une taille moyenne des particules de 200 à 2000 µm.
  11. Composition d'adjuvant selon au moins l'une des revendications 1 à 10, qui est sous forme de granulés broyés ayant une taille moyenne des particules de 0,1 à 300 µm.
  12. Composition d'adjuvant selon au moins l'une des revendications 1 à 11, dans laquelle le résidu de dissolution d'une solution aqueuse à 0,25%, à 20°C et après une agitation de 20 minutes, est inférieur ou égal à 50%.
  13. Produit de lavage ou de nettoyage, comprenant au moins une composition d'adjuvant selon au moins l'une des revendications 1 à 12.
  14. Produit de nettoyage selon la revendication 13, qui est un produit pour lave-vaisselle.
  15. Produit de lavage ou de nettoyage selon la revendication 13 et/ou 14, qui comprend .
    a) 0,5% à 98% en poids de la composition d'adjuvant,
    b) éventuellement 0,5% à 80% en poids de co-adjuvants,
    c) éventuellement 1% à 50% en poids de tensio-actifs,
    d) éventuellement 0,5% à 80% en poids de régulateurs de pH,
    e) éventuellement 1% à 70% en poids d'agents de blanchiment,
    f) le complément jusqu'à 100% en poids d'autres ingrédients classiques.
  16. Composant d'un système de détergent modulaire qui comprend 60% à 100% en poids d'une composition d'adjuvant selon au moins l'une des revendications 1 à 12.
  17. Adoucisseur d'eau comprenant au moins une composition d'adjuvant selon au moins l'une des revendications 1 à 12.
  18. Adoucisseur d'eau selon la revendication 17, qui comprend
    a) 0,5% à 99% en poids de la composition d'adjuvant,
    b) éventuellement 0,5% à 80% en poids de co-adjuvants,
    c) éventuellement 0% à 10% en poids de tensio-actifs et
    d) éventuellement 0,5% à 80% en poids de régulateurs de pH.
  19. Produit de lavage ou de nettoyage, adoucisseur d'eau ou composant d'un système de détergent modulaire, qui comprend au moins une composition d'adjuvant selon au moins l'une des revendications 1 à 12, sous la forme d'un mélange composé de
    a) 70% à 99,5% en poids de la composition d'adjuvant et
    b) 0,5% à 30% en poids d'un tensio-actif anionique, cationique, non ionique et/ou zwitterionique.
  20. Produit de lavage ou de nettoyage, adoucisseur d'eau ou composant d'un système de détergent modulaire, qui comprend au moins une composition d'adjuvant selon au moins l'une des revendications 1 à 12, sous la forme d'un mélange composé de
    a) 50% à 99% en poids de la composition d'adjuvant et
    b) 0,01% à 10% en poids de colorant et
    c) le complément jusqu'à 100% en poids d'autres ingrédients classiques.
  21. Composition ou composant selon au moins l'une des revendications 13 à 20, qui est sous forme de comprimés.
EP01126163A 2000-11-14 2001-11-03 Composition d' adjuvant Expired - Lifetime EP1205537B1 (fr)

Applications Claiming Priority (2)

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DE10056346 2000-11-14
DE10056346A DE10056346A1 (de) 2000-11-14 2000-11-14 Builder-Zusammensetzung

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EP1205537A2 EP1205537A2 (fr) 2002-05-15
EP1205537A3 EP1205537A3 (fr) 2002-06-19
EP1205537B1 true EP1205537B1 (fr) 2006-03-08

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DE10121051A1 (de) * 2001-04-28 2002-10-31 Clariant Gmbh Builder-Zusammensetzung
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 (de) * 2004-12-30 2006-07-13 Henkel Kgaa Verfahren zur Herstellung von Farbschutzwirkstoff-Granulaten
ES2639442T3 (es) * 2009-01-28 2017-10-26 The Procter And Gamble Company Composición para lavado de ropa en bolsa multicompartimental
JP2014523469A (ja) * 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 酵素の洗浄能力を高めるための第二パラフィンスルホネートの使用
WO2013007366A1 (fr) * 2011-07-12 2013-01-17 Clariant International Ltd Utilisation d'une association d'un sulfonate de paraffine secondaire et d'amylase pour augmenter le pouvoir détergent de liquides lessiviels
MX2021009869A (es) 2019-02-19 2022-09-14 Unilever Ip Holdings B V Barras duras con alto contenido de agua que comprenden una combinacion de tipo y cantidad de electrolitos.
WO2020169306A1 (fr) 2019-02-19 2020-08-27 Unilever N.V. Pain de savon extrudé à haute teneur en eau

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DE50109142D1 (de) 2006-05-04
US6844310B2 (en) 2005-01-18
EP1205537A2 (fr) 2002-05-15
JP2002180089A (ja) 2002-06-26
DE10056346A1 (de) 2002-05-16
ES2259641T3 (es) 2006-10-16
US20020155982A1 (en) 2002-10-24
EP1205537A3 (fr) 2002-06-19

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