EP1979453B1 - Produit liquide de lavage ou de nettoyage contenant un agent blanchissant a base de peracide sous forme de particules - Google Patents

Produit liquide de lavage ou de nettoyage contenant un agent blanchissant a base de peracide sous forme de particules Download PDF

Info

Publication number
EP1979453B1
EP1979453B1 EP06819915A EP06819915A EP1979453B1 EP 1979453 B1 EP1979453 B1 EP 1979453B1 EP 06819915 A EP06819915 A EP 06819915A EP 06819915 A EP06819915 A EP 06819915A EP 1979453 B1 EP1979453 B1 EP 1979453B1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
surfactants
agent according
acids
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
EP06819915A
Other languages
German (de)
English (en)
Other versions
EP1979453A1 (fr
Inventor
Peter Schmiedel
Luca Bellomi
Wolfgang Von Rybinski
Bernhard Orlich
Hermann Jonke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=37863686&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1979453(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL06819915T priority Critical patent/PL1979453T3/pl
Publication of EP1979453A1 publication Critical patent/EP1979453A1/fr
Application granted granted Critical
Publication of EP1979453B1 publication Critical patent/EP1979453B1/fr
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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • the present patent application relates to hydrous liquid detergents or cleaners which contain peroxycarboxylic acid particles.
  • phthalimidoperoxoalkanoic acids such as 6-phthalimidoperoxohexanoic acid (PAP) are highly efficient bleaches, but are chemically very unstable in conventional liquid detergent formulations. In most cases, they completely decompose in a few days. Even if these liquid agents are freed from possible reactants of the peroxycarboxylic acid, such as unsaturated compounds, aldehydes, amines, chloride, etc., they still decompose in the presence of the surfactants, even if they are not oxidatively attacked.
  • PAP 6-phthalimidoperoxohexanoic acid
  • phthalimidoperoxoalkanoic acids are stable as only slightly water-soluble solids, they dissolve in the presence of surfactants, are highly reactive in this form, and are soluble in solution both via a bimolecular reaction with elimination of singlet oxygen and through hydrolysis the Phthalimidoalkanklare and H 2 O 2 decompose.
  • the latter is practically not at low washing temperatures and in the concentrations occurring bleach active, so that in total the bleaching action of the agent is lost during storage.
  • EP 0 890 635 A2 Surfactant-containing liquid compositions are known which contain unimpregnated phthalimidoperoxohexanoic acid umd a maximum of 4 wt .-% magnesium sulfate.
  • GB 2 281 744 A describes acidic liquid bleaches containing surfactants, uncovered amido-peracid, xanthan gum and a pH-jump system, and optionally magnesium sulfate.
  • EP 0 504 952 A1 The opinion is expressed that magnesium sulfate increases the water solubility of amido peracids by Mg salt formation.
  • EP 0 240 481 A1 liquid bleaches containing alkanediperoxyacids, linear alkylbenzenesulfonate and magnesium sulfate are known.
  • EP 0 435 379 A1 describes imidoperoxycarboxylic acids which are coated with water-impermeable materials and which can be used in liquid agents, wherein they are stabilized in them by alkali alkylbenzenesulfonates.
  • a problem with such formulations with, for example, sodium sulfate is the phase stability and the storage stability, especially under climatic changing conditions. Under alternating climate, the solubility of the sodium sulfate changes very strongly, which can lead to precipitation and the growth of partially very large sulfate crystals in the liquid agents. In addition, the flow behavior of these agents is satisfactory and the production is complicated in practice, since also during the Manufacturing process due to the hydrate formation of sodium sulfate can first form large crystals that do not dissolve again in the thickened recipe.
  • Another approach to stabilize the bleaching agent is to coat it. It has been found, however, that the mere application of coating materials by no means always leads to an increase in the stability of the PAP. Coating, even with chemically inert materials such as paraffin in the systems under consideration, often even destabilizes the PAP. A coating that should be soluble in the application of the agent, usually in a water-containing product not completely diffusion-tight against water. Thus, although such a coating may possibly suppress the dissolution of the PAP, it does not suppress its hydrolysis to H 2 O 2.
  • the present invention which aims to contribute to this, is an aqueous surfactant and bleach-containing liquid washing or cleaning agent having a particulate peroxycarboxylic acid and characterized in that it is the peroxycarboxylic acid which is solid at room temperature and which is a phthalimidoperoxoalkanoic acid Form and from over 4 wt .-% to 30 wt .-% magnesium sulfate.
  • Magnesium sulfate may be present in compositions of the invention in amounts up to 30% by weight. Preferably, amounts in the range of about 4 wt .-% to 20 wt.%, In particular in the range of 6 wt .-% to 10 wt.%. Magnesium sulfate may optionally also be used in mixtures with sodium and / or potassium sulfate.
  • compositions according to the invention is preferably between 2 and 6, in particular between 3 and 5.5 and more preferably between 3.5 and 5.
  • water in inventive compositions can be added in amounts of up to 90% by weight, in particular 20% by weight. % to 75 wt .-%, be included; if necessary, however, these areas can also be exceeded or fallen short of.
  • the content of peroxycarboxylic acid in the compositions according to the invention is preferably 1% by weight to 25% by weight, in particular 2% by weight to 20% by weight and especially preferably 3% to 15% by weight.
  • 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid and mixtures of these come into consideration.
  • Preferred peracids include 6-phthalimidoperoxohexanoic acid (PAP).
  • the Peroxocarbonchureteilchen contained in the agent according to the invention are coated. It is important that the coating material dissolves as little as possible in the liquid surrounding the coated Peroxocarbonchureteilchen, but under the conditions of use of the agent (at higher temperature, by dilution with water changing pH, or the like) releases the coated peroxycarboxylic acid.
  • a preferred coating material is one which consists, at least in part, of saturated fatty acid.
  • the chain length of the fatty acid is preferably greater than C 12 , particularly preferred is stearic acid. It has been found that, especially at low pH, the stability of PAP is very good, so that a coating for stabilizing the PAP may be unnecessary.
  • a coating of the peroxycarboxylic acid stabilizes enzymes when they are contained in an agent according to the invention. In particular, in the presence of enzymes, therefore, a PAP coating is advantageous.
  • a wrapping material is preferably applied to the particulate peroxycarboxylic acid in amounts such that the coated peroxycarboxylic acid particles consist of from 5% to 50% by weight of the wrapping material.
  • the diameters of the coated PeroxocarbonTexreteilchen are preferably in Range from 100 ⁇ m to 1000 ⁇ m; Therefore, it starts from correspondingly finely divided Peroxocarbonchurematerial and covers it with the wrapping material.
  • the procedure is to spray a fluidized bed of the peroxycarboxylic acid particles to be coated with a solution or slurry, preferably an aqueous solution, or a melt of the coating material, if present, removing the solvent or slurry, preferably water, by evaporation or solidified melted wrapping material by cooling and discharges the coated PeroxocarbonTalkreteilchen in a conventional manner from the fluidized bed.
  • a solution or slurry preferably an aqueous solution, or a melt of the coating material, if present
  • removing the solvent or slurry preferably water
  • preference is given to melt-coating.
  • a liquid detergent or cleaning agent according to the invention may contain all conventional ingredients in such agents, such as solvents, builders, enzymes and other auxiliaries such as soil repellants, thickeners, dyes and perfumes or the like.
  • it contains nonionic surfactants and / or organic solvents and optionally anionic surfactants, cationic surfactants and / or amphoteric surfactants.
  • Surfactants of the sulfonate type, alk (en) ylsulfates, alkoxylated alk (en) ylsulfates, ester sulfonates and / or soaps are preferably used as anionic surfactants.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, such as those from C 12 -C 18 monoolefins having terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 10 -C 18 fatty alcohols, for example of coconut fatty alcohol, Tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 8 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis.
  • C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates and C 14 -C 16 -alkyl sulfates are particularly preferred.
  • 2,3-alkyl sulfates which may for example be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 Fatty alcohols containing 1 to 4 EO are suitable. Due to their high foaming behavior, they are usually used in detergents only in relatively small amounts, for example in amounts of from 0 to 5% by weight.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • anionic surfactants are particularly soaps into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, for. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100 wt .-% of saturated C 12 -C 14 fatty acid soaps and 0 to 50 wt .-% of oleic acid soap.
  • Ethercarboxylic acids are water hardness insensitive and have excellent surfactant properties.
  • Cationic surfactants contain the surface activity of the high molecular weight hydrophobic residue upon dissociation in aqueous solution in the cation.
  • R 1 is C 1 -C 8 -alk (en) yl
  • R 2 to R 4 are each independently C n H 2n + 1-px - (Y 1 (CO) R 5 ) p - (Y 2 H) x
  • n stands for integers without 0 and p and x stand for integers or 0.
  • Y 1 and Y 2 are each independently O, N or NH.
  • R 5 denotes a C 3 -C 23 -alk (en) yl chain.
  • X is a counterion, which is preferably selected from the group of alkyl sulfates and alkyl carbonates. Particularly preferred are cationic surfactants in which the nitrogen group is substituted by two long acyl and two short alk (en) yl radicals.
  • Amphoteric or ampholytic surfactants have a plurality of functional groups which can ionize in aqueous solution and thereby - depending on the conditions of the medium - give the compounds anionic or cationic character. Near the isoelectric point, the amphoteric surfactants form internal salts, rendering them difficult or insoluble in water. Amphoteric surfactants are subdivided into ampholytes and betaines, the latter being present in solution as zwitterions. Ampholytes are amphoteric electrolytes, ie, compounds that have both acidic and basic hydrophilic groups and thus behave acidic or basic depending on the condition. Betaines are compounds with the atomic group R 3 N + -CH 2 -COO - which show typical properties of zwitterions.
  • the nonionic surfactants used are preferably alkoxylated and / or propoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol.
  • EO ethylene oxide
  • PO propylene oxide
  • C 8 -C 16 -alcohol alkoxylates advantageously ethoxylated and / or propoxylated C 10 -C 15 -alcohol alkoxylates, in particular C 12 -C 14 -alcohol alkoxylates, having a degree of ethoxylation of between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5.
  • the stated degrees of ethoxylation and propoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
  • Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP). additionally Fatty alcohols with more than 12 EO can also be used for these nonionic surfactants. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x , z. B. as compounds, especially with anionic surfactants, are used, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.1 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.
  • Particularly preferred are C 12 -C 18 fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer". This spacer is usually a carbon chain which should be long enough for the hydrophilic groups to have a carbon chain have enough distance to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates.
  • End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality.
  • the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.
  • the amount of surfactants present in the agents according to the invention is preferably 0.1% by weight to 50% by weight, in particular 10% by weight to 40% by weight, and particularly preferably 20% by weight to 70% by weight. -%.
  • Polydiols, ethers, alcohols, ketones, amides and / or esters in amounts of from 0 to 90% by weight, preferably 0.1 to 70% by weight, in particular 0.1 to 60% by weight, may preferably be used as organic solvents. %, in each case based on the amount of water available. Preference is given to low molecular weight polar substances, such as, for example, methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof.
  • polar substances such as, for example, methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol,
  • Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these Hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.
  • the proportion of enzymes or enzyme mixtures may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 3 wt .-%. They are preferably used in preparations according to the invention in particulate form.
  • Further detergent ingredients may be builders, cobuilders, soil repellents, alkaline salts and foam inhibitors, complexing agents, enzyme stabilizers, grayness inhibitors, optical brighteners and UV absorbers.
  • fine crystalline, synthetic and bound water-containing zeolite can be used, preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite may preferably be used as a spray-dried powder.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates can also be used as builders.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x-1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” also "X-ray amorphous" understood.
  • the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle.
  • the silicate particles may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments.
  • densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are especially preferred.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.
  • Their content is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished agent.
  • tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing power.
  • Preferred amounts of phosphates are below 10 wt .-%, especially at 0 wt .-%.
  • Suitable organic builder substances which are useful as co-builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Further useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.
  • Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as an aqueous solution or, preferably, as a powder.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100.
  • DE dextrose equivalent
  • Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol are useful.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. These are products oxidized at C 6 and / or with ring opening at C 2 / C 3 of the saccharide ring. A product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • compositions may also contain components which positively influence the oil and Fettauswaschles from textiles, so-called soil repellents. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, and known from the prior art polymers phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes.
  • the salts of polyphosphonic come into consideration.
  • the sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, but also diethylene triamine penta methylene phosphonate or ethylenediamine tetramethylene phosphonate are preferably used in amounts of from 0.1% to 5% by weight of the composition. Preference is given to nitrogen-free complexing agents.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of (co) polymeric carboxylic acids, glue, gelatin, salts of ethercarboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, for. Degraded starch, aldehyde levels, etc. Also, polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, Hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of 0.1 to 5 wt.%, Based on the means used.
  • the funds can optical brighteners such.
  • brighteners of the substituted diphenylstyrene type may be present, e.g.
  • UV absorbers can also be used. These are compounds with pronounced ultraviolet radiation absorptivity which contribute to improving the light fastness of dyes and pigments as well as textile fibers as light stabilizers (UV stabilizers) and also protect the wearer's skin from textile exposure to UV radiation.
  • the compounds which are active by radiationless deactivation are derivatives of benzophenone whose substituents, such as hydroxyl and / or alkoxy groups, are usually in the 2- and / or 4-position.
  • substituted benzotriazoles are also suitable, furthermore in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic nickel complexes and natural products such as umbelliferone and the body's own urocanic acid.
  • the UV absorbers absorb UV-A and UV-B radiation and optionally UV-C radiation and radiate back with wavelengths of blue light, so that they additionally have the effect of an optical brightener.
  • Preferred UV absorbers are also triazine derivatives, eg. B.
  • UV absorbers can also be used to absorb ultraviolet radiation pigments such as titanium dioxide.
  • compositions may contain further conventional thickeners and anti-settling agents and also viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamines and any desired mixtures thereof.
  • viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamines and any desired mixtures thereof.
  • Preferred agents have a viscosity between 100 and 10,000 mPa.s when measured with a Brookfield viscometer at a temperature of 20 ° C and a shear rate of 20 min -1 .
  • compositions may contain other typical detergent and cleaner components such as perfumes and / or dyes, preference being given to those dyes which have no or negligible coloring action on the textiles to be washed.
  • Preferred quantitative ranges of the totality of the dyes used are less than 1% by weight, preferably less than 0.1% by weight, based on the agent.
  • the agents may optionally also white pigments such.
  • Preferred agents have densities of 0.5 to 2.0 g / cm 3 , in particular 0.7 to 1.5 g / cm 3 , on.
  • the density difference between the PeroxocarbonTexreteilchen and the liquid phase of the composition is preferably not more than 10% of the density of the two and is particularly so low that the PeroxocarbonTexreteilchen and preferably also optionally other suspended in the funds solid particles float in the liquid phase.
  • Example 1 Preparation of an agent according to the invention
  • An agent V1 was otherwise prepared as in Example 1, but containing no magnesium sulfate (replaced by water).
  • An agent V2 was otherwise prepared as in Example 1, but magnesium sulfate was replaced with the same amount of sodium sulfate.
  • the agents of Examples 1 to 3 were evaluated for phase stability and bleach loss.
  • the characterization was carried out after a storage period of 1 week under changing climatic conditions (temperature cycles between 25 ° C and 40 ° C) and constant 35 ° C.
  • V1 showed unacceptable bleach loss.
  • V2 showed crystal formation and phase instability under alternating climate storage conditions. The benefits of E1 outweigh.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)

Claims (9)

  1. Agent de lavage ou de nettoyage liquide aqueux contenant un agent tensioactif et un agent de blanchiment, qui présente un acide peroxocarboxylique particulaire, caractérisé en ce qu'il contient l'acide peroxocarboxylique solide à la température ambiante, qui représente un acide phtalimidoperoxoalcanoïque, sous forme enrobée et du sulfate de magnésium en une quantité de plus de 4 % en poids à 30 % en poids.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient de 1 % en poids à 25 % en poids d'acide peroxocarboxylique, en particulier de 2 % en poids à 20 % en poids.
  3. Agent selon la revendication 1 ou 2, caractérisé en ce que l'acide peroxocarboxylique est l'acide 6-phtalimidoperoxohexanoïque (PAP).
  4. Agent selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il contient jusqu'à 20 % en poids, du sulfate de magnésium.
  5. Agent selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il contient de 6 % en poids à 10 % en poids de sulfate de magnésium.
  6. Agent selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il contient de 0,1 % en poids à 50 % en poids d'agent tensioactif, en particulier de 10 % en poids à 40 % en poids.
  7. Agent selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'il contient un mélange d'agents tensioactifs anioniques et non ioniques.
  8. Agent selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il présente une valeur de pH dans la plage de 2 à 6, en particulier entre 3 et 5,5.
  9. Agent selon l'une quelconque des revendications 1 à 8, caractérisé en ce que les densités des particules d'acide peroxocarboxylique le cas échéant enrobées et de la phase liquide de l'agent ne s'écartent pas l'une de l'autre à concurrence de plus de 10 %.
EP06819915A 2005-12-30 2006-12-06 Produit liquide de lavage ou de nettoyage contenant un agent blanchissant a base de peracide sous forme de particules Not-in-force EP1979453B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06819915T PL1979453T3 (pl) 2005-12-30 2006-12-06 Ciekły środek piorący lub czyszczący ze środkiem bielącym spośród kwasu nadtlenowego w postaci cząstek

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005063180A DE102005063180A1 (de) 2005-12-30 2005-12-30 Flüssiges Wasch- oder Reinigungsmittel mit teilchenförmigem Persäure-Bleichmittel
PCT/EP2006/069384 WO2007077088A1 (fr) 2005-12-30 2006-12-06 Produit liquide de lavage ou de nettoyage contenant un agent blanchissant a base de peracide sous forme de particules

Publications (2)

Publication Number Publication Date
EP1979453A1 EP1979453A1 (fr) 2008-10-15
EP1979453B1 true EP1979453B1 (fr) 2012-03-07

Family

ID=37863686

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06819915A Not-in-force EP1979453B1 (fr) 2005-12-30 2006-12-06 Produit liquide de lavage ou de nettoyage contenant un agent blanchissant a base de peracide sous forme de particules

Country Status (7)

Country Link
EP (1) EP1979453B1 (fr)
JP (1) JP2009522386A (fr)
AT (1) ATE548442T1 (fr)
DE (1) DE102005063180A1 (fr)
ES (1) ES2382388T3 (fr)
PL (1) PL1979453T3 (fr)
WO (1) WO2007077088A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011005917A1 (fr) * 2009-07-09 2011-01-13 The Procter & Gamble Company Procédé de blanchissage de tissus à l'aide d'une composition liquide de détergent pour le linge
US20180362892A1 (en) * 2017-06-20 2018-12-20 The Procter & Gamble Company Systems comprising a bleaching agent and encapsulates
DE102018213192A1 (de) * 2018-08-07 2020-02-13 Henkel Ag & Co. Kgaa Flüssiges bleichmittelvorläuferhaltiges Wasch- oder Reinigungsmittel

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU600263B2 (en) * 1986-03-31 1990-08-09 Procter & Gamble Company, The Stable liquid diperoxyacid bleach
US5073285A (en) * 1989-06-12 1991-12-17 Lever Brothers Company, Division Of Conopco, Inc. Stably suspended organic peroxy bleach in a structured aqueous liquid
EP0435379A3 (en) * 1989-12-22 1991-07-31 Akzo N.V. Suspension, coating, agglomeration and uses of imidoperoxycarboxylic acids
EP0504952A1 (fr) * 1991-02-15 1992-09-23 The Procter & Gamble Company Agent de blanchiment liquide stable à base d'acide peroxyamidique
CA2126382C (fr) * 1993-06-30 1998-12-15 Josephine L. Kong-Chan Compositions de detersifs a lessive aqueuses liquides et stables contenant du peroxyacide comme agent de blanchiment
IT1293587B1 (it) * 1997-07-08 1999-03-08 Manitoba Italia Spa Composizioni a base di acidi percarbossilici come smacchianti e igienizzanti

Also Published As

Publication number Publication date
JP2009522386A (ja) 2009-06-11
PL1979453T3 (pl) 2012-08-31
ES2382388T3 (es) 2012-06-07
WO2007077088A1 (fr) 2007-07-12
ATE548442T1 (de) 2012-03-15
EP1979453A1 (fr) 2008-10-15
DE102005063180A1 (de) 2007-07-05

Similar Documents

Publication Publication Date Title
EP1735422B2 (fr) Particules d'agent de blanchiment a enrobage soluble dans l'eau
EP1735423B1 (fr) Nettoyant ou detergent liquide a agent de blanchiment enrobe d'un materiau soluble dans l'eau
DE19956382A1 (de) Verfahren zur Herstellung von mikroverkapselten Enzymen
US20090018045A1 (en) Liquid Washing or Cleaning Composition Comprising Particulate Peracid Bleach
EP2132288B1 (fr) Composition détergente contenant un agent de blanchiment
DE102007028509A1 (de) Flüssiges, hochschäumendes Wasch- oder Reinigungsmittel mit stabiler Viskosität
DE19954831A1 (de) Tensid-haltige Wasch- und Reinigungsmittel
EP1979453B1 (fr) Produit liquide de lavage ou de nettoyage contenant un agent blanchissant a base de peracide sous forme de particules
EP2007864B1 (fr) Particules enrobées d'acide imidoperoxocarboxylique
DE102007005419A1 (de) Enzym-haltiges Wasch- oder Reinigungsmittel mit verbesserter Stabilität
WO2000078676A1 (fr) Utilisation de silicates stratifies actifs dans des detergents liquides non aqueux
DE102006034902A1 (de) Wasch- oder Reinigungsmittel mit verbessertem Dispergievermögen
DE19953870A1 (de) Verfahren zur Herstellung einer wasserarmen Enzymzubereitung
WO2009056447A1 (fr) Agent de lavage ou détergent sous forme liquide contenant un agent de blanchiment
DE102004018787A1 (de) Bleichmittelhaltiges flüssiges Wasch- oder Reinigungsmittel
DE19961660A1 (de) Pflegemittel für Wasch- und Geschirrspülmaschinen
EP2108038B1 (fr) Lessive ou détergent à viscosité stable
EP2716747A1 (fr) Mélange des agents tensioactifs tres performant et composition detergente le contenant
DE102007016709A1 (de) Bleichmittelhaltiges Wasch- oder Reinigungsmittel
DE102007057351A1 (de) Bleichmittelhaltiges Wasch- oder Reinigungsmittel
EP3578629B1 (fr) Procédé de fabrication d'un agent de lavage ou de nettoyage liquide contenant une solution de substance colorante sans agent conservateur
DE102008050091A1 (de) Bleichmittelhaltiges Wasch- oder Reinigungsmittel
EP1113067B1 (fr) Préparation contenant des tensioactifs
DE10123622A1 (de) Verfahren zur Herstellung von Tensidgranulaten
DE19722767A1 (de) Wasch- oder Reinigungsmittel mit erhöhter Reinigungsleistung

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: 20080322

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 LV MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20091229

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
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 LV MC NL PL 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

Ref country code: AT

Ref legal event code: REF

Ref document number: 548442

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120315

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502006011098

Country of ref document: DE

Effective date: 20120503

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2382388

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20120607

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120307

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120307

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: 20120307

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20120307

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: 20120608

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: 20120307

Ref country code: LV

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: 20120307

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

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

Ref country code: CY

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

Effective date: 20120307

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: 20120707

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: 20120307

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: 20120307

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: 20120307

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: 20120307

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: 20120307

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: 20120709

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: RECKITT BENCKISER N.V.

Effective date: 20121207

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: 20120307

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502006011098

Country of ref document: DE

Effective date: 20121207

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

BERE Be: lapsed

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

Effective date: 20121231

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: 20121231

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: 20120607

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: 20121206

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: BE

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

Effective date: 20121231

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: 20121231

Ref country code: IE

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

Effective date: 20121206

Ref country code: LI

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

Effective date: 20121231

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: 20121206

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 548442

Country of ref document: AT

Kind code of ref document: T

Effective date: 20121206

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: 20120307

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: 20121206

Ref country code: AT

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

Effective date: 20121206

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: 20061206

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 502006011098

Country of ref document: DE

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

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

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20141006

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 502006011098

Country of ref document: DE

Effective date: 20141006

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

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

Ref country code: CZ

Payment date: 20181204

Year of fee payment: 13

Ref country code: DE

Payment date: 20181210

Year of fee payment: 13

Ref country code: PL

Payment date: 20181123

Year of fee payment: 13

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

Ref country code: FR

Payment date: 20181220

Year of fee payment: 13

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

Ref country code: IT

Payment date: 20181220

Year of fee payment: 13

Ref country code: ES

Payment date: 20190123

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502006011098

Country of ref document: DE

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

Ref country code: CZ

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

Effective date: 20191206

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

Ref country code: DE

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

Effective date: 20200701

Ref country code: FR

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

Effective date: 20191231

Ref country code: IT

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

Effective date: 20191206

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20210601

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: 20191207

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 NON-PAYMENT OF DUE FEES

Effective date: 20191206