EP1733015B1 - Waschmittel - Google Patents

Waschmittel Download PDF

Info

Publication number
EP1733015B1
EP1733015B1 EP05722230A EP05722230A EP1733015B1 EP 1733015 B1 EP1733015 B1 EP 1733015B1 EP 05722230 A EP05722230 A EP 05722230A EP 05722230 A EP05722230 A EP 05722230A EP 1733015 B1 EP1733015 B1 EP 1733015B1
Authority
EP
European Patent Office
Prior art keywords
silane
dispersion
detergent
silica particles
acid
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.)
Not-in-force
Application number
EP05722230A
Other languages
English (en)
French (fr)
Other versions
EP1733015A1 (de
Inventor
Peter Greenwood
Hans Lagnemo
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.)
Akzo Nobel NV
Nouryon Pulp and Performance Chemicals AB
Original Assignee
Akzo Nobel NV
Eka Chemicals AB
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 Akzo Nobel NV, Eka Chemicals AB filed Critical Akzo Nobel NV
Priority to EP05722230A priority Critical patent/EP1733015B1/de
Publication of EP1733015A1 publication Critical patent/EP1733015A1/de
Application granted granted Critical
Publication of EP1733015B1 publication Critical patent/EP1733015B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D3/162—Organic compounds containing Si

Definitions

  • the present invention relates to a detergent composition comprising silane-modified silica particles.
  • Detergent compositions are currently being used in many cleaning applications including cleaning of hard and soft surfaces e.g. textile, and many other applications in household and industrial use.
  • US patent application 2002/0111287 A1 discloses a method of providing a detergent composition comprising hydrophilic silicate-containing particles.
  • these kinds of detergent compositions are not always sufficiently stable and may be liable to precipitation over time which of course is detrimental to the cleaning effect.
  • US2002/0192367 regards a method of treating fabric comprising applying to the fabric a treatment composition comprising coated particles of a solid core in the range from 10-700 nm and a coating of silicone polymer covalently bonded to the solid core.
  • the invention relates to a method of preparing an aqueous detergent dispersion comprising mixing at least one silane compound, colloidal silica particles, and a detergent, as described in claim 1, to form an aqueous detergent dispersion comprising silanized colloidal silica particles.
  • This method can be performed without environmental hazard and health problems for process operators handling the components of the forming aqueous detergent dispersion.
  • silane and colloidal silica particles are preferably carried out continuously, preferably at a temperature from about 20 to about 95, more preferably from about 50 to about 75, and most preferably from about 60 to about 70 °C.
  • silane is slowly added to the silica particles under vigorous agitation at a temperature of about 60 °C and at a controlled rate, which suitably is from about 0.01 to about 100, preferably from about 0.1 to about 10, more preferably from about 0.5 to about 5, and most preferably from about 1 to about 2 silane molecules per nm 2 colloidal silica surface area (on the colloidal silica particles) and hour.
  • the addition of silane can be continued for any suitable time depending on the addition rate, amount of silane to be added, and degree of desired silanisation.
  • the addition of silane is preferably continued for about 0.1 to about 6, preferably from about 0.3 to about 3, and most preferably from about 1 to about 2 silane molecules per nm 2 surface area of the colloidal silica particles.
  • Continuous addition of silane to the colloidal particles may be particularly important when preparing highly concentrated silanized silica sol dispersions having a silica content up to about 80 wt%.
  • the silica content suitably is from about 20 to about 80, preferably from about 25 to about 70, and most preferably from about 30 to about 60 wt%.
  • the colloidal silica particles and silane are mixed in a weight ratio of silane to silica of from 0.01 to 1.5, preferably from 0.05 to 1, and more preferably from 0.1 to 0.5.
  • the silane compound(s) is diluted before mixing it with the colloidal silica particles, preferably with water to form a premix of silane and water, suitably in a weight ratio of from about 1:8 to about 8:1, preferably from about 3:1 to about 1:3, and most preferably from about 1.5:1 to about 1:1.5.
  • the resulting silane-water solution is substantially clear and stable and easy to mix with the colloidal silica particles.
  • the mixing preferably continues from about 1 second to about 30 minutes, preferably from about 1 minute to about 10 minutes after the addition of silane stopped.
  • the mixing according to the invention may be carried out at a pH from about 1 to about 13, preferably from about 6 to about 12, more preferably from about 7.5 to about 11, and most preferably from about 9 to about 10.5.
  • stable particularly in the context of a “stable dispersion” is meant a stable compound, mixture or dispersion that does not substantially gel or precipitate within a period of preferably at least about 2 months, more preferably at least about 4 months, and most preferably at least about 5 months at normal storage in room temperature, i.e. at a temperature from about 15 to about 35 °C.
  • colloidal silica particles also referred to as silica sols herein, may be derived from e.g. precipitated silica, micro silica (silica fume), pyrogenic silica (fumed silica) or silica gels with sufficient purity, and mixtures thereof.
  • colloidal silica particles and silica sols according to the invention may be modified and can contain other elements such as amines, aluminium and/or boron, which can be present in the particles and/or the continuous phase.
  • Boron-modified silica sols are described in e.g. US 2,630,410 .
  • the aluminium modified silica particles suitably have an Al 2 O 3 content of from about 0.05 to about 3 wt%, preferably from about 0.1 to about 2 wt%.
  • the procedure of preparing an aluminium modified silica sol is further described in e.g. " The Chemistry of Silica", by Iler, K. Ralph, pages 407-409, John Wiley & Sons (1979 ) and in US 5 368 833 .
  • the colloidal silica particles suitably have an average particle diameter ranging from about 2 to about 150 nm, preferably from about 3 to about 50 nm, and most preferably from about 5 to about 40 nm.
  • the colloidal silica particles have a specific surface area from about 20 to about 1500, preferably from about 50 to about 900, and most preferably from about 70 to about 600 m 2 /g.
  • the colloidal silica particles preferably have a narrow particle size distribution, i.e. a low relative standard deviation of the particle size.
  • the relative standard deviation of the particle size distribution is the ratio of the standard deviation of the particle size distribution to the mean particle size by numbers.
  • the relative standard deviation of the particle size distribution preferably is lower than about 60 % by numbers, more preferably lower than about 30 % by numbers, and most preferably lower than about 15 % by numbers.
  • the colloidal silica particles are suitably dispersed in an aqueous solvent, suitably in the presence of stabilising cations such as K + , Na + , Li + , NH 4 + , organic cations, primary , secondary, tertiary, and quaternary amines, or mixtures thereof so as to form an aqueous silica sol.
  • stabilising cations such as K + , Na + , Li + , NH 4 + , organic cations, primary , secondary, tertiary, and quaternary amines, or mixtures thereof so as to form an aqueous silica sol.
  • dispersions comprising organic solvents, e.g. lower alcohols, acetone or mixtures thereof may be used, suitably in an amount of from about 1 to about 20, preferably from about 1 to about 10, and most preferably from about 1 to about 5 volume percent of the total solvent volume.
  • aqueous silica sols without any further solvents are preferably used
  • the silica sol preferably has an S-value from about 20 to about 100, more preferably from about 30 to about 90, and most preferably from about 60 to about 90.
  • the S-value characterises the extent of aggregation of colloidal silica particles, i.e. the degree of aggregate or microgel formation.
  • the S-value has been measured and calculated according to the formulas given in J. Phys. Chem. 60(1956), 955-957 by Iler, R.K. & Dalton, R.L.
  • the S-value depends on the silica content, the viscosity, and the density of the colloidal silica particles.
  • a high S-value indicates a low microgel content.
  • the S-value represents the amount of SiO 2 in percent by weight present in the dispersed phase of e.g. a silica sol.
  • the degree of microgel can be controlled during the production process as further described in e.g. US 5368833 .
  • the silane compounds can form stable covalent siloxane bonds (Si-O-Si) with the silanol groups or be linked to the silanol groups, e.g. by hydrogen bondings, on the surface of the colloidal silica particles.
  • Si-O-Si stable covalent siloxane bonds
  • the silica particles are surface-modified.
  • silanes which may be used in the present invention.
  • the most preferred silanes are epoxy silanes and silane compounds containing a glycidoxy or glycidoxypropyl group, particularly gamma-glycidoxypropyltrimethoxysilane and/or gamma glycidoxypropyltmethyldiethoxysilane.
  • the detergent comprises at least one surfactant and may include further builders, co-builders, fillers, enzymes, pH regulators, hydrophilising agents, optical brighteners, anti-dye transition agents such as e.g. CMC, bleaching chemicals such as e.g. hydrogen peroxide, activators, complexing agents, softening agents, perfumes, viscosity modifiers and other ingredients typically used in liquid detergents.
  • any detergent ingredients as mentioned in WO01/83662 ; US 6617303 , EP 929639 , WO 91/09100 or US2002/0111287 appearing in liquid detergents may also be used.
  • the detergent i.e. the total weight of the detergent ingredients is mixed to yield a total detergent content in the formed aqueous detergent dispersion of 2 to 80 wt%.
  • the total detergent content in the aqueous detergent dispersion is preferably from about 2 to about 10, most preferably from about 2 to about 5 wt%.
  • the total detergent content in the aqueous detergent dispersion is preferably from about 50 to about 80, most preferably from about 60 to about 70 wt%.
  • the total detergent content in the aqueous detergent dispersion is preferably from about 30 to about 50, most preferably from about 40 to about 50 wt%.
  • the surfactants or interface-active substances may be anionic, non-ionic, cationic, amphoteric, and/or zwitterionic surfactants.
  • Suitable anionic surfactants of the sulphonate type are preferably the known (C 9 -C 13 )-alkylbenzenesulphonates, alpha-olefinsulphonates and alkanesulphonates. Also suitable are esters of sulpho fatty acids or the disalts of alpha-sulpho fatty acids. Further suitable anionic surfactants are sulphated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as are obtained during the preparation by esterification by 1 mol of monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
  • Suitable alkyl sulphates are, in particular, the sulfuric monoesters of (C 12 -C 18 )-fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and the fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil which may additionally comprise fractions of unsaturated alcohols, e.g. oleyl alcohol.
  • anionic surfactants may for example be selected from alcohol-ethoxysulphates, alkali metal sarcosinates or alkyl ester sulfonates.
  • Suitable further anionic surfactants are, in particular, soaps.
  • Saturated fatty soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and, in particular, soap mixtures derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids, are suitable.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts, and in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Particularly preferred nonionic surfactants are alkyl alkoxylates, gluconamides and alkyl polyglycosides.
  • alkyl alkoxylates preference is given to using ethoxylated alcohols.
  • 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 or 13 EO units, (C 14 -C 15 )-alcohols having 4, 7 or 8 EO units, (C 16 -C 18 )-alcohols having 8, 11, 15, 20, 25, 50 or 80 EO units and mixtures thereof.
  • the degrees of ethoxylation given are statistical average values which may be an integer or a fractional number for a specific product.
  • fatty alcohol-EO/PO adducts such as, for example, the .RTM.Genapol grades 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.
  • alkyl glycosides of the formula RO(G) x can be used, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is a glycose unit having 5 or 6 carbon atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any desired number between 1 and 10; preferably 1.2 to 1.4.
  • Suitable cationic surfactants are quaternary ammonium compounds, cationic polymers and emulsifiers of the type used in hair care preparations and also in fabric conditioners.
  • Cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N + X - wherein R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl,
  • Ampholytic surfactants can be incorporated into the detergent dispersion. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No.
  • ampholytic surfactants can also be incorporated into the detergent dispersion. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants. Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • the builders are preferably crystalline alumino silicates, alkali metal carbonates, bicarbonates, sesquicarbonates, phosphates such as alkali metal orthophosphates, alkali metal pyrophosphates and alkali metal polyphosphates such as tripolyphosphates, ammonium, crystalline phyllosilicates, crystalline alkali metal silicates without a layer structure and/or X-ray amorphous alkali metal silicates, zeolites such as Zeolite A (e.g. Zeolite 4A), Zeolite B, Zeolite P, Zeolite X, or Zeolite HS, Zeolite MAP, silicates such as crystalline layered disilicates (e.g.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the dispersion in acid form, but can also be added in the form of a neutralized salt.
  • alkali metals such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates.
  • a number of ether polycarboxylates have been disclosed for use as detergent builders.
  • useful ether polycarboxylates include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964 , and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972 .
  • a specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula: CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A is H or OH; B is H or -O-CH(COOX)-CH 2 (COOX); and X is H or a salt-forming cation.
  • a and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts.
  • TDS tartrate disuccinic acid
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679 ; 3,835,163 ; 4,158,635 ; 4,120,874 and 4,102,903 .
  • ether hydroxypolycarboxylates represented by the structure: HO-[C(R)(COOM)-C(R)(COOM)-O] n -H wherein M is hydrogen or a cation wherein the resultant salt is water- soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C 1-4 alkyl or C 1-4 substituted alkyl (preferably R is hydrogen).
  • Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.
  • Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, and nitrilotriacetic acid.
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e. g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations, but can also be used in granular dispersions.
  • carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973 .
  • succinic acid builders include the C 5 -C 20 alkyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • Alkyl succinic acids typically are of the general formula R-CH(COOH)CH 2 (COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C 10 - C 20 alkyl or alkenyl, preferably C 12 -C 16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • R is hydrocarbon, e.g., C 10 - C 20 alkyl or alkenyl, preferably C 12 -C 16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
  • Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2- pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 0,200,263, published November 5, 1986 .
  • useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-hexane-hexacarboxylate, cis- cyclopentane-tetracarboxylate, water-soluble polyacrylates (these polyacrylates having molecular weights to above about 2,000 can also be effectively utilized as dispersants), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • polyacetal carboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979 .
  • These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
  • Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967 .
  • Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid and methylenemalonic acid.
  • organic builders known in the art can also be used.
  • monocarboxylic acids, and soluble salts thereof, having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps.” Chain lengths of C 10 -C 20 are typically utilized.
  • the hydrocarbyls can be saturated or unsaturated.
  • carboxylic acids examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), providing its use is not ecologically unsafe, and mixtures thereof.
  • Preferred salts are the salts of the polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids per se may also be used. Besides their builder effect, the acids also typically have the property of an acidifying component and, hence, also serve to establish a relatively low and mild pH value in detergents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof are particularly mentioned in this regard.
  • the hydrophilizing agents are preferably selected from ethanol, n- or i- propanol, butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or monoethyl ether, diisopropylene glycol monomethyl or monoethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2- propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, alcohols, more particularly C 1-4 alkanols, glycols, polyethylene glycols, preferably with a molecular weight of 100 to 100, 000 and more particularly in the range from
  • H 2 O 2 which is a preferred bleaching agent and compounds yielding H 2 O 2 in water which serve as bleaching agents, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are particularly important.
  • Other useful bleaching agents are, for example, persulfates and mixed salts with persulfates, such as the salts commercially available as CARAT®, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid or phthaloiminoperacids, such as phthaliminopercaproic acid.
  • Bleach systems which may be included in the detergent are preferably active chlorine carriers and/or organic or inorganic active oxygen carriers, bleach activators (e.g. TAED, TAGU, SNOBS (sodium nonoyl benzene sulphonate), PAG (penta acetyl glucose) or diacylated diperoxy carboxylic acids, bleach catalysts, enzymes for removing discolorations, perborates and/or percarbonates.
  • the pH regulators are preferably sodium carbonate, citric acid, sodium citrate and/or bicarbonate.
  • the detergent may also comprise enzymes.
  • Enzymes suitable for use in the dispersion are enzymes from the class of oxidases, proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example proteases, such as LAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase® and/or Savinase®; amylases, such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and/or Purafect® OxAm; lipases, such as Lipolase®, Lipomax®, Lumafast® and/or Lipozym®; cellulases, such as Celluzyme® and/or Carazeme®.
  • proteases such as LAP®, Optimase®, Opticlean®, Maxa
  • the invention also relates to an aqueous detergent dispersion obtainable from the method as defined herein.
  • the invention also relates to an aqueous detergent dispersion comprising silanized colloidal silica particles and a detergent as described in claim 5.
  • the detergent and the silanized silica particles are preferably homogeneously dispersed in the aqueous phase.
  • the aqueous detergent dispersion may comprise up to about 80, preferably from about 0.01 to about 20, more preferably from about 0.1 to about 10, and most preferably from about 0.3 to about 5 wt% (dry) silica.
  • the aqueous detergent dispersion has a detergent content from 2 to 80 wt%.
  • the preferred detergent contents are as described herein.
  • the stability of the dispersion facilitates the handling and application thereof in any use since it allows for storage and need not be prepared on site immediately before usage.
  • the already prepared dispersion can thus easily be directly used.
  • the dispersion is also beneficial in the sense that it does not involve hazardous amounts of toxic solvents components.
  • the dispersion is substantially aqueous dispersion.
  • a suitable organic solvent miscible with water may be comprised in the substantially aqueous dispersion in an amount from 1 to 20, preferably from 1 to 10, and most preferably from 1 to 5 volume percent of the total dispersion volume. This is due to the fact that for some applications, a certain amount of organic solvents may be present without any detrimental environmental effects.
  • the dispersion may contain besides silanized colloidal silica particles also, at least to some extent, non-silanized colloidal silica particles depending on the size of the silica particles, weight ratio of silane to silica, type of silane compound, reaction conditions etc, Suitably, at least about 40 of the colloidal silica particles are silanized (silane-modified), preferably at least about 65, more preferably at least about 90, and most preferably at least about 99 wt%.
  • the dispersion may comprise besides silane in the form of silane groups or silane derivatives bound or linked to the surface of the silica particles also at least to some extent freely dispersed unbound silane compounds.
  • At least about 40 preferably, at least about 60, more preferably at least about 75, even more preferably at least about 90, and most preferably at least about 95 wt% of the silane compounds are bound or linked to the surface of the silica particles.
  • At least about 1 % by number of the silanol surface groups on the colloidal silica particles are capable of binding or linking to silane groups on the silane compounds, preferably at least about 5 %, more preferably at least about 10 %, even more preferably at least about 30 %, and most preferably at least about 50 % bind or link to a silane group.
  • the weight ratio of the total silane content to the total silica content in the dispersion is from about 0.01 to about 1.5, more preferably from about 0.05 to about 1, and most preferably from about 0.1 to about 0.5.
  • the total content of silica comprises silica in modified silanized silica particles and non-modified silica particles which also may be present in the prepared dispersion.
  • the total content of silane is based on all freely dispersed silane and all linked or bound silane groups or derivatives.
  • the detergent dispersion can be used for the treatment of hard surfaces, but also for the treatment of fibre and textile surfaces.
  • Hard surfaces are, in particular, surfaces encountered in the home, i.e. surfaces of stone, ceramics, wood, plastics, metals, such as stainless steel, incl. floor coverings, such as carpets, etc.
  • the cleaner dispersion can be of different types; e.g. glass cleaners, all purpose cleaners, bath cleaners, kitchen cleaners etc.
  • Textile surfaces include any synthetic and natural textiles, the particles used in accordance with the invention preferably being used for the treatment of cotton and cotton/wool blends in e.g. for the pretreatment and aftertreatment of textiles and for the washing of textiles.
  • the particles may also be used for textile treatment in the textile industry, in which case they may be used both for the permanent and for the temporary treatment of textiles.
  • the detergent dispersion is preferably also used as hand dishwashing detergents, machine dishwashing detergents, machine dishwashing cleaners and rinse aids.
  • the detergent dispersion may also be further used as automobile and paint cleaners for manual use and for automatic use in car washes.
  • the detergent dispersion may also be used in anti-soil treatment for e.g. coil-coating.
  • Table 1 lists the liquid detergents used in the following examples.
  • Table 1 Liquid Detergents No Name Type - surface Content Content (%) 1 Ariel® Colour(liquid) Laundry detergent Cat+Non, So, An ⁇ 5, 5-15, 15-30 2 Ajax® Double Action Glass cleaner(pH ⁇ 8) An ⁇ 5 3 Ajax® Allrengöring APC (pH-7) An + Non + So ⁇ 5 4 DER GENERAL® APC(pH ⁇ 10) An+So, Non, H. A.
  • Table 2 lists the silica sols used in the following examples, some of which have been silane modified by addition of Silquest A-187 (gamma-glycidoxypropoxytrimethoxysilane) available from General Electric Silicones.
  • Silquest A-187 gamma-glycidoxypropoxytrimethoxysilane
  • Table 2 lists the silica sols used in the following examples, some of which have been silane modified by addition of Silquest A-187 (gamma-glycidoxypropoxytrimethoxysilane) available from General Electric Silicones.
  • Silquest A-187 gamma-glycidoxypropoxytrimethoxysilane
  • the particle size D p for each sol in table 2 is based on the specific surface area on the non-modified sol for each particle size respectively.
  • the colloidal silica dispersions as listed in table 2 were added to the liquid detergents as listed in table 1 under good agitation in accordance with table 3.
  • the amount of detergent, to which the colloidal silica dispersion is added, is 100 g if not stated otherwise.
  • the stability is controlled initially and finally after one month's storage at 55 °C for precipitation and separation (inhomogeneous sample). The stability was controlled by optical inspection.
  • Table 3 Detergent dispersions and stability No Sol Amount of added sol product (g) Detergent (as in table 1) Initial Stability Final Stability (one month, 55 °C) 1 5 1.0 1 OK precipitated* (separation) 2 8 1.0 1 OK OK** 3 5 2.0 2 precipitated --- 4 6 2.4 2 OK precipitated 5 7 2.0 2 OK OK 6 8 2.0 2 OK OK 7 5 2.0 3 precipitated --- 8 8 2.0 3 OK OK 9 9 9 3.3 4 OK precipitated (26 d, 20 °C) 10 8 3.3 4 OK OK 11 5 2.0 5 precipitated --- 12 8 2.0 5 OK OK 13 5 2.0 6 precipitated --- 14 9 10.0 6 OK precipitated 15 10 8.0 6 OK OK 16 5 10.0 7 precipitated --- 17 6 12.0 7 OK precipitated (1 day) 18 8 10.0 7 OK OK 19 12 2.0 7 OK OK 20 12 10.0 7 OK OK OK 21 6 2.4 8 precipitated --- 22 3 4.0 8 precipitated --- 23 4 2.2 8 OK OK 24 1 4.0 8 precipitated --- 25 2 5.0 8 OK
  • silane modified sols in the detergent application had the same technical effect as can be seen from table 4 below.
  • 1.5 g silica sol aqueous product was added to 100 g Ajax Double Action (glass cleaner) at good agitation at room temperature. The cleaner was then used as described in the method below.
  • Exterior windows were used in the test.
  • the detergents (with the silica sol) were sprayed onto vertical windows and the surplus was then removed by a rubber scraper.
  • the windows were let to dry for 5 minutes.
  • Standard soil (Krefeld) solution (1 %) was sprayed onto a part of the cleaned window. Water was also sprayed onto another part of the cleaned window.
  • the spread and wetting of the soil were studied (spread and soil release). The hydrophily was indicated by the wetting of the sprayed water.
  • the windows were let to dry for another 5 minutes. Water was sprayed onto the windows.
  • the soil removal was studied. As can be clearly seen in table 4, the soil removal, release, and spread of detergent dispersions 2-4 are much better than reference 1 without silica sol.

Landscapes

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

Claims (8)

  1. Verfahren zur Herstellung einer wässrigen Detergentien-Dispersion, umfassend Mischen von mindestens einer Silanverbindung und kolloidalen Kieselsäurepartikeln in einem Gewichtsverhältnis von Silan zu Kieselsäure von 0,01 bis 1,5 in einer wässrigen Dispersion, welche optional ein mit Wasser mischbares organisches Lösemittel in einer Menge von 1 bis 20 Volumenprozent des Gesamtdispersionsvolumens umfasst, um eine wässrige Dispersion silanisierter kolloidaler Kieselsäurepartikel zu bilden,
    Hinzufügen eines Detergens, das mindestens ein Tensid umfasst zu der Dispersion, um eine wässrige Detergentien-Dispersion, umfassend silanisierte kolloidale Kieselsäurepartikel zu bilden,
    wobei das Detergens in einer Menge zugegeben wird, die einen Detergentiengehalt von 2 bis 80 Gewichtsprozent in der Detergentien-Dispersion ergibt, und wobei der wässrigen Dispersion kein Organosiloxan oder Silicon zur Herstellung einer Siliconbeschichtung auf Kieselsäurepartikeln oder Silan-modifizierten Kieselsäurepartikeln beigemengt wird.
  2. Verfahren gemäß Anspruch 1, wobei die Silanverbindung ein Epoxysilan ist.
  3. Verfahren gemäß Anspruch 1 oder 2, wobei die Silanverbindung ein Epoxysilan mit einer Glycidoxy-Gruppe ist.
  4. Verfahren gemäß einem der Ansprüche 1 bis 3, wobei das Silan mit den Kieselsäurepartikeln in einem Gewichtsverhältnis von Silan zu Kieselsäure von 0,05 bis 1 gemischt wird.
  5. Wässrige Dispersion, umfassend silanisierte kolloidale Kieselsäurepartikel und ein Detergens welches zumindest ein Tensid umfasst mit einem Gehalt von 2 bis 80 Gewichtsprozent, wobei das Gewichtsverhältnis von Silan zu Kieselsäure von 0,01 bis 1,5 beträgt, wobei die silanisierten kolloidalen Kieselsäurepartikel keine Siliconbeschichtung tragen.
  6. Dispersion gemäß Anspruch 5, wobei der Kieselsäuregehalt von 0,01 bis 20 Gewichtsprozent beträgt.
  7. Verwendung der in Anspruch 5 oder 6 definierten Dispersion für Reinigungsanwendungen.
  8. Verwendung der in Anspruch 5 oder 6 definierten Dispersion für schmutzabweisende Behandlung.
EP05722230A 2004-04-08 2005-03-16 Waschmittel Not-in-force EP1733015B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05722230A EP1733015B1 (de) 2004-04-08 2005-03-16 Waschmittel

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04445047 2004-04-08
EP05722230A EP1733015B1 (de) 2004-04-08 2005-03-16 Waschmittel
PCT/SE2005/000384 WO2005097961A1 (en) 2004-04-08 2005-03-16 Detergent composition

Publications (2)

Publication Number Publication Date
EP1733015A1 EP1733015A1 (de) 2006-12-20
EP1733015B1 true EP1733015B1 (de) 2010-06-16

Family

ID=34932980

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05722230A Not-in-force EP1733015B1 (de) 2004-04-08 2005-03-16 Waschmittel

Country Status (11)

Country Link
EP (1) EP1733015B1 (de)
JP (1) JP4970246B2 (de)
CN (1) CN1938413B (de)
AT (1) ATE471365T1 (de)
AU (1) AU2005230956B2 (de)
BR (1) BRPI0509106B1 (de)
CA (1) CA2562256C (de)
DE (1) DE602005021868D1 (de)
ES (1) ES2347447T3 (de)
TW (1) TWI304093B (de)
WO (1) WO2005097961A1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2154111A1 (de) 2008-07-10 2010-02-17 Cognis IP Management GmbH Wasserlösliche Silikate und deren Verwendung
WO2012012349A2 (en) * 2010-07-17 2012-01-26 Enginuity Worldwide, LLC Novel methods for improving surface characteristics
EP2652106B1 (de) 2010-12-16 2019-10-09 Nouryon Chemicals International B.V. Entfettungsmittel mit niedriger streifenbildung
WO2013064358A1 (en) 2011-11-01 2013-05-10 Unilever N.V. Glass cleaner
JP6316574B2 (ja) * 2013-11-21 2018-04-25 アズビル株式会社 粒子検出装置及び粒子の検出方法
JP6316573B2 (ja) * 2013-11-21 2018-04-25 アズビル株式会社 粒子検出装置及び粒子の検出方法
CN103666874A (zh) * 2013-11-22 2014-03-26 南通信一服饰有限公司 一种织物用油漆清洗剂
CN107418784A (zh) * 2017-05-30 2017-12-01 花舜 一种多用途洗涤剂

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2920045A (en) * 1955-09-06 1960-01-05 Colgate Palmolive Co Heavy duty liquid detergent compositions
DE3607674A1 (de) * 1986-03-08 1987-09-17 Henkel Kgaa Verfahren zur herstellung eines entschaeumergemisches
JPH10310406A (ja) * 1997-03-12 1998-11-24 Catalysts & Chem Ind Co Ltd 有機化合物修飾無機化合物ゾル
US6015843A (en) * 1998-01-14 2000-01-18 Dendreon Corporation Process for making silanized colloidal silica
DE10061897A1 (de) * 2000-12-12 2002-06-13 Clariant Gmbh Wasch- und Reinigungsmittel, enthaltend mikrodisperse silikathaltige Partikel
EP1383860B1 (de) * 2001-04-30 2005-10-12 Unilever Plc Zusammensetzungen zur textilpflege

Also Published As

Publication number Publication date
EP1733015A1 (de) 2006-12-20
BRPI0509106B1 (pt) 2016-07-26
CA2562256A1 (en) 2005-10-20
AU2005230956B2 (en) 2008-02-14
CA2562256C (en) 2012-05-29
ES2347447T3 (es) 2010-10-29
BRPI0509106A (pt) 2007-08-28
WO2005097961A1 (en) 2005-10-20
AU2005230956A1 (en) 2005-10-20
JP4970246B2 (ja) 2012-07-04
CN1938413B (zh) 2010-06-23
TW200535237A (en) 2005-11-01
ATE471365T1 (de) 2010-07-15
DE602005021868D1 (de) 2010-07-29
CN1938413A (zh) 2007-03-28
TWI304093B (en) 2008-12-11
JP2007532713A (ja) 2007-11-15

Similar Documents

Publication Publication Date Title
EP1733015B1 (de) Waschmittel
US20210355253A1 (en) Itaconic acid polymers
EP3116924B1 (de) Itaconsäurepolymere und -copolymere
KR101891228B1 (ko) 낮은 스트리크 탈지 조성물
US6784149B2 (en) Laundry detergents and cleaners comprising microdisperse silicate-containing particles
JPH10507788A (ja) 低起泡性液体洗剤組成物
US8361946B2 (en) Detergent composition
CN1120231C (zh) 涉及预混修饰的聚胺制备洗涤剂组合物的喷雾干燥法
US10822506B2 (en) Methods and formulations for paint deposit removal
JPH07501564A (ja) 粉末形態の界面活性剤混合物
JP2007511647A (ja) 溶解性ビルダー系
JPH069999A (ja) 非イオン性粉末洗浄剤組成物
JP4188222B2 (ja) 漂白洗浄剤組成物
JPH11181484A (ja) 洗浄剤組成物
MXPA97005986A (en) Compositions of automatic washing of dishes that include catalysts of cobalt quelata

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: 20061006

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 IS IT LI LT LU MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20070420

DAX Request for extension of the european patent (deleted)
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 IS IT LI LT LU MC NL PL PT RO SE SI SK TR

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

REF Corresponds to:

Ref document number: 602005021868

Country of ref document: DE

Date of ref document: 20100729

Kind code of ref document: P

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

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

Ref country code: LT

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: 20100616

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2347447

Country of ref document: ES

Kind code of ref document: T3

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20100616

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: 20100616

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: 20100616

Ref country code: AT

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: 20100616

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

Ref country code: PL

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: 20100616

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: 20100616

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: 20100917

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

Ref country code: EE

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

Effective date: 20100616

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

Ref country code: IS

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: 20101016

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: 20100616

Ref country code: BE

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: 20100616

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: 20100616

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: 20100616

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: 20101018

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: 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: 20100616

26N No opposition filed

Effective date: 20110317

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602005021868

Country of ref document: DE

Effective date: 20110316

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: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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 NON-PAYMENT OF DUE FEES

Effective date: 20110316

Ref country code: LI

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

Effective date: 20110331

Ref country code: CH

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: LU

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

Effective date: 20110316

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

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: 20100916

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: 20100616

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: 20100616

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

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

Ref country code: NL

Payment date: 20170326

Year of fee payment: 13

Ref country code: SE

Payment date: 20170329

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602005021868

Country of ref document: DE

Representative=s name: VOSSIUS & PARTNER PATENTANWAELTE RECHTSANWAELT, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 602005021868

Country of ref document: DE

Owner name: AKZO NOBEL CHEMICALS INTERNATIONAL B.V., NL

Free format text: FORMER OWNER: AKZO NOBEL N.V., 6824 ARNHEIM/ARNHEM, NL

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: AKZO NOBEL CHEMICALS INTERNATIONAL B.V.

Effective date: 20180122

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20180111 AND 20180117

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Owner name: AKZO NOBEL CHEMICALS INTERNATIONAL B.V., NL

Effective date: 20180515

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

Ref country code: SE

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

Effective date: 20180317

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20180401

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

Ref country code: NL

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

Effective date: 20180401

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

Ref country code: GB

Payment date: 20220328

Year of fee payment: 18

Ref country code: DE

Payment date: 20220329

Year of fee payment: 18

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

Ref country code: IT

Payment date: 20220322

Year of fee payment: 18

Ref country code: FR

Payment date: 20220325

Year of fee payment: 18

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

Ref country code: ES

Payment date: 20220401

Year of fee payment: 18

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602005021868

Country of ref document: DE

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

Effective date: 20230316

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

Ref country code: GB

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

Effective date: 20230316

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

Ref country code: GB

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

Effective date: 20230316

Ref country code: FR

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

Effective date: 20230331

Ref country code: DE

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

Effective date: 20231003

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: 20230316

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20240430