EP1347037B1 - Additif pour detergents a teneur elevée en tensioactifs non ioniques et solubilité rapide - Google Patents

Additif pour detergents a teneur elevée en tensioactifs non ioniques et solubilité rapide Download PDF

Info

Publication number
EP1347037B1
EP1347037B1 EP03006115A EP03006115A EP1347037B1 EP 1347037 B1 EP1347037 B1 EP 1347037B1 EP 03006115 A EP03006115 A EP 03006115A EP 03006115 A EP03006115 A EP 03006115A EP 1347037 B1 EP1347037 B1 EP 1347037B1
Authority
EP
European Patent Office
Prior art keywords
detergent additive
weight
granules
surfactant
previous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03006115A
Other languages
German (de)
English (en)
Other versions
EP1347037A1 (fr
Inventor
Ulrich Dr. Sohling
Wolfgang Dr. Heininger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sued Chemie AG
Original Assignee
Sued Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sued Chemie AG filed Critical Sued Chemie AG
Publication of EP1347037A1 publication Critical patent/EP1347037A1/fr
Application granted granted Critical
Publication of EP1347037B1 publication Critical patent/EP1347037B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • 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
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite 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
    • C11D3/02—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
    • C11D3/02—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
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a detergent additive with a high content of nonionic surfactants (nonionic surfactants) and fast dissolving power.
  • Nonionic surfactants are used as one of the major surfactant components in powdered detergents and, for this application, because of their liquid consistency, must be applied to solid carriers in granular form. If granules with a high content of nonionic surfactants are added to a washing powder, these granules only dissolve very slowly in many cases. The slow dissolution rate is based on the phase behavior of nonionic surfactants in mixtures with water.
  • phase separations as well as high viscosity gel phases may occur when diluted with water.
  • these highly viscous gel phases can penetrate water only very slowly. This can lead to some undesirable effects when using the washing powder.
  • the granules can form sticky residues in the drawer of the washing machine and thus prevent complete flushing of the washing powder in the drum.
  • detergent residues also remain on the clothes to be washed.
  • complications occur even when granules are incorporated at a low dissolution rate in washing powder for hand washing, since in this case the washing powder is usually only very briefly stirred with the water.
  • a particularly low solubility is found in mixtures of pure bentonitancem granules and nonionic surfactants. This may be due to the fact that the bentonite swells and acts as a thickener and thus prevents the rapid disintegration of the agglomerates.
  • detergent additives which do not constitute surfactants but increase the solubility of nonionic surfactants on detergent granules or surfactant granules.
  • these include, for example, alcohols, glycerol and polyglycols. That's how it describes DE-A-196 12 085 the use of alkylated polyglycol ethers having from 5 to 25 ethylene glycol units, which may be branched in the alkyl radical, for improving the dissolution rate of nonionic surfactants.
  • at least 10% of these additives must be used to achieve a large increase in solubility.
  • DE-A-196 49 150 The DE-A-196 49 150 .
  • DE-A-196 47 609 and DE-A-196 48 504 also describe additives for increasing the dissolution rate of particulate detergent formulations in water.
  • These additives are crosslinked alkoxylated alcohols, compounds of at least trihydric alcohols and their alkoxylation products or hydrophobic, alkoxylated, at least trihydric alcohols.
  • the disadvantage of these additives is that they have no positive influence on the washing properties of the nonionic surfactants and the total washing powder.
  • a particulate detergent and cleaner containing from 20 to 94% by weight of builder and from 50 to 60% by weight of nonionic surfactant.
  • the granules additionally contain from 1 to 20% by weight of cellulose or cellulose derivatives and are prepared by mixing the nonionic surfactant with the builder and then roll compaction with the cellulose.
  • cellulose microcrystalline cellulose, ie a typical dispersing agent, is described here.
  • Such a composition has the disadvantage that the microcrystalline celluloses are expensive and have no positive effects on the washing process.
  • the production process for the granules is very complicated, since a roll compaction must be carried out after mixing the builder with the nonionic surfactants. Experience has shown that such granules are difficult to crush and sieve after roll compaction.
  • the WO 99/32591 describes particulate detergents or cleansers or compounds therefor which comprise (a) 40 to 80% by weight of zeolite, in particular of the faujasite type, and; (B) 20 to 60 wt .-% of one or more alkoxylated C 8 -C 18 alcohols and alkyl polyglycosides.
  • the claimed agents can contain large amounts of liquid nonionic surfactants without losing their flowability and show a good dissolution rate.
  • the WO 99/36493 describes detergent granules with improved dissolving power, containing 10 to 60 wt .-% of surfactants (eg nonionic surfactants, linear alkylbenzenesulfonates and mixtures thereof).
  • the detergent granules additionally contain from 0.1 to 10% by weight of water-insoluble dispersing aids, such as starch derivatives, Veegum, cellulose, kaolin, crosslinked carboxymethylcellulose, microcrystalline cellulose, crosslinked polyvinylpyrrolidone.
  • the low dissolution rate of the detergent granules is to be increased by the fact that the granules disintegrate when taking up little water into small granules, which dissolve faster due to their larger surface area.
  • the use of the dispersing aids has the disadvantage that they have no influence on the washing properties of the washing powder and are also very expensive. Furthermore, the use of large amounts of such dispersing aids can lead to deposits on the laundry.
  • the WO 99/46359 describes a process for producing detergent granules which are said to have a fast solubility and particularly good washing properties.
  • a liquid component which contains an anionic surfactant, a nonionic surfactant and a so-called structuring agent is mixed with a solid support material in an agglomeration process, whereupon the mixture is optionally dried and / or cooled becomes.
  • the structuring agent is included in the liquid component in amounts such that it is pumpable at 50 ° C but causes solidification of the mixture upon storage and / or drying of the product.
  • the granules can be incorporated into bleach-containing detergent compositions. Compared with comparison blends, the fibers of the washed fabrics should be spared.
  • the detergent compositions should have a high solubility.
  • the structuring agents are described very generally, but in particular soap is preferred as structuring agent. Overall, the structuring agents lead to a reduction in the total surfactant content because the absorption capacity of the support materials is partially consumed by these structuring agents.
  • the DE-A-4 320 8511 describes a detergent with discoloration-inhibiting properties, which contains 10 to 30% by weight of nonionic surfactants 0 to 5% by weight of anionic surfactants, 1 to 6% by weight of fatty acids and 20 to 60% by weight of builders from the group of zeolites and phyllosilicates (eg bentonite), but is free of polyvinylpyrrolidone (PVP).
  • the detergent granules are prepared by extrusion. A characterization of the granules regarding their solubility was not carried out.
  • nonionic surfactant contents are substantially below 30 wt .-%.
  • the WO 00/32742 describes a surfactant mixture in solid form for use as detergents and cleaners containing surfactants and builders as well as other conventional ingredients, wherein the surfactants and builders and the other ingredients are distributed in individual units of 2 to 8 mm; ie the reactive ones Active substances should be kept separate from each other.
  • the US 5,736,501 relates to a process for preparing nonionic surfactant granules, wherein the following components are mixed: (i) at least one nonionic surfactant and an aqueous nonionic surfactant solution; (ii) an acid precursor of a nonionic surfactant capable of lamellar orientation; (iii) at least one alkali builder and / or an alkaline porous oil absorbing carrier to provide a mixture of surfactant starting materials containing the nonionic surfactant as the major surfactant component, and then heating the resultant mixture to at least a temperature corresponding to that of Neutralization of the acid precursor of the anionic surfactant allows.
  • the WO 97/17422 describes a process for the preparation of alkali metal silicate granular granules, wherein a mixture is prepared comprising: (a) a crystalline alkali metal silicate; (b) a nonionic surfactant; and (c) an acid precursor of an anionic surfactant capable of lamellar orientation.
  • the object of the invention was to increase the dissolution rate of detergent additives in granular form which have a high content of nonionic surfactants on a solid silicate carrier.
  • the invention thus provides a detergent additive in granular form according to claim 1.
  • the detergent additive is preferably characterized in that at least part of the anionic surfactants is present in the acid form (protonated form) during production.
  • the anionic surfactant in the preparation in the acid form is practically anhydrous available and usable ,
  • Alcohol ethoxylates or their derivatives are preferably used as nonionic surfactants.
  • anionic surfactant preference is given to using linear alkylsulfonates (LAS) in the acid form.
  • LAS linear alkylsulfonates
  • the detergent additive contains 0.1 to 15 wt .-% of linear alkylbenzenesulfonate.
  • the agglomerate particles preferably have a size of about 0.1 to 2 mm, in particular from about 0.1 to 1.9 mm, particularly preferably from about 0.4 to 1.6 mm.
  • the agglomerate particles preferably have a bulk density of about 400 to 1000 g / l.
  • the solid silicate support comprises a layered silicate, a zeolite and / or precipitated silica, the latter also being referred to as a "silicate support" for purposes of the present specification.
  • the layered silicate represents a bentonite or a hectorite; the zeolite is preferably a type A or MAP zeolite.
  • the detergent additive according to the invention preferably additionally contains an alkaline substance in order to at least partially neutralize the acid form of the anionic surfactant, the neutralizing substance preferably being soda.
  • the soda content is preferably about 4 to 40, especially about 5 to 30 wt .-%.
  • the detergent additive according to the invention may additionally contain an alkali metal sulfate, an alkali citrate, an alkali metal silicate and / or sodium tripolyphosphate; Furthermore, it can be coated with a flow aid.
  • the invention further provides a process for the preparation of the detergent additive according to the invention, which comprises mixing the solid silicate carrier during agglomeration in an intensive mixer with a mixture of the nonionic surfactant (s) and the anionic surfactant (s) ( en) is applied.
  • "Agglomeration" in the present context means that no extrusion is carried out.
  • the resulting granules are optionally dried and coated after agglomeration with a known powdery inorganic Rieselangesstoff.
  • the invention further provides the use of an anionic surfactant in the acid form (protonated form) for increasing the solubility of a detergent additive in granular form containing at least about 30% by weight of nonionic surfactant (s) and at least one siliceous carrier.
  • the carrier substance mentioned is primarily bentonite, although other carrier substances as stated in claim 9 may also be used.
  • bentonite In so-called "2 in 1 detergents" bentonite is used to increase the softness.
  • the bentonite concentrations used for this purpose are typically in the range of 5 to 10 wt .-%, based on the total formulation.
  • the bentonite in granulated form can subsequently be added to the washing powder formulation. This has the advantage that the bentonite does not have to be incorporated directly into the formulation, which can be difficult for processing-technical reasons, because the bentonite can already have a strongly thickening effect in concentrations of a few percent.
  • this detergent additive it would be conceivable to add a nonionic surfactant to a given detergent formulation simultaneously with the bentonite.
  • the dissolution behavior of highly nonionic surfactant-containing bentonite granules can be improved if anionic surfactants from the group of linear alkylbenzenesulfonates are added during the granulation process.
  • anionic surfactants from the group of linear alkylbenzenesulfonates are added during the granulation process. This effect may be explained by the fact that during the dissolution of the granules, the anionic surfactants sit on the edges of the bentonite platelets and prevent the formation of so-called card house structures, which can lead to an increase in viscosity.
  • Alcohol ethoxylates and their derivatives are preferably used as nonionic surfactants.
  • nonionic surfactants include Fatty alcohol polyethylene glycol ethers, fatty alcohol polyglycol ether methyl esters, fatty acid methyl ester ethoxylates, sorbitan esters or mixtures thereof.
  • Particular preference is given to fatty alcohol polyethylene glycol ethers, fatty alcohol polyglycol ether methyl esters or mixtures thereof.
  • the agglomerates according to the invention can be dissolved surprisingly rapidly.
  • fatty alcohol polyethylene glycol ethers those customary in detergent applications, i. have the degrees of ethoxylation between 1 and 12 and alkyl chain radicals having 10 to 17 carbon units.
  • Fatty alcohol polyethylene glycol ethers containing a few ethoxylate units are preferably used in mixtures with higher ethoxylated fatty alcohol polyethylene glycol ethers.
  • nonionic surfactants are dependent on the specific requirements of the detergent and can be determined in each case by a person skilled in the art on the basis of routine experiments.
  • the linear alkylbenzenesulfonates can be used to prepare the granules both in their acid form and in the form of their alkali metal salts.
  • the latter are mainly in the form of aqueous pastes commercially.
  • these have the advantage over the acid form of the surfactant that the pH is not lowered, on the other hand water is introduced into the granules by using this formulation, which may adversely affect the storage behavior of the granules in washing powders and in particular detergent tablets.
  • These formulations are therefore desirably dried after granulation.
  • the anionic surfactants in their acid form are, in particular, the linear alkyl sulfonates (LAS).
  • LAS linear alkyl sulfonates
  • Such products are commercially available from the companies Unger (Ufacid® K), Hüls / Condea (Marlon® AS 3 ), BASF (Lutensit® A-LBS).
  • the aqueous LAS pastes are, for example, the commercial products Ufasan® 50, Ufasan® 65 or Ufasan® 60a from Unger, Marlon® A 350, Marlon® A 360 or Marlon® A 375 from Condea and Lutensit® A from BASF.
  • the increase in the solubility of the granules by the additives used according to the invention can be verified by different measuring methods.
  • Such a method is a measurement of the interfacial tension in water as a function of stirring time at a constant Granulatzugabe. After another test, a defined amount of granules in a defined amount of water and determined after a fixed stirring time under certain stirring geometry, the residue by sieving through Metal sieve and subsequent drying to constant weight (see examples).
  • the described granules are expediently prepared in an agglomeration process, wherein known mixers can be used.
  • the granulation can be carried out both continuously and batchwise. In this case, it may be necessary to coat the granules with inorganic powders in a second step, which increases their whiteness and / or improves their flowability.
  • the described agglomerates can also be prepared in a batch process. If a batch process is used and a coating is required, this can be carried out in a second step in the same mixer by addition of the inorganic powder and by a short additional mixing step.
  • soda contents of ⁇ 20% by weight are particularly preferred. If granulation is carried out in the presence of zeolite with linear alkylbenzenesulfonic acid in the surfactant system, it must also be considered that, when zeolites are used as support materials, solubilization or dissolution of the zeolite can occur when high contents of linear alkylbenzenesulfonic acid are used.
  • the granules with a high content of nonionic surfactants which are prepared by the process according to the invention, have the advantage of a very high solubility.
  • additives such as dispersing aids, as in the WO 99/36493 described, unnecessary.
  • structuring agents such as eg soaps (cf. WO 99/46359 ). From experience, these are difficult to incorporate into liquid surfactant mixtures.
  • the avoidance of these additives makes it possible to further increase the content of nonionic surfactants, based on certain carrier mixtures and to avoid the addition of expensive auxiliaries, which do not contribute to the washing performance.
  • Dispersing aids such as microcrystalline cellulose have no positive influence on the cleaning effect of a washing powder.
  • the bentonite leads in such surfactant-containing granules to improve the soft touch and to reduce the graying of the laundry.
  • the invention is illustrated by the following examples in a non-limiting manner.
  • an Eirich intensive mixer R02E was used unless otherwise stated.
  • the low setting (level 1) for the speed of rotation of the plate and the maximum speed of rotation for the whirler were selected.
  • the agglomeration parameters were chosen below such that more than 50% by weight of the granules were in a particle size range of 0.4 to 1.6 mm.
  • the mean particle size can be modified as known in the art, of course by appropriate choice of the production parameters.
  • the agglomerates In order to reduce the stickiness of the agglomerates, they have in many cases been coated with inorganic powders, such as, for example, talc or zeolites.
  • inorganic powders such as, for example, talc or zeolites.
  • the following methods were used: According to a first variant, the material was transferred into a plastic bag, whereupon the inorganic powder was added and shaken for about 2 minutes.
  • the coating was carried out in the Eirich mixer. For this purpose, after the agglomeration, the inorganic powder was added to the coating, whereupon the agglomerate / powder mixture was again mixed for 20 to 30 seconds at 50% of the maximum turbulence number of revolutions.
  • the total surfactant content is virtually independent of the surfactant composition.
  • sample a) shows, the granules prepared from Laundrosil® DGA and Genapol® OA 070 are poorly soluble according to the test method described above.
  • the solubility value is only 24%.
  • Ufacid® K anionic surfactant in the acid form
  • Ufacid® K anionic surfactant in the acid form
  • Laundrosil® DGA / soda blends with different soda contents were agglomerated with pure Genapol OA 070 and with Genapol OA 070 with an addition of 10% by weight Ufacid K.
  • the results of the experiments are listed in Table III.
  • the table shows that by adding in particular 10% by weight of Ufacid® K to the nonionic surfactant Genapol® OA 070 it is possible to obtain agglomerates which have a significantly higher solubility than the agglomerates containing 100% by weight of nonionic surfactant.
  • the table further shows that up to 10% by weight of soda can be incorporated into the agglomerates without the surfactant content or the solubility significantly changing with additions of 10% by weight of Ufacid® K.
  • Laundrosil® DGA (comparative value from example 1) 100% by weight - 34 24 Laundrosil® DGA + 5% by weight soda 90% by weight 10% by weight 37.2 67.2 Laundrosil® DGA + 10% by weight soda 90% by weight - 38.0 31.3 Laundrosil® DGA + 10% by weight soda 90% by weight 10% by weight 36.8 63.2 Laundrosil® DGA + 20% by weight soda 90% by weight 10% by weight 36.4 50 Laundrosil® DGA + 30% by weight soda 90% by weight 10% by weight 34 44
  • Laundrosil® DGA and Wessalith® XD (Degussa AG, a zeolite X) were agglomerated in a weight ratio of 1: 2 with the surfactants listed in Table IV. Initially, pure Genapol® OA 070 was used. In further samples, in each case 5, 10 and 15% by weight of Marlon® AS 3 were added. All granules have the same surfactant content. To determine the solubility, the granules are coated with 10 wt .-% Wessalith D and sieved to sizes of 0.4 to 1.6 mm.
  • a drastic increase in solubility is observed, in particular with the addition of 5% by weight of Marlon® AS 3 (increase from 22 to 81% by weight).
  • the solubility can be increased from 5 to 15 wt .-% to values up to 96 wt .-% with an increase of the Marlon AS 3 content.
  • the results show that the solubility of high nonionic surfactant granules containing zeolites as the major carrier component can be drastically improved even by a small addition of alkylbenzenesulfonic acid.
  • agglomerates were prepared by the same method and with the same support materials containing known additives which are said to suppress gel formation upon dissolution of the granules and to improve their solubility.
  • additives which are said to suppress gel formation upon dissolution of the granules and to improve their solubility.
  • These are the alkyl polyglycoside Glucopon® 600 CSUP from Henkel / Cognis, polyglycol 200 and polyglycol 4000 from Clariant and Pluriol® ES 9985 from BASF.
  • the last product is a modified polyalkylene glycol which, according to the manufacturer, reduces the gelling of nonionic surfactants. The results are listed in Table V.
  • compositions according to the invention have, at equal or higher contents of nonionic surfactants, a drastically increased solubility compared with the prior art. Furthermore, the compositions according to the invention have the advantage that the solubility improvement is achieved by combination with a surfactant. This eliminates the use of additives such as polyethylene glycol, which have no function in the washing process and which, as the tables show, additionally reduce the nonionic content of the granules.
  • the disintegration promoter used was a microcrystalline cellulose (Vivapur® 101 from Rettenmaier).
  • the granules were prepared as in the previous examples with an Eirich mixer and coated with 10 wt .-% Wessalith P or in the case of using Wessalith XD as a carrier with 10 wt .-% Wessalith XD and to sizes of 0.4 screened to 1.6 mm.
  • the solubility was determined as in the previous examples.
  • the composition of the three granules is listed in the following Table VI together with the surfactant content (based on Genapol® OA 070) and the solubility.
  • the content of the three granules of microcrystalline cellulose was between 5.9 and 6.4 wt .-%. ⁇ u> Table VI ⁇ / u> Carrier [wt%] Disintegration promoter Vivapur® 101 [% by weight] Surfactant content (Genapol® OA070) [% by weight] Solubility [%] Laundrosil® DGA Light soda Wessalith®XD 58 - - 6.4 36 25 54.6 3.2 - 6.4 35.8 26 17.9 - 35.4 5.9 41 47
  • solubility is much lower than that which can be achieved by adding 5% by weight of linear alkylbenzenesulfonate.
  • a solubility of 81 wt .-% was achieved at a slightly higher surfactant content, without the need to add a material which has no function in the washing process.
  • compositions according to the invention are described with surfactant contents above 35%, which are based on support materials of mixtures of bentonite, zeolites and precipitated silicas.
  • the carrier used was a mixture of Wessalith P, Sipernat® 22 and Laundrosil® DGA in a weight ratio of 4: 1: 1 (66.7% by weight Wessalith P, 16.7% by weight Laundrosil® DGA, 16.7% by weight). -% Sipernat® 22). It was always worked with approaches of 600 g.
  • Glucopon® 600 CSUP did not mix well with Genapol OA 070. There was a settling effect after a short time.
  • the examples clearly show the improved solubility of the granules with addition of linear alkylbenzenesulfonates. This is significantly higher than in the case of an addition of the additives known from the prior art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (12)

  1. Additif de détergent sous forme de granulat avec au moins un support solide au silicate, contenant un silicate stratifié, un acide silicique précipité et/ou une zéolithe, caractérisé par la composition suivants :
    - au moins 30 % en poids d'éthoxylate d'alcool ;
    - jusqu'à 30 % en poids d'autres additifs, comme des sulfates alcalins, des citrates alcalins, des silicates alcalins et/ou des tripolyphosphates alcalins ;
    - 0,1 à 15 % en poids de benzènesulfate alkylique linéaire ;
    - le reste du mélange du support qui contient les composants principaux suivantes :
    5 à 100 parties en poids de bentonite ;
    0 à 80 parties en poids d'acide silicique précipité ;
    0 à 95 parties en poids de zéolithes ;
    l'additif de détergent ne contenant aucun auxiliaire de dispersion ou composant formateur de structure, comme du savon.
  2. Additif de détergent selon l'une quelconque des revendications précédentes, caractérisé en ce que les particules d'agglomérat présentent une taille d'environ 0,1 à 2 mm, de préférence d'environ 0,1 à 1,9 mm, notamment d'environ 0,4 à 1,6 mm.
  3. Additif de détergent selon l'une quelconque des revendications précédentes, caractérisé en ce que les particules d'agglomérat présentent une masse volumique apparente d'environ 400 à 1000 g/l.
  4. Additif de détergent selon l'une quelconque des revendications précédentes, caractérisé en ce que la zéolithe représente une zéolithe du type A ou MAP.
  5. Additif de détergent selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient en outre une substance alcaline, notamment de la soude.
  6. Additif de détergent selon l'une quelconque des revendications précédentes, caractérisé en ce que la teneur en soude se situe entre environ 5 et 40 % en poids, de préférence jusqu'à environ 5 à 30 % en poids.
  7. Additif de détergent selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient un sulfate alcalin, un citrate alcalin, un silicate alcalin et/ou du tripolyphosphate de sodium.
  8. Additif de détergent selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il est enduit d'un auxiliaire de lavage.
  9. Procédé pour la fabrication d'un additif de détergent selon l'une quelconque des revendications précédentes, caractérisé en ce que le support solide au silicate est sollicité pendant l'agglomération dans un mélangeur intensif avec un mélange du/des tensioactif(s) non ionique(s) et du/des tensioactif(s) anionique(s).
  10. Procédé selon la revendication 9, caractérisé en ce que l'on sèche éventuellement les granulats.
  11. Procédé selon la revendication 9 ou 10, caractérisé en ce que l'on enduit l'additif de détergent après l'agglomération d'un auxiliaire de lavage anorganique, sous forme de poudre.
  12. Procédé selon l'une quelconque des revendications 9 à 11, caractérisé en ce qu'au moins une partie du tensioactif anionique est présente sous forme acide lors de la fabrication.
EP03006115A 2002-03-19 2003-03-18 Additif pour detergents a teneur elevée en tensioactifs non ioniques et solubilité rapide Expired - Lifetime EP1347037B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10212169A DE10212169A1 (de) 2002-03-19 2002-03-19 Waschmittelzusatz mit hohem Gehalt an nichtionischen Tensiden und schnellem Auflösevermögen
DE10212169 2002-03-19

Publications (2)

Publication Number Publication Date
EP1347037A1 EP1347037A1 (fr) 2003-09-24
EP1347037B1 true EP1347037B1 (fr) 2010-08-18

Family

ID=27771432

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03006115A Expired - Lifetime EP1347037B1 (fr) 2002-03-19 2003-03-18 Additif pour detergents a teneur elevée en tensioactifs non ioniques et solubilité rapide

Country Status (4)

Country Link
EP (1) EP1347037B1 (fr)
AT (1) ATE478130T1 (fr)
DE (2) DE10212169A1 (fr)
ES (1) ES2350092T3 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10344938A1 (de) * 2003-09-27 2005-04-21 Clariant Gmbh Tensid-Compounds enthaltend Fettalkoholalkoxylate
GB2569938B (en) * 2016-06-12 2022-03-02 Sichuan Jinzhuang Tech Co Ltd Ornament of an instant detergent and detergent
CN106085632A (zh) * 2016-06-12 2016-11-09 四川省眉山市金庄新材料科技有限公司 一种速溶洗衣粉点缀物及洗衣粉

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US532455A (en) * 1895-01-15 Bridle-bit
AT330930B (de) * 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
WO1993004154A1 (fr) * 1991-08-20 1993-03-04 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de granulats carbonates
DE4216775A1 (de) * 1992-05-21 1993-11-25 Henkel Kgaa Pulverförmige Tensidmischung
WO1994005767A1 (fr) * 1992-09-08 1994-03-17 Unilever Plc Composition de detergent et procede de production
DE4304062A1 (de) * 1993-02-11 1994-08-18 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
DE4314885A1 (de) * 1993-05-05 1994-11-10 Sued Chemie Ag Verfahren zur Neutralisation der Säureform von anionischen Tensiden, danach erhaltene Agglomerate und Waschmittel
TW326472B (en) * 1994-08-12 1998-02-11 Kao Corp Method for producing nonionic detergent granules
DE19524464C2 (de) * 1995-07-10 2000-08-24 Cognis Deutschland Gmbh Verfahren zur Herstellung von Zuckertensidgranulaten
AUPN535095A0 (en) * 1995-09-12 1995-10-05 Procter & Gamble Company, The Compositions comprising hydrophilic silica particulates
US6521585B1 (en) * 1995-11-06 2003-02-18 Kao Corporation Method for producing crystalline alkali metal silicate granules and granular high density detergent
DE19601841A1 (de) * 1996-01-19 1997-07-24 Henkel Kgaa Niotensidreiche Granulate und Verfahren zu ihrer Herstellung
DE19735788A1 (de) * 1997-08-18 1999-02-25 Henkel Kgaa Verfahren zur Herstellung hochtensidhaltiger Granulate
DE19753310A1 (de) * 1997-12-02 1999-06-10 Henkel Kgaa Rohstoff-Compounds mit hohem Schüttgewicht
DE19756696A1 (de) * 1997-12-19 1999-07-01 Clariant Gmbh Schichtsilikathaltige Wasch- und Reinigungsmittelkomponente
DE19757216A1 (de) * 1997-12-22 1999-06-24 Henkel Kgaa Teilchenförmiges Wasch- und Reinigungsmittel
DE19822942A1 (de) * 1998-05-22 1999-11-25 Henkel Kgaa Granulation von Aniontensidsäuren
DE19822941A1 (de) * 1998-05-22 1999-11-25 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmitteln
DE19822943A1 (de) * 1998-05-22 1999-11-25 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmitteln
DE19844523A1 (de) * 1998-09-29 2000-03-30 Henkel Kgaa Granulationsverfahren
DE19855380A1 (de) * 1998-12-01 2000-06-08 Henkel Kgaa Granulationsverfahren
DE19858859A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Granulate
DE19910789A1 (de) * 1999-03-11 2000-09-14 Henkel Kgaa Granulationsverfahren
DE19936614B4 (de) * 1999-08-04 2008-12-24 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines Waschmittels
DE19944221C2 (de) * 1999-09-15 2003-03-06 Cognis Deutschland Gmbh Tensidgranulate
DE19961333B4 (de) * 1999-12-17 2006-12-14 Henkel Kgaa Verfahren zur Herstellung von Zuckertensidgranulaten
DE10123622A1 (de) * 2001-05-15 2002-11-28 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten

Also Published As

Publication number Publication date
ATE478130T1 (de) 2010-09-15
ES2350092T3 (es) 2011-01-18
DE10212169A1 (de) 2003-10-02
DE50312986D1 (de) 2010-09-30
EP1347037A1 (fr) 2003-09-24

Similar Documents

Publication Publication Date Title
DE69216191T2 (de) Waschmittelpulver und Verfahren zu deren Herstellung
DE69232364T2 (de) Teilchenförmige Detergenszusammensetzung oder Komponente
EP0536110B1 (fr) Procede pour fabriquer des granules tensio-actifs
DE69226029T2 (de) Waschmittel und Verfahren zu ihrer Herstellung
DE3400008A1 (de) Zur verwendung in tensidhaltigen mitteln geeignetes schaumregulierungsmittel
DE3838086A1 (de) Verfahren zur herstellung zeolithhaltiger granulate hoher dichte
WO1985001039A1 (fr) Suspension aqueuse, stabilisee a base de zeolithe
EP0814153A2 (fr) Compositon détergente solide ayant une dispersibilité améliorée
DE69203217T2 (de) Waschmittelzusammensetzungen und Verfahren zu deren Herstellung.
EP0544670B1 (fr) Additif d'avivage seche par pulverisation pour agents de lavage
EP1347037B1 (fr) Additif pour detergents a teneur elevée en tensioactifs non ioniques et solubilité rapide
WO1991009927A1 (fr) Additif d'agent de lavage granulaire, a effet avivant et procede pour sa fabrication
DE69825487T2 (de) Granuläre zusammensetzungen mit verbesserter auflösung
EP0633923B1 (fr) Additif granulaire sans phosphate contenant des tensioactifs non ioniques pour produits de lavage et detergents
EP0881279B1 (fr) Procédé de préparation de granules contenant un tensioactif cationique
EP0473622B1 (fr) Additif granulaire sans phosphates contenant des agents tensio-actifs non ioniques pour produit a lessive
EP0874684B1 (fr) Procede de production d'un additif granule
EP1257628B1 (fr) Agglomeres contenant du mineral en feuillets et des tensioactifs non ioniques
EP0903401B1 (fr) Additif antimicrobien pour détergents
EP0926232A2 (fr) Composition détergente sous forme de particules
WO2000071657A1 (fr) Procede de preparation de granulat de tensio-actifs
WO2000071654A1 (fr) Procede de preparation de granulat de tensio-actifs
EP1042439A1 (fr) Detergent et nettoyant particulaire
DE602004006480T2 (de) Verfahren zur Herstellung einer Bleichaktivatorzusammensetzung
WO1996041862A1 (fr) Preparations detergentes-actives solides et fortement concentrees avec solubilite amelioree meme pour des bains a basse temperature

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030318

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: AL LT LV MK

AKX Designation fees paid

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

17Q First examination report despatched

Effective date: 20050520

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 50312986

Country of ref document: DE

Date of ref document: 20100930

Kind code of ref document: P

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: STOLMSSR & PARTNER C/O GERNOT SPRINGER

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20100818

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Effective date: 20110105

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

Ref country code: FI

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

Effective date: 20100818

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

Ref country code: SI

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

Effective date: 20100818

Ref country code: PT

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

Effective date: 20101220

Ref country code: CY

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

Effective date: 20100818

Ref country code: BG

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

Effective date: 20101118

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

Ref country code: GR

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

Effective date: 20101119

Ref country code: NL

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

Effective date: 20100818

Ref country code: SE

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

Effective date: 20100818

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

Ref country code: IE

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

Effective date: 20100818

Ref country code: DK

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

Effective date: 20100818

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

Ref country code: SK

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

Effective date: 20100818

Ref country code: EE

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

Effective date: 20100818

Ref country code: RO

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

Effective date: 20100818

Ref country code: CZ

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

Effective date: 20100818

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

26N No opposition filed

Effective date: 20110519

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 50312986

Country of ref document: DE

Effective date: 20110519

BERE Be: lapsed

Owner name: SUD-CHEMIE A.G.

Effective date: 20110331

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

Ref country code: MC

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

Effective date: 20110331

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20111130

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

Ref country code: BE

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

Effective date: 20110331

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

Ref country code: FR

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

Effective date: 20110331

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: SUED-CHEMIE IP GMBH & CO. KG

Free format text: SUED-CHEMIE AG#LENBACHPLATZ 6#80333 MUENCHEN (DE) -TRANSFER TO- SUED-CHEMIE IP GMBH & CO. KG#LENBACHPLATZ 6#80333 MUENCHEN (DE)

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20120802 AND 20120808

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: SUD-CHEMIE IP GMBH & CO.KG

Effective date: 20121002

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: STOLMAR AND PARTNER, CH

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 478130

Country of ref document: AT

Kind code of ref document: T

Effective date: 20110318

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 50312986

Country of ref document: DE

Effective date: 20121025

Representative=s name: STOLMAR & PARTNER, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 50312986

Country of ref document: DE

Owner name: SUED-CHEMIE IP GMBH & CO. KG, DE

Free format text: FORMER OWNER: SUED-CHEMIE AG, 80333 MUENCHEN, DE

Effective date: 20121025

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

Ref country code: AT

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

Effective date: 20110318

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

Ref country code: LU

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

Effective date: 20110318

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

Ref country code: TR

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

Effective date: 20100818

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

Ref country code: HU

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

Effective date: 20100818

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCAR

Free format text: NEW ADDRESS: SEEFELDSTRASSE 69, 8008 ZUERICH (CH)

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 50312986

Country of ref document: DE

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

Ref country code: CH

Payment date: 20180323

Year of fee payment: 16

Ref country code: GB

Payment date: 20180329

Year of fee payment: 16

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

Ref country code: ES

Payment date: 20180423

Year of fee payment: 16

Ref country code: DE

Payment date: 20180530

Year of fee payment: 16

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

Ref country code: IT

Payment date: 20180323

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50312986

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20190318

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

Ref country code: CH

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

Effective date: 20190331

Ref country code: LI

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

Effective date: 20190331

Ref country code: DE

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

Effective date: 20191001

Ref country code: GB

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

Effective date: 20190318

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

Ref country code: IT

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

Effective date: 20190318

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20200727

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

Ref country code: ES

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

Effective date: 20190319