EP2291504B1 - Additif de detergents se presentant sous forme de particules - Google Patents

Additif de detergents se presentant sous forme de particules Download PDF

Info

Publication number
EP2291504B1
EP2291504B1 EP09772258A EP09772258A EP2291504B1 EP 2291504 B1 EP2291504 B1 EP 2291504B1 EP 09772258 A EP09772258 A EP 09772258A EP 09772258 A EP09772258 A EP 09772258A EP 2291504 B1 EP2291504 B1 EP 2291504B1
Authority
EP
European Patent Office
Prior art keywords
water
microcapsules
perfume
particles
particles according
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.)
Revoked
Application number
EP09772258A
Other languages
German (de)
English (en)
Other versions
EP2291504A1 (fr
Inventor
Matthias Sunder
Mario Sturm
Tobias Segler
Noelle Wrubbel
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=40874847&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2291504(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 PL09772258T priority Critical patent/PL2291504T3/pl
Publication of EP2291504A1 publication Critical patent/EP2291504A1/fr
Application granted granted Critical
Publication of EP2291504B1 publication Critical patent/EP2291504B1/fr
Revoked 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the present invention relates to particles suitable for use in detergents, cleaners and personal care products which have a water-soluble or water-dispersible carrier and active-ingredient-containing microcapeins. Furthermore, it relates to a process for the preparation of such particles as well as washing, cleaning or care agents containing such particles. Finally, it also relates to the use of such in textile laundering or textile treatment.
  • the consumer In the textile laundry, the consumer generally pursues not only the goal of freeing the laundry for hygienic and visual reasons of soiling, but he also wants an added value that goes beyond the mere textile cleaning. This added value can e.g. The reason for this is that the textiles may smell good after washing or that the textiles are cared for during washing so that e.g. a softer feel of the textile results.
  • the WO 2005/059083 A1 discloses coated granules having a functional core whose coating contains encapsulated perfumes.
  • a particle according to claim 1 suitable for use in washing, cleaning or care products, comprising a water-soluble or water-dispersible carrier and active substance-containing microcapsules.
  • Microcapsules as such are known.
  • the diameter of usable microcapsules are in the range of a few nanometers to millimeters.
  • solid and / or liquid active substances are included in the microcapsules according to the invention.
  • Suitable materials for the capsules are usually high molecular weight compounds such as protein compounds (eg., Gelatin, albumin, casein and others), cellulose derivatives (eg methylcellulose, ethylcellulose, cellulose acetate, cellulose nitrate, carboxymethylcellulose and others) and especially synthetic Polymers (eg polyamides, polyethylene glycols, polyurethanes, epoxy resins and others). More details will be given later.
  • microencapsulation in particular as the encapsulation of liquid or solid phases by coating with film-forming (eg the abovementioned) polymers which, after emulsification and coacervation or interfacial polymerization, are to be enveloped on the surface to be enveloped
  • film-forming eg the abovementioned
  • Precipitate material Active-ingredient-containing microcapsules, e.g. fragrance-containing microcapsules are widely available commercially.
  • the particles of the invention can be used in particular in the main wash of an automatic washing or cleaning process, in particular as an additive to be dosed in addition to a normal washing or cleaning agent or as an integral part of a detergent or cleaning agent.
  • the particles can be added, for example, together with the detergent or cleaning agent in the drum or the dispenser of a washing machine.
  • the active ingredients contained in the microcapsules help to achieve the added value to be realized, which goes beyond the mere cleaning of the textiles.
  • this added value can be manifested in particular in an improved textile scenting, in an improved textile care and / or even in the effecting of cosmetic skin care effects, depending on the choice of the active ingredients implemented.
  • a particle according to the invention comprises, in addition to microcapsules as an essential ingredient, a water-soluble or water-dispersible carrier.
  • the water-soluble or water-dispersible carrier comprises carbohydrates, in particular selected from dextrose, fructose, galactose, isoglucose, glucose, sucrose, raffinose or mixtures thereof, other water-soluble or water-dispersible carriers, material (s) include inorganic alkali metal salts, organic alkali metal salts, inorganic alkaline earth metal salts, organic alkaline earth metal. metal salts, organic acids, silicates, urea or mixtures thereof.
  • Such support materials are not only inexpensive, but usually dissolve very well in water. In addition, these materials are odorless.
  • Suitable materials include inorganic alkali metal salts such as sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium bicarbonate, potassium bicarbonate or mixtures thereof, organic alkali metal salts such as sodium acetate, potassium acetate, sodium citrate, sodium tartrate or potassium sodium tartrate, inorganic alkaline earth metal salts such as calcium chloride, magnesium sulfate or magnesium chloride , organic alkaline earth metal salts such as calcium lactate, carbohydrates, organic acids such as citric acid or tartaric acid, silicates such as water glass, sodium silicate or potassium silicate, urea and mixtures thereof.
  • the water-soluble or water-dispersible carrier used is based on carbohydrates at least 80% by weight, preferably at least 90% by weight, in particular at least 95% by weight or even completely.
  • the usable carbohydrate may be, for example, candy or hail sugar.
  • the use of crystalline sugar allows aesthetically pleasing particles with increased consumer acceptance.
  • the particles of the invention are characterized in that the carrier is in the form of crystals.
  • the water-soluble or water-dispersible carrier may also contain mixtures of said materials, e.g. Mixtures of salts, e.g. Sodium citrate and carbohydrates.
  • the proportion of the water-soluble or water-dispersible carrier in a further preferred embodiment is from 50 to 99% by weight, preferably from 75 to 95% by weight.
  • microcapsules may also readily contain solids, e.g. in the form of dispersions, for example, very fine hydrophobic silica dispersed in a perfume oil.
  • fragrances In the following, some statements are made on fragrances, textile care substances and skin care substances. It should be noted that all of these substances can be present on or in the particles according to the invention both outside and inside the microcapsules.
  • skin-care substances preferably as active substances in the microcapsules
  • they preferably exert their effect indirectly via the treated textile, which further transfers the skin-care substance to the skin upon contact with the skin, from which the skin can then derive a cosmetic benefit.
  • fragrances especially in combination with fabric care fabrics (such as silicone oil, etc.) and / or in combination with skin care agents (such as almond oil, etc.).
  • fragrances are particularly cost-intensive ingredients of detergents and cleaners, one endeavors to use them only in small quantities. The loss of these ingredients (for example in a washing machine) is equally unsatisfactory for the manufacturers and consumers of such agents.
  • the particles according to the invention if they are fragrance-containing, when washing or cleaning the surfaces, in particular of textiles, a particularly advantageous fragrance impression (increased favor / higher intensity / better durability) can be achieved, especially if the used particles contain water-insoluble, fragrance-containing microcapsules.
  • fragrances or perfume oils or fragrances are used synonymously here
  • individual fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures as are available from plant sources.
  • perfume oils which are generally associated with certain impressions.
  • a perfume oil may advantageously evoke associations to impressions such as “cleanliness” and “freshness,” which are generally associated with the use of detergents.
  • Another perfume oil can advantageously support the impression of "care”. It is advantageous, e.g. the fragrances, which give the impression of "care” to incorporate by the majority in the microcapsules and the perfumes, which awaken associations with impressions such as “cleanliness” and “freshness”, mostly incorporate outside of the microcapsules in the particle, or vice versa.
  • Fragrances preferred in the context of this invention which can be used to advantage to give the impression of "cleanliness” and "freshness", are bergamot oil, tangerine oil, dimethyl anthranilate, aldehyde C 11 (s), dihydromyrcenol, 4- tert-butylcyclohexyl acetate, allylamyl glycolate, tetrahydrolinalool, 6-methyl-gamma-ionone, isobornyl acetate, cyclovertal, ethyllinalool, aldehyde C 12, dynascone 10, limonene, orange oil, isobornyl acetate, eucalyptus oil (globulus), callose, cyclovertal, ethyl 2-methyl butyrate, Tetrahydrolinalool, aldehyde C 10, styrolyl acetate, Otbca, waterfruit base, citronitrile, undecavertol, st
  • fragrances which can be used to enhance the appearance of a "nourishing effect" are aldehyde C14, decalactone gamma, cyclamen aldehyde, lilial, troenan, canthoxal, citronellol, geraniol, musk, phenylethyl alcohol , Dihydrofloriffone, Dmbca, Phenirat, Phenylethylisobutyrate, Rose Oxide, Jasmelia, Hexylcinnamic Aldehyde (alpha), Jonon beta, Ylang, Cyclohexyl Salicylate, Hexenyl Salicylate (cis-3), Sandelice, Santobar, Bacdanol, Guaiacolite, Iso E Super, Timberol (forte), Norlimbanol , Ambroxan, cinnamyl alcohol, cyclopentadecanolides, nirvanol, Java
  • the product according to the invention contains at least one fragrance, preferably 2, 3 or more fragrances, from the list galaxolide, dihydromyrcenol, 4-tert-butylcyclohexylacetate, gamma-iso-methylionone, tetrahydro-linalool, hexylcinnamaldehyde, lilial, linalool, Amyl cinnamaldehyde, 6-methyl-gamma-ionone, methyl oleate, neryl acetate, 15-pentadecalactone, phenoxyethyl isobutyrate, phenylethyl methanoate, ⁇ -pinenes, ⁇ -pinenes, rose oxides, sabinene, anethole, benzoic acid 2-hydroxy-pentyl ester, diphenyl ether, benzophenone, cyclamen aldehyde ,
  • perfume precursors are also very advantageous, preferably when they are contained in the (preferably water-insoluble) microcapsule.
  • a perfume precursor is a compound which releases a desired odor and / or perfume molecule by the breaking of a chemical bond, for example by hydrolysis.
  • a desired perfume raw material is chemically combined with a carrier, preferably a slightly volatile or moderately volatile carrier. The combination results in a less volatile and more hydrophobic perfume precursor with improved attachment to fabrics.
  • the perfume is then released by disrupting the binding between the perfume raw material and the carrier, for example, by a change in pH (eg, by transpiration in the Wear), humidity, heat and / or sunlight during storage or drying on the clothesline.
  • the perfume raw material for use in perfume precursors are typically saturated or unsaturated volatile compounds containing an alcohol, an aldehyde and / or a ketone group. Fragrance raw materials useful herein include any fragrant substances or mixtures of substances.
  • inventively employable perfume precursors obey the formula in which R is hydrogen, linear C 1 -C 8 -alkyl, branched C 3 -C 20 -alkyl, cyclic C 3 -C 20 -alkyl, branched cyclic C 6 -C 20 -alkyl, linear C 6 -C 20 -alkenyl, branched C 6 -C 20 -alkenyl, cyclic C6- C20 alkenyl, branched cyclic C6-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, and mixtures thereof;
  • R 1 , R 2 and R 3 are independently linear, branched or substituted C 1 -C 20 alkyl; linear, branched or substituted C 2 -C 20 alkenyl; substituted or unsubstituted C3-C20 cyclic alkyl; substituted or unsubstituted C 6 -C 20 aryl, substituted or unsub
  • a preferred embodiment is when the inventively employable fragrance precursor releases compounds, obeying the formula wherein R is hydrogen, methyl, ethyl, phenyl and mixtures thereof; R 1 is selected from the group consisting of 4- (1-methylethyl) cyclohexanemethyl, 2,4-dimethyl-3-cyclohexen-1-ylmethyl, 2,4-dimethylcyclo-hex-1-ylmethyl, 2,4,6 Trimethyl-3-cyclohexen-1-ylmethyl, 2-phenylethyl, 1- (4-isopropylcyclohexyl) ethyl, 2,2-dimethyl-3- (3-methylphenyl) propan-1-yl, 3-phenyl-2-propene 1-yl, 2-methyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) -2-buten-1-yl, 3-methyl-5-phenyl-pentan-1-yl , 3-Methyl-5- (2,2,3-trimethyl-3-cyclopen
  • perfume precursors obey the formula wherein R 1 , R 2 , R 3 and R 4 are independently linear, branched or substituted C 1 -C 20 -alkyl; linear, branched or substituted C 2 -C 20 alkenyl; substituted or unsubstituted C5-C20 cyclic alkyl; substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 2 -C 40 alkyleneoxy; substituted or unsubstituted C3-C40 alkyleneoxyalkyl; substituted or unsubstituted C6-C40-alkylarylene; substituted or unsubstituted C6-C32 aryloxy; substituted or unsubstituted C6-C40 alkylene-oxyaryl; C6-C40 oxyalkylenearyl; and mixtures thereof.
  • R 1 , R 2 , R 3 and R 4 are independently linear, branched or substituted C 1 -C
  • the fragrances used comprise silicic acid ester mixtures which are silicic acid esters of the formulas and wherein all R are independently selected from the group consisting of H, straight or branched, saturated or unsaturated, substituted or unsubstituted C 1-6 hydrocarbon radicals, and the perfume alcohol radicals and / or biocide alcohol radicals, and m is from 1 to Preferably, at least one of R in both formula (I) and formula (II) is a perfume alcohol moiety and / or biocide alcohol moiety.
  • the silicic acid ester mixtures preferably make up at least 2% by weight of the total amount of fragrance,% by weight, based on all the fragrances of the entire particle.
  • the silicic acid ester mixtures are used in particular in the (preferably water-insoluble) microcapsules.
  • Particularly suitable perfume precursors are reaction products of compounds comprising at least one primary and / or secondary amine group, for example an amino-functional polymer, especially an amino-functional silicone, and a perfume ingredient selected from ketone, aldehyde and mixtures thereof.
  • an amino-functional polymer especially an amino-functional silicone
  • a perfume ingredient selected from ketone, aldehyde and mixtures thereof is particularly suitable.
  • the perfume oil contained in the particle in particular in the (preferably water-insoluble) microcapsules, further comprises fragrances having a boiling point above 250 ° C and a logP value of ⁇ 3.0, so is a preferred embodiment.
  • fragrances especially in the (preferably water-insoluble) microcapsules, allows an even further improvement of the fragrance effect, as far as favor, intensity and durability of the scent impression are concerned.
  • perfume oil contained in the (preferably water-insoluble) microcapsules to at least 1, 5 or 10 wt .-% of fragrances (wt .-% based on the contained in the microcapsules perfume oil) having a boiling point above 250 ° C and a logP value of ⁇ 3.0, there is a preferred embodiment. It has been found that particles according to the invention which contain such minimum amounts of perfumes having a boiling point above 250 ° C. and a log P value of ⁇ 3.0 in the (preferably water-insoluble) microcapsules have particularly advantageous scent properties. For example, an even longer lasting fragrance impression on the laundry can be achieved.
  • the octanot / water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. Since the distribution coefficients of the perfume ingredients are often high, e.g. 1000 or higher, they are more conveniently given in the form of their base 10 logarithm, one speaks of the so-called log P value.
  • the logP value of numerous fragrances is documented; For example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc., (Daylight CIS), Irvine, California, contains numerous logP values, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP” program, which is also available from Daylight CIS. This program also lists the experimental logP values if they are available in the Pomona92 database.
  • the "calculated logP" (ClogP value) is determined by the fragment approximation according to Harsch and Leo (see Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Harsch, PG Sammens, JB Taylor and CA Ransden, Eds., P.
  • the fragment approximation is based on the chemical structure of each of the perfume ingredients, taking into account the numbers and types of atoms, the atomic bonding ability, and the chemical bond.
  • the ClogP values which are the most reliable and widely used estimates for this physicochemical property, are preferably used in the present invention instead of the experimental logP values in the selection of perfume ingredients useful in the present invention.
  • boiling point values can be obtained, for example, from various known chemical manuals and databases. If a boiling point is given only at a different pressure, usually a pressure lower than the normal pressure of 760 mm Hg, the boiling point at normal pressure can be determined approximately with the help of boiling point pressure nomographs such as those in " The Chemist's Companion, AJ Gordon and RA Ford, John Wiley & Sons Publishers, 1972, pp. 30-36 , specified, estimated. Where applicable, the boiling point values can also be calculated by computer programs based on the molecular structure data such as those described in " Computer-assisted Prediction of Normal Boiling Points of Pyrans and Pynoles ", DT Starton et al. Chem. Inf. Comput.
  • the particle as such may also contain fragrances or perfume oil outside the microcapsules. Accordingly, a preferred embodiment of the invention relates to such a particle which contains a perfume oil outside the microcapsules, wherein preferably the composition of the perfume oil outside the microcapsules differs from the perfume oil optionally contained in the microcapsules.
  • perfume oil is contained in or on the particles both in the microcapsules and outside the microcapsules. These perfume oils may be the same, but it is preferred if these perfume oils differ in order to generate an additional fragrance impression.
  • An advantage of the particles according to the invention, which contain in particular fragrance-containing (preferably water-insoluble) microcapsules, is that in particular ordinary perfumed sugar crystals may have the disadvantage that they require rather high perfume concentrations, e.g. to achieve a desired long-lasting scent effect of the treated textiles.
  • the use of (preferably water-insoluble) encapsulated perfume oils, especially with long-lasting properties, enables a more effective and thus resource-saving use of perfume oils.
  • a high perfume content can lead to process-technical difficulties in perfume application, in particular with perfume-laden sugar crystals.
  • the fragrances Due to the limited absorptivity of the crystals, the fragrances can essentially only be applied to the surface, for example in combination with a coating layer.
  • a perfume-PEG melt Used to coat the crystals, e.g. used a perfume-PEG melt, the melting point of the PEG is greatly reduced at high perfume content, thus inhibiting the solidification of the mixture. As a result, the formation of a stable coating layer is problematic. Such problems are overcome by our invention.
  • the total amount of perfume contained in the particle is from 0.1 to 30% by weight, preferably from 0.3 to 15% by weight and in particular from 0.5 to 7% by weight, based on the total weight Particles, so is also a preferred embodiment of the invention.
  • the amount of the perfume oil contained in the microcapsules is from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, based on the total particles, then again a preferred embodiment of the invention is present ,
  • a further preferred embodiment of the invention is when the amount of the perfume oil not contained in the microcapsules is 0-10% by weight, preferably 0.05-5% by weight, based on the total particles.
  • the active substances in the microcapsules can also comprise textile care substances.
  • textile care substances a provision of detergents or cleaning agents or additives with textile-care properties is made possible.
  • the textiles to be cleaned are also maintained so that they can be used e.g. get a pleasantly soft grip.
  • the fabric care agents may be present in the particles of the invention within the microcapsules and / or outside the microcapsules.
  • a particle according to the invention may advantageously comprise fabric-softening clays as a textile care fabric.
  • the softening clay can, however, be applied particularly well outside the microcapsules. If softening clay is to be applied to the particle, it is e.g. it is possible first to coat the water-soluble or water-dispersible carrier with the softening clay and then to apply microcapsules and thermoplastic polymer. Alternatively, a mixture of microcap, softening clay and thermoplastic polymer can be applied. Alternatively, it is possible finally to dust off with fabric-softening clay, which corresponds to a particularly preferred embodiment.
  • smectite clay As a fabric softening clay, for example, smectite clay is suitable.
  • Preferred smectite clays are beidellite clays, hectorite clays, laponite clays, montmorillonite clays, nontronite clays, saponite clays, sauconite clays, and mixtures thereof.
  • Montmorillonite clays are the preferred softening clays. Bentonites contain mainly montmorillonites and can serve as a preferred source of fabric softening clay.
  • Suitable bentonites are sold, for example, under the names Laundrosil® by Süd-Chemie or under the name Detercal by Laviosa.
  • the amount of fabric softening clay in the particles according to the invention can be, for example, between 0.1 and 10% by weight and preferably 1 to 5% by weight. According to another embodiment, no textile softening clay is contained in the particles according to the invention or only a very small amount, for example ⁇ 0.1% by weight. A reasonable upper limit can also be, for example, 15% by weight.
  • a major component that can be used in combination with, or independently of, fabric softening clay is an organic fatty acid softener. This may also be present in the particles according to the invention within the microcapsules and / or outside the microcapsules.
  • the organic plasticizer may consist of anionic, cationic or nonionic fatty chains (C10-C22, preferably C12-C18).
  • Anionic softeners include fatty acid soaps.
  • Preferred organic plasticizers are nonionic compounds such as fatty acid esters, ethoxylated fatty acid esters, fatty alcohols and polyol polymers.
  • the organic plasticizer is most preferably a higher fatty acid ester of a pentaerythritol compound, the term used in this specification to describe higher fatty acid esters of pentaerythritol, higher fatty acid esters of pen-taerythritol oligomers, higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol, and higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol oligomers ,
  • a particle according to the invention may contain, for example, a textile-softening polymer, in particular a polysiloxane and / or a cationic polymer, as potential textile care substance.
  • the fabric softening polymer may be contained in and / or outside of the microcapsules.
  • Suitable cationic polymers include in particular those described in " CTFA International Cosmetic Ingredient Dictionary, Fourth Edition, JM Nikitakis, et al, Editors, published by the Cosmetic, Toiletry, and Fragrance Association, 1991 are described and summarized under the collective name "Polyquaternium".
  • the cationic polymers have a fabric softening, thus textile-care effect, and in addition they can make skin-care contribution.
  • a particle according to the invention may also comprise further suitable textile-care compounds, preferably eg fluorescers, anti-redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing auxiliaries, UV absorbers, repellents, impregnating agents.
  • suitable textile-care compounds preferably eg fluorescers, anti-redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing auxiliaries, UV absorbers, repellents, impregnating agents.
  • a particle of the invention contains thermoplastic polymer, preferably in amounts of 0.01-25 wt .-%, in particular 0.05-10 wt .-%.
  • thermoplastic polymer preferably in amounts of 0.01-25 wt .-%, in particular 0.05-10 wt .-%.
  • Polyethylene glycols (PEG), polyvinyl alcohols, polyacrylate, PVP or polyester are preferably suitable as the thermoplastic polymer.
  • Particularly suitable are solid at room temperature polyethylene glycols having a melting point of about 65 ° C ⁇ 20 ° C, for example having a melting point of about 60 ° C or e.g. of 65 ° C or e.g. from about 55 ° C.
  • a particle according to the invention may also comprise water-binding substances. If the particle according to the invention thus comprises water-binding substances, preferably in amounts of 0.1-10% by weight, based on the total particles, the water-binding substance being in particular selected from zeolite, silica, fabric softening clay, starch and / or their derivatives and / or cellulose (derivatives), such as preferably carboxymethylcellulose, so is a preferred embodiment of the invention.
  • the particle of the invention is characterized in that the water-soluble or water-dispersible carrier is coated with a mixture comprising thermoplastic polymer and microcapsules.
  • coating e.g. also water-binding substances and water may be included.
  • the particle core is formed by the water-soluble or water-dispersible carrier, wherein the core is coated with thermoplastic polymer and microcapsules.
  • a particle of the invention i. a thermoplastic polymer-microcapsule-coated particle is further powdered with a powdering agent, particularly comprising zeolite, silica, fabric softening clay (e.g., bentonite), starch and / or its derivatives and / or cellulose (derivatives) such as preferably carboxymethylcellulose.
  • a powdering agent particularly comprising zeolite, silica, fabric softening clay (e.g., bentonite), starch and / or its derivatives and / or cellulose (derivatives) such as preferably carboxymethylcellulose.
  • the particle according to the invention is free of surface-active agents, plasticizers and builders.
  • the microcapsules which can be used according to the invention may be water-soluble and / or water-insoluble microcapsules, but are preferably water-insoluble microcapsules.
  • the water insolubility of the microcapsules has the advantage that this allows a washing application lasting outgoing separation of active ingredients can be made possible.
  • the water-insoluble microcapsules are reusable microcapsules, the wall material of the microcapsules comprising polyurethanes, polyolefins, polyamides, polyesters, polysaccharides, epoxy resins, silicone resins and / or polycondensation products of carbonyl compounds and compounds containing NH groups.
  • reusable microcapsules means those microcapsules which, when attached to textile treated therewith, can be opened or wiped by mechanical rubbing or pressure such that release of contents results only as a result of mechanical action, for example when using a towel on which such microcapsules are deposited, dries hands.
  • reusable microcapsules have average diameters in the range of 0.05 to 500 .mu.m, preferably between 5 and 150 .mu.m, in particular between 10 and 100 .mu.m, for example between 10 and 80 .mu.m.
  • the shell of the microcapsules enclosing the core or (filled) cavity has an average thickness in the range between approximately 0.01 and 50 ⁇ m, preferably between approximately 0.1 ⁇ m and approximately 30 ⁇ m, in particular between approximately 0.5 ⁇ m and approximately 8 microns. Microcapsules are particularly easy to squeeze if they are within the ranges given above regarding the mean diameter and the average thickness.
  • microcapsule preparation as such is well known to those skilled in the art. Suitable methods for producing microcapsules are familiar to the person skilled in the art and are described, for example, in US Pat US 3,870,52 , in US 3,516,941 , in US 3,415,758 or in EP 0 026 914 A1 described. The latter describes, for example, the microcapsule preparation by acid-induced condensation of melamine-formaldehyde precondensates and / or their C 1 -C 4 -alkyl ethers in water in which the hydrophobic material forming the capsule core is dispersed, in the presence of a protective colloid.
  • melamine-urea-formaldehyde microcapsules or melamine-formaldehyde microcapsules or urea-formaldehyde microcapsules can be used, for example obtainable from 3M Corporation or BASF.
  • Usable microcapsules are also used in EP 1 244 768 A2 described, to which we refer herewith.
  • the microcapsules to be used can be processed, for example, directly in the dispersion, as they usually occur in the ordinary production process. Possibly. one can modify the dispersion, e.g. thicken and / or adjust the water content of the dispersion so that it contains 5 to 80 wt .-%, preferably 40 to 80 wt .-% microcapsules. It is also possible to previously mix the microcapsule dispersion to be used with water-binding substances. This corresponds to a preferred embodiment of the invention. The slurry can e.g. also be modified by the use of thickeners or by adjusting the water content. On the other hand, one can use the microcapsules as such, i. in dry form and not in dispersed form.
  • a preferred particle according to the invention is characterized in that the water-soluble or water-dispersible carrier has a particle size in the range from 0.1 to 30 mm, in particular 0.2 to 7 mm and particularly preferably 0.5 to 3 mm, e.g. in the range of 0.8 to 2.5 mm.
  • the particle may have a particle size in the range ⁇ 0.1 to 30 mm, preferably ⁇ 0.2 to 10 mm, in particular ⁇ 0.5 to 5 mm, e.g. in the range 0.8 to 3 mm.
  • dyes In order to improve the aesthetic impression of the particles, they can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents or cleaning agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
  • a particle according to the invention may also contain a pearlescing agent to increase the gloss.
  • suitable pearlescing agents are ethylene glycol mono- and distearate (for example Cutina AGS from Cognis) and PEG-3-distearate.
  • the particles of the present invention may preferably have a bulk density in the range of 300 to 900 g / l or 400 to 800 g / l, for example, in the vicinity of 650 g / l.
  • steps (a) and (b) can be carried out in the usual mixing apparatuses.
  • microcapsules in step (a) can be added in dry form or else as aqueous slurry.
  • step (a) the microcapsules are mixed into the melt together with water-binding substances as aqueous slurry, a preferred embodiment of the invention is present.
  • the slurry can e.g. also be modified by the use of thickeners or by adjusting the water content.
  • the water-soluble or water-dispersible carrier material used in step (b) has previously been premodified by mixing the actual carrier with a fabric softening clay in the presence of textile or skin care compounds and / or in particular in the presence of perfume, another preferred Embodiment of the invention before.
  • the particle is still powdered with a powdering agent, preferably comprising textile softening clay, another preferred embodiment of the invention is present.
  • Another object of the present invention is a washing, cleaning or care agent containing particles according to the invention as described above or as obtainable by a method according to the invention.
  • the particles of the invention can be easily introduced into a solid detergent or cleaning agent.
  • a preferred solid detergent or cleaner may be 0.1 to 20% by weight, preferably 1 to 10 wt .-%, of the particles according to the invention, which are mixed in, for example, simply.
  • Another object of the present invention is the use of the particles according to the invention, as described above, or the washing, cleaning or care agent according to the invention, as described above, in the textile washing or treatment, preferably in an automatic washing machine.
  • the detergents or cleaners according to the invention may preferably also contain surfactant (s), it being possible to use anionic, nonionic, zwitterionic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants.
  • the total surfactant content of a detergent is preferably above 5% by weight, better above 10% by weight, but advantageously below 40% by weight and particularly preferably below 35% by weight, based on the total detergent.
  • nonionic surfactants it is possible to use preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be 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 which 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 1.2 to 1.4.
  • Alkyl glycosides are known, mild surfactants.
  • nonionic surfactants that are used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • 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.
  • the optional content of nonionic surfactants in the washing or cleaning agents is preferably> 0.1% by weight, for example 5 to 30% by weight, preferably 7 to 20% by weight and in particular 9 to 15% by weight, in each case based on the total washing or cleaning agent.
  • the washing or cleaning agent does not contain any nonionic surfactants or only small amounts, for example ⁇ 0.5% by weight.
  • anionic surfactants for example, those of the sulfonate type and sulfates can be used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • anionic surfactants are sulfated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • Particularly preferred anionic surfactants are soaps.
  • Suitable are saturated and unsaturated 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants, including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the optional content of preferred detergents or cleaning agents to anionic surfactants is preferably> 0.1 wt .-%, for example 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-%, respectively based on the entire detergent or cleaning agent.
  • washing or cleaning agents may contain further ingredients which further improve the performance and / or aesthetic properties of the washing or cleaning agent.
  • preferred washing or cleaning agents may additionally comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents , Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, neutral filler salts and UV absorbers.
  • Suitable builders which may be present in the detergents or cleaners are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • the washing or cleaning agent contains no zeolite.
  • Organic builders which are present in the washing or detergents may include polycarboxylate polymers such as polyacrylates and acrylic acid / maleic acid copolymers, polyaspartates and monomeric polycarboxylates such as citrates, gluconates, succinates or malonates, which are preferably used as sodium salts.
  • the total amount of optionally contained builders comprising, for example, zeolite, polycarboxylate, sodium citrate is preferably 1-70% by weight. Meaningful lower limits can z. B. at 10, 15, 20 or 30 wt .-% are. Useful upper limits may be, for example, 40, 55 or 60 wt .-%.
  • bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthalimino peracid or diperdodecanedioic acid.
  • the total amount of bleaching agents optionally included may be, for example, 5-25% by weight, or preferably 10-20% by weight, if the presence of bleaching agent is desired.
  • the washing or cleaning agent may contain enzymes in encapsulated form and / or directly in the washing or cleaning agent.
  • Suitable enzymes include in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, ⁇ -glucanases, oxidases, peroxidases, perhydrolases and / or laccases and mixtures the enzymes mentioned in question.
  • the enzymes may be adsorbed to carriers to protect against premature degradation.
  • the proportion of enzymes or enzyme granules directly in the washing or cleaning agent may be, for example, about 0.01 to 5 wt .-%, preferably 0.12 to about 2.5 wt .-%.
  • the washing or cleaning agent optionally contains one or more perfumes in an amount of usually up to 10 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1 to 3 wt .-%.
  • the amount of perfume used is also dependent on the type of detergent or cleaning agent. However, it is particularly preferred that perfume is at least partially introduced into the washing or cleaning agent via the particles according to the invention. However, it is also possible for the washing or cleaning agent to contain perfume which is not introduced into the washing or cleaning agent via the particles according to the invention.
  • Soil-release polymers can usually be used in amounts of between 0% and, for example, 5% by weight, based on the finished washing or cleaning agent.
  • Optical brighteners can usually be found in Amounts between 0% and 0.3 wt .-%, based on the final detergent or cleaning agent used.
  • the amount of optional color transfer inhibitor based on the total amount of the detergent or cleaning agent is preferably from 0.01 to 2% by weight, preferably from 0.05 to 1% by weight, and more preferably from 0.1 to 0.5% by weight .-%.
  • Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • anionic polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates, which in preferred detergents or cleaners in amounts of 0.01 to 2.5 wt .-%, preferably 0.02 to 2 wt .-% and in particular from 0.03 to 1, 5 wt .-% are included.
  • These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which can be used mostly in the form of their ammonium or alkali metal salts.
  • organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobut
  • neutral fillers such as sodium sulfate or sodium carbonate may be included in the solid detergents or cleaners.
  • washing or cleaning agents according to the invention can be used in particular for cleaning and conditioning textile fabrics.
  • the detergent or cleaning agent without the particles according to the invention is first prepared by known processes, which may comprise, for example, drying steps, mixing steps, densification steps, shaping steps and / or the subsequent addition of heat-sensitive ingredients ("post-addition") , Subsequently, the product obtained is mixed with the particles according to the invention.
  • the mixing step may be followed by further compaction and / or shaping steps.
  • Table 1 shows particles E1 to E3 according to the invention. The numbers in Table 1 are given in wt .-%. Table 1: E1 E2 E3 Sucrose crystals (0.5 to 3 mm) 70.998 78.9989 77.998 bentonite 4 4 4 silica 4 3 4 Perfume 3 4 2 polydimethylsiloxane 7 - - Polyquaternium-7 - 1 - Polyquaternium-10 - - 2 Perfume microcapsules 5 4 4 PEG 6000 6 5 6 dye 0,002 0,002 0,002

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)

Claims (11)

  1. Particules, appropriées pour une utilisation dans des produits de lavage, de nettoyage ou de soin, comprenant un support soluble ou dispersible dans l'eau ainsi que des microcapsules contenant une/des substance(s) active(s), le support soluble ou dispersible dans l'eau comprenant un hydrate de carbone, en particulier choisi parmi le dextrose, le fructose, le galactose, l'isoglucose, le glucose, le saccharose, le raffinose ou leurs mélanges et le support soluble ou dispersible dans l'eau étant revêtu par un mélange, comprenant un polymère thermoplastique et des microcapsules et le support se trouvant sous forme de cristaux.
  2. Particules selon la revendication 1, caractérisées en ce que les microcapsules contiennent une substance active de préférence liquide, qui convient à des fins de lavage, de nettoyage, de soin et/ou d'ennoblissement, en particulier
    (a) des substances odoriférantes,
    (b) des produits de soin pour textiles, tels que de préférence les huiles de silicone, les polymères cationiques, et/ou
    (c) des produits de soin pour la peau, tels que de préférence la vitamine E, les huiles naturelles, l'extrait d'aloe vera, l'extrait de thé vert, le D-panthénol, l'extrait de plancton, la vitamine C, l'urée et/ou la glycine.
  3. Particules selon l'une quelconque des revendications 1 ou 2, caractérisées en ce que la quantité totale contenue de parfum est de 0,1 à 30% en poids, de préférence de 0,3 à 15% en poids et en particulier de 0,5 à 7% en poids, les % en poids se rapportant à la totalité des particules.
  4. Particules selon l'une quelconque des revendications 1 à 3, caractérisées en ce que la quantité de l'huile parfumée contenue dans les microcapsules est de 0,01 à 20% en poids, de préférence de 0,05 à 10% en poids, les % en poids se rapportant à la totalité des particules.
  5. Particules selon l'une quelconque des revendications 1 à 4, caractérisées en ce qu'elles comprennent le polymère thermoplastique en des quantités de 0,01-25% en poids, en particulier de 0,05-10% en poids.
  6. Particules selon l'une quelconque des revendications 1 à 5, caractérisées en ce qu'elles comprennent des substances liant l'eau, de préférence en des quantités de 0,1-10% en poids, les % en poids se rapportant à la totalité des particules, la substance liant l'eau étant en particulier choisie parmi la zéolithe, la silice, l'argile assouplissant les textiles, l'amidon et/ou ses dérivés et/ou la cellulose ou ses dérivés, tels que de préférence la carboxyméthylcellulose.
  7. Particules selon l'une quelconque des revendications 1 à 6, caractérisées en ce qu'il s'agit, pour les microcapsules, de microcapsules solubles et/ou insolubles dans l'eau, de préférence cependant de microcapsules insolubles dans l'eau.
  8. Particules selon l'une quelconque des revendications 1 à 7, caractérisées en ce que le support soluble ou dispersible dans l'eau présente une grosseur de particules dans la plage de 0,1 à 30 mm, en particulier de 0,2 à 7 mm et de manière particulièrement préférée de 0,5 à 3 mm.
  9. Procédé pour la préparation de particules selon l'une quelconque des revendications 1 à 8, comprenant
    (a) la préparation d'un mélange de microcapsules et de polymère thermoplastique, comme par exemple un PEG, un PVA, un polyacrylate, une PVP ou un polyester sous forme d'une masse fondue contenant les microcapsules
    (b) le mélange de la masse fondue de l'étape (a) avec un matériau support soluble ou dispersible dans l'eau.
  10. Procédé selon la revendication 9, dans lequel, dans l'étape (a), les microcapsules sont intégrées sous forme de suspension aqueuse, ensemble avec des substances liant l'eau, dans la masse fondue.
  11. Agent de lavage, de nettoyage ou de soin, contenant des particules selon l'une quelconque des revendications précédentes 1-8.
EP09772258A 2008-07-03 2009-06-05 Additif de detergents se presentant sous forme de particules Revoked EP2291504B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09772258T PL2291504T3 (pl) 2008-07-03 2009-06-05 Dodatek w postaci cząstek do środków piorących i czyszczących

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008031212A DE102008031212A1 (de) 2008-07-03 2008-07-03 Wasch- und Reinigungsmitteladditiv in Partikelform
PCT/EP2009/056906 WO2010000558A1 (fr) 2008-07-03 2009-06-05 Additif de détergents se présentant sous forme de particules

Publications (2)

Publication Number Publication Date
EP2291504A1 EP2291504A1 (fr) 2011-03-09
EP2291504B1 true EP2291504B1 (fr) 2012-11-14

Family

ID=40874847

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09772258A Revoked EP2291504B1 (fr) 2008-07-03 2009-06-05 Additif de detergents se presentant sous forme de particules

Country Status (6)

Country Link
US (1) US20110097369A1 (fr)
EP (1) EP2291504B1 (fr)
DE (1) DE102008031212A1 (fr)
ES (1) ES2396926T3 (fr)
PL (1) PL2291504T3 (fr)
WO (1) WO2010000558A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103966032A (zh) * 2013-01-30 2014-08-06 石家庄菠莉亚日用化工有限公司 环保型中性浓缩片状洗涤剂
US9347022B1 (en) 2014-12-17 2016-05-24 The Procter & Gamble Company Fabric treatment composition
US9545460B2 (en) 2014-12-17 2017-01-17 The Procter & Gamble Company Process for freshening air
US11441106B2 (en) 2017-06-27 2022-09-13 Henkel Ag & Co. Kgaa Particulate fragrance enhancers

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012022034A1 (fr) 2010-08-18 2012-02-23 Unilever Plc Améliorations apportées à des compositions de traitement des tissus comprenant des agents améliorants cibles
EP2646002B1 (fr) 2010-12-01 2019-02-27 ISP Investments LLC Microcapsules à base d'hydrogel
DE102011006315A1 (de) 2011-03-29 2012-10-04 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit modifizierten Riechstoffen
BR112014003418B1 (pt) 2011-08-24 2020-03-17 Unilever N.V. Partícula de fornecimento de agente de benefício, composição de tratamento para lavanderia, pele ou cabelo, composição de tratamento para lavanderia, composição de tratamento de cabelos e processo de produção de partículas de fornecimento de agente de benefício
DE102012214848A1 (de) 2012-08-21 2014-02-27 Henkel Ag & Co. Kgaa Duftstoff-(Halb-)Metalloxid-Zubereitungen
EP2806018A1 (fr) * 2013-05-20 2014-11-26 The Procter & Gamble Company Produits encapsulés
US20150152351A1 (en) * 2013-11-29 2015-06-04 Amorepacific Corporation Perfume composition for reproducing fragrance of abies koreana of jeju island
WO2017066400A1 (fr) * 2015-10-13 2017-04-20 The Sun Products Corporation Système à plusieurs étages d'administration d'un agent bénéfique
ES2739662T3 (es) * 2015-12-16 2020-02-03 Procter & Gamble Artículo de dosis unitaria soluble en agua
EP3181674A1 (fr) * 2015-12-16 2017-06-21 The Procter and Gamble Company Article de dose unitaire soluble dans l'eau
CN108778730B (zh) 2016-01-14 2021-02-09 Isp投资有限公司 易碎的外壳微胶囊、其制备方法和其使用方法
CN109310601B (zh) 2016-06-08 2022-05-24 高砂香料工业株式会社 香料材料
EP3478249A4 (fr) * 2016-07-01 2020-03-04 International Flavors & Fragrances Inc. Compositions de microcapsules stables
US20180044616A1 (en) * 2016-08-03 2018-02-15 Henkel IP & Holding GmbH Fragranced pastille for laundry application
WO2018055114A1 (fr) * 2016-09-26 2018-03-29 Henkel Ag & Co. Kgaa Sucre employé comme matière porteuse de parfum
US11008535B2 (en) 2017-02-10 2021-05-18 Henkel IP & Holding GmbH Particulate fragrance enhancers
US10683475B2 (en) 2017-05-31 2020-06-16 Henkel IP & Holding GmbH Fragranced pastille for laundry application
DE102017218991A1 (de) 2017-10-24 2019-04-25 Henkel Ag & Co. Kgaa Feste parfümhaltige Zusammensetzung
DE102017130878A1 (de) * 2017-12-21 2019-06-27 Buck Group AG Duftzusatz für Wäsche
US10787629B2 (en) * 2018-01-29 2020-09-29 The Procter & Gamble Company Particulate laundry softening wash additive comprising a branched polyester
US10781413B2 (en) 2018-01-29 2020-09-22 The Procter & Gamble Company Dryer sheets comprising branched polyester polymers
EP3746533A1 (fr) 2018-01-29 2020-12-09 The Procter & Gamble Company Agents liquides améliorant l'état des textiles comprenant des molécules de polyester ramifié
US11104871B2 (en) 2018-05-30 2021-08-31 The Procter & Gamble Company Dryer sheets comprising branched polyester polymers
US11046917B2 (en) 2018-05-30 2021-06-29 The Procter & Gamble Company Liquid fabric enhancers comprising branched polyester molecules
JP7208263B2 (ja) * 2018-05-30 2023-01-18 ザ プロクター アンド ギャンブル カンパニー 粒子状洗濯用柔軟化洗浄添加剤
JP2021529869A (ja) 2018-07-09 2021-11-04 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ パッケージ化組成物
US11718815B2 (en) * 2018-09-26 2023-08-08 Firmenich Sa Powder detergent composition
WO2020226614A1 (fr) * 2019-05-06 2020-11-12 Colgate-Palmolive Company Compositions de soin de tissu solides et leurs procédés
CN115038778A (zh) * 2020-02-27 2022-09-09 联合利华知识产权控股有限公司 洗衣组合物
EP4349950A3 (fr) 2020-05-14 2024-06-19 The Procter & Gamble Company Composition d'entretien de tissus
WO2024052101A1 (fr) * 2022-09-08 2024-03-14 Unilever Ip Holdings B.V. Composition de lessive
WO2024052102A1 (fr) * 2022-09-08 2024-03-14 Unilever Ip Holdings B.V. Composition de lessive
WO2024052103A1 (fr) * 2022-09-08 2024-03-14 Unilever Ip Holdings B.V. Composition de lessive

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007115872A1 (fr) * 2006-04-06 2007-10-18 Henkel Ag & Co. Kgaa Composition solide de soin des textiles comprenant un polymere hydrosoluble

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US387052A (en) 1888-07-31 Spring-vehicle
US3415758A (en) 1960-03-09 1968-12-10 Ncr Co Process of forming minute capsules en masse
US3455838A (en) * 1966-04-22 1969-07-15 Nat Starch Chem Corp Method of encapsulating water-insoluble substances and product thereof
US3516941A (en) 1966-07-25 1970-06-23 Minnesota Mining & Mfg Microcapsules and process of making
US3686025A (en) * 1968-12-30 1972-08-22 Procter & Gamble Textile softening agents impregnated into absorbent materials
US4234627A (en) * 1977-02-04 1980-11-18 The Procter & Gamble Company Fabric conditioning compositions
DE2940786A1 (de) 1979-10-08 1981-04-16 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von mikrokapseln
US5066419A (en) * 1990-02-20 1991-11-19 The Procter & Gamble Company Coated perfume particles
DE10000223A1 (de) * 2000-01-05 2001-07-12 Basf Ag Mikrokapselzubereitungen und Mikrokapseln enthaltende Wasch- und Reinigungsmittel
EP1214892B1 (fr) * 2000-12-15 2005-03-09 Quest International B.V. Composition stable à l'humidité et l'oxygène, et procédé de preparation
CA2549854C (fr) 2003-12-19 2012-09-18 Unilever Plc Granules detergents et leur procede de fabrication
DE102006016575A1 (de) * 2006-04-06 2007-10-11 Henkel Kgaa Feste, textil- und/oder hautpflegende Zusammensetzung
WO2007113326A1 (fr) * 2006-04-06 2007-10-11 Henkel Ag & Co. Kgaa Composition solide, permettant de prendre soin des textiles comprenant un polymère soluble dans l'eau
BRPI0603808A2 (pt) * 2006-04-20 2009-03-10 Procter & Gamble partÍcula de liberaÇço contendo ativo
US7786027B2 (en) * 2006-05-05 2010-08-31 The Procter & Gamble Company Functionalized substrates comprising perfume microcapsules
DE102006047230A1 (de) * 2006-10-04 2008-04-10 Henkel Kgaa Duftmediumabgabesystem
DE102007010109A1 (de) * 2007-02-28 2008-09-04 Henkel Ag & Co. Kgaa Wirkstoffträgersysteme

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007115872A1 (fr) * 2006-04-06 2007-10-18 Henkel Ag & Co. Kgaa Composition solide de soin des textiles comprenant un polymere hydrosoluble

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103966032A (zh) * 2013-01-30 2014-08-06 石家庄菠莉亚日用化工有限公司 环保型中性浓缩片状洗涤剂
CN103966032B (zh) * 2013-01-30 2017-11-24 石家庄菠莉亚日用化工有限公司 环保型中性浓缩片状洗涤剂
US9347022B1 (en) 2014-12-17 2016-05-24 The Procter & Gamble Company Fabric treatment composition
US9545460B2 (en) 2014-12-17 2017-01-17 The Procter & Gamble Company Process for freshening air
US11441106B2 (en) 2017-06-27 2022-09-13 Henkel Ag & Co. Kgaa Particulate fragrance enhancers

Also Published As

Publication number Publication date
EP2291504A1 (fr) 2011-03-09
ES2396926T3 (es) 2013-03-01
US20110097369A1 (en) 2011-04-28
WO2010000558A1 (fr) 2010-01-07
DE102008031212A1 (de) 2010-01-07
PL2291504T3 (pl) 2013-04-30

Similar Documents

Publication Publication Date Title
EP2291504B1 (fr) Additif de detergents se presentant sous forme de particules
EP2001986B1 (fr) Composition solide de soin des textiles comprenant un polymere hydrosoluble
WO2011029772A1 (fr) Composition parfumante solide
EP2358859B1 (fr) Détergent ou nettoyant parfumé
EP2291505B1 (fr) Composition solide contenant un polysaccharide et destinée à l'entretien des textiles
EP2334778B1 (fr) Stabilisation de suspensions de microcapsules
DE60012345T2 (de) Reinigungsmittelzusammensetzung parfumteilchen enthaltend
EP1863895B1 (fr) Produit nettoyant ou detergent transparent a limite d'ecoulement
EP2711414B1 (fr) Stabilisation de systèmes de capsule dans des produits de nettoyage et de lavage
WO2007113069A1 (fr) Composition solide permettant de prendre soin de la peau et/ou des textiles
DE102008047361A1 (de) Textilspülmittel
EP2061864B1 (fr) Composition solide, textile et/ou de soin de la peau
DE102008047233A1 (de) Feste, Textil-pflegende Zusammensetzung mit einem Polysaccharid
DE102007019372A1 (de) Flüssiges Textilbehandlungsmittel
EP2029716B1 (fr) Composition solide a base de savon pour le soin des textiles
WO2007113326A1 (fr) Composition solide, permettant de prendre soin des textiles comprenant un polymère soluble dans l'eau
EP2046927A1 (fr) Esterquats contenant des groupes oh pour rendements améliorés de substances odorantes
WO2008090025A1 (fr) Procédé de préparation de compositions particulaires d'agent de blanchiment
DE102008032206A1 (de) Parfümiertes Wäscheweichspülmittel
DE102007019374A1 (de) Photokatalytisches Material enthaltende Flüssigsysteme

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: 20100921

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 HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA RS

RIN1 Information on inventor provided before grant (corrected)

Inventor name: SEGLER, TOBIAS

Inventor name: SUNDER, MATTHIAS

Inventor name: STURM, MARIO

Inventor name: WRUBBEL, NOELLE

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20120202

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 HR HU IE IS IT LI LT LU LV MC MK MT NL NO 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: 584030

Country of ref document: AT

Kind code of ref document: T

Effective date: 20121115

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: 502009005390

Country of ref document: DE

Effective date: 20130110

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2396926

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20130301

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20121114

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: HR

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: 20121114

Ref country code: NO

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: 20130214

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: 20121114

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: 20121114

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: 20121114

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: 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: 20121114

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: 20130314

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: 20130215

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: 20121114

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: 20121114

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: 20130214

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: 20121114

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: 20121114

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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

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: 20121114

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: 20121114

26 Opposition filed

Opponent name: UNILEVER PLC / UNILEVER NV

Effective date: 20130807

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20130814

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

Free format text: ORIGINAL CODE: EPIDOSNOBS2

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502009005390

Country of ref document: DE

Effective date: 20130807

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: 20121114

BERE Be: lapsed

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

Effective date: 20130630

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

Effective date: 20121114

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

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: 20130605

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: 20130630

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

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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: 20130605

Ref country code: LI

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

Effective date: 20130630

Ref country code: CH

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

Effective date: 20130630

Ref country code: GB

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

Effective date: 20130605

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

Ref country code: MT

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: 20121114

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

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: 20121114

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 502009005390

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 502009005390

Country of ref document: DE

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

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: 20130605

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; INVALID AB INITIO

Effective date: 20090605

Ref country code: MK

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: 20121114

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

Ref country code: DE

Payment date: 20150619

Year of fee payment: 7

Ref country code: ES

Payment date: 20150626

Year of fee payment: 7

Ref country code: CZ

Payment date: 20150604

Year of fee payment: 7

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 584030

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140605

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

Ref country code: PL

Payment date: 20150525

Year of fee payment: 7

Ref country code: IT

Payment date: 20150622

Year of fee payment: 7

Ref country code: FR

Payment date: 20150619

Year of fee payment: 7

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

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

Ref country code: AT

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

Effective date: 20140605

27W Patent revoked

Effective date: 20150702

REG Reference to a national code

Ref country code: AT

Ref legal event code: MA03

Ref document number: 584030

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150702

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: 20130314