EP2553077A1 - Agent détergent pour textiles délicats - Google Patents

Agent détergent pour textiles délicats

Info

Publication number
EP2553077A1
EP2553077A1 EP11711356A EP11711356A EP2553077A1 EP 2553077 A1 EP2553077 A1 EP 2553077A1 EP 11711356 A EP11711356 A EP 11711356A EP 11711356 A EP11711356 A EP 11711356A EP 2553077 A1 EP2553077 A1 EP 2553077A1
Authority
EP
European Patent Office
Prior art keywords
detergent
hydrophobically
modified
polymer
detergent 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.)
Granted
Application number
EP11711356A
Other languages
German (de)
English (en)
Other versions
EP2553077B1 (fr
Inventor
Evelyn Langen
Ulrich Pegelow
Paula Barreleiro
Kerstin Ziganke
Sheila Edwards
Gabriele HÜRTGEN
Luca Bellomi
Karin Kania
Carolin Trenka
Andreas Wagner
Johannes Zipfel
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=44201984&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2553077(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE201010003535 external-priority patent/DE102010003535A1/de
Priority claimed from DE201110006147 external-priority patent/DE102011006147A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL11711356T priority Critical patent/PL2553077T3/pl
Publication of EP2553077A1 publication Critical patent/EP2553077A1/fr
Application granted granted Critical
Publication of EP2553077B1 publication Critical patent/EP2553077B1/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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the invention relates to a detergent for delicate textiles.
  • the invention also relates to the use of the detergent and to a process for its preparation.
  • Detergents which are also suitable for the gentle cleaning of highly sensitive textiles made of wool and / or silk are known per se. They generally have a neutral to slightly alkaline pH and, in addition to anionic surfactants such as alkylbenzenesulfonate, fatty alcohol sulfate or alkyl glycol ether sulfate, often contain nonionic and / or cationic compounds.
  • anionic surfactants such as alkylbenzenesulfonate, fatty alcohol sulfate or alkyl glycol ether sulfate.
  • the nonionic surfactants are said to enhance detergency while the cationic compounds are said to improve the softness and feel of the laundered fabrics.
  • the addition of softening cationic surfactants leads to a decrease in washing performance and product stability in the simultaneous presence of anionic surfactants.
  • the cleaning performance of a detergent can be increased by movement, increased washing temperatures and / or longer contact time of the textile fabrics with the (aqueous) washing solution.
  • textile fabrics of wool become entangled with time and become heavily impacted when subjected to a water-based washing process, particularly in a household washing machine.
  • the unintended dimensional change (shrinkage and / or loss of shape) of the textile fabrics under the influence of mechanics, water and / or heat is also referred to as shrinkage. This also changes the haptic properties of the textile.
  • the detergent further contains 0.02 to 5% by weight of polyalkylene glycol.
  • hydrophobically modified, cationic polymer can be stably incorporated into a detergent by the addition of an alkylene glycol.
  • the polymer contains as a backbone a polysaccharide selected from the group comprising cellulose and cellulose derivatives. These polysaccharides have long been used as backings for fabric conditioning polymers due to their ready availability and structural similarity to cotton fibers. In addition, these compounds can easily be modified cationically and hydrophobically. It is preferred that the polymer as the backbone is a cellulose or a cellulose derivative selected from the group comprising methylcellulose, ethylcellulose, propylcellulose, methylethylcellulose,
  • Hydroxypropylmethylcellulose ethylhydroxyethylcellulose and methylethylhydroxyethylcellulose.
  • the polymer be used as cationic groups
  • Trialkylammoniumhydroxypropyl phenomenon and / or Trialkylammoniumethyl phenomenon contains.
  • the polymer having a C 8 -24 alkyl group is hydrophobically modified. It is particularly preferred that the polymer with a C 8 . 2 4-
  • Alkyldialkylammoniumhydroxypropyl distr and / or a C 8 -24-Alkyldialkylammoniumethyl distr is hydrophobically modified.
  • the hydrophobically-modified cationic polymer comprises one having trimethylammonium hydroxypropyl groups and C 8 .
  • the anionic surfactant comprises a mixture of at least three anionic surfactant compounds. Surprisingly, it has been found that when using a combination of at least three anionic surfactant compounds, a particularly stable detergent, in particular with regard to the presence of a cationic compound, is obtained with high cleaning performance.
  • the polyalkylene glycol is a polyethylene glycol having an average molecular weight between 200 and 400.
  • Polyethylene glycols having an average molecular weight between 200 and 400 are non-volatile liquids at room temperature and can be incorporated particularly well into a liquid detergent.
  • the invention relates to the use of the detergent according to the invention for reducing the shrinkage tendency during cleaning and / or conditioning of textile fabrics, in particular textile fabrics of wool and / or silk.
  • the invention also relates to the use of the detergent according to the invention
  • the invention relates to the use of the detergent according to the invention for reducing the residual expansion of textile fabrics, in particular of textile
  • the invention also encompasses a process for producing a detergent comprising a) from 5 to 15% by weight of anionic surfactant and b) from 0.01 to 1% by weight of a hydrophobically modified, cationic polymer in which the hydrophobically modified , cationic polymer is added in the last step in the form of an aqueous solution having a pH of 8.0 ⁇ 0.2.
  • Detergent can be incorporated and the resulting detergent is then clear.
  • the invention also relates to a process for producing a detergent comprising a) from 5 to 15% by weight of anionic surfactant, b) from 0.01 to 1% by weight of a hydrophobically modified, cationic polymer and c) from 0.02 to 5 % By weight of polyalkylene glycol, in which the hydrophobically modified, cationic polymer is added in the last step in the form of a slurries with the polyalkylene glycol.
  • the detergents according to the invention are described in detail below, inter alia, by way of examples.
  • the detergent necessarily contains a certain amount of anionic surfactant and a hydrophobically modified, cationic polymer.
  • the hydrophobically modified, cationic polymer serves to impart improved haptic properties, in particular softness, to the textiles treated therewith and to improve their elasticity and shrinkage tendency.
  • the amount of hydrophobically modified, cationic polymer in the detergent is 0.01 to 1 wt .-%, preferably 0.1 to 0.7 wt .-%, each based on the total detergent.
  • the polymer may comprise as a skeleton a polysaccharide selected from the group comprising glycogen, starch, chitin, callose, cellulose, dextran, tunicin, inulin, alginic acid, xanthan, gellan, guar, locust bean gum, carrageenan and derivatives.
  • the polymer contains as a backbone a cellulose or a cellulose derivative, wherein methylcellulose, ethylcellulose, propylcellulose, methylethylcellulose, hydroxyethylcellulose,
  • Ethylhydroxyethylcellulose or methylethylhydroxyethylcellulose is particularly preferred
  • the cationic modification of the polymer backbone is preferably carried out by means of
  • Trialkylammonium hydroxypropyl groups and / or trialkylammoniumethyl groups include, for example
  • Trimethylammoniumhydroxypropyl groups triethylammoniumhydroxypropyl groups
  • Ethyldimethylammoniumhydroxypropyl groups diethylmethylammoniumhydroxypropyl groups, with trimethylammoniumhydroxypropyl groups being preferred.
  • these groups also each include an anion, which is preferably a chloride.
  • the polymer be hydrophobically modified. It is particularly preferred that the polymer having a C 8 -24 alkyl group is hydrophobically modified. Particularly preferred C 8 -24 alkyl groups include C. 8 2 4- Alkyldialkylammoniumhydroxypropyl phenomenon and / or C 8 -24-Alkyldialkylammoniumethyl phenomenon. These groups can be easily introduced into the polymer backbone with the aid of the appropriate halides, halohydrins or epoxides. These groups also contain a charge-balancing anion, which is preferably a chloride.
  • the hydrophobically-modified cationic polymer comprises one having trimethylammonium hydroxypropyl groups and C 8 . 2 4-
  • Alkyldimethylammoniumhydroxypropyl groups substituted hydroxyethylcellulose. It has been found to be advantageous that the incorporation of such a substituted cellulose in liquid Detergent does not lead to an undesirably high increase in viscosity, as is partially observed in other cationically modified cellulose (derivatives) n.
  • the C 8 _24 alkyl group may preferably have an octyl group, nonyl group, decyl group,
  • the C 8 -24 alkyl group is a dodecyl group.
  • the hydrophobically-modified, cationic polymer comprises one having trimethylammonium hydroxypropyl groups and
  • Dodecyldimethylammonium hydroxypropyl substituted hydroxyethylcellulose It has been shown that these hydrophobically modified, cationic polymers not only efficiently on cotton fibers, but also particularly efficient on protein fibers, such as wool and / or silk, raise.
  • Trimethylammoniumhydroxypropyl substituents and dodecyldimethylammonium hydroxypropyl substituents is available, for example, under the name Softcat Polymer SX 400 H from Dow Chemicals.
  • the detergents contain anionic surfactant.
  • the anionic surfactant used is preferably sulfonates, sulfates, soaps, alkyl phosphates, anionic silicone surfactants and mixtures thereof.
  • Suitable surfactants of the sulfonate type are preferably C 9 .i 3 -alkylbenzenesulfonates and olefin isonates. Also suitable are C 2 -i 8-alkanesulfonates and the esters of a-sulfofatty acids (ester sulfonates), for example, the ⁇ -sulfonated Methylester of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Alk (en) ylsulfates are the alkali metal and in particular the sodium salts of
  • Sulfuric acid semi-esters of Ci 2 -C 8 fatty alcohols for example from coconut fatty alcohol,
  • Tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Ci 0 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred.
  • the Ci 2 -Ci 6 alkyl sulfates and Ci 2 -Ci 5 alkyl sulfates and Ci 4 -Ci 5 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with 1 to 6 moles of ethylene oxide are suitable.
  • 2 i-alcohols such as 2-methyl-branched Cg-n-alcohols having on average 3.5 mol of ethylene oxide (EO) or Ci 2 _i 8 -Fettalkohole with 1 to 4 EO, are suitable.
  • 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 magnesium or ammonium salts.
  • the anionic surfactants are in the form of their sodium salts.
  • Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine or methylethylamine.
  • the anionic surfactant used is a mixture of at least three different anionic surfactant compounds. Particularly preferred is a combination of C 9 .i 3 -Alkylbenzolsulfonat, fatty acid soap and
  • the content of a detergent to anionic surfactants is 5 to 15 wt .-% and
  • the detergents may contain further surfactants, with mixtures of anionic and nonionic surfactants being preferred from an application point of view.
  • the total surfactant content of a detergent is preferably below 25% by weight, and more preferably below 20% by weight, based on the total
  • Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated
  • Fatty acid alkyl esters Fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per Mol of alcohol is preferred.
  • the preferred ethoxylated alcohols include, for example, C12-14-alcohols with 3 EO, 4 EO or 7 EO, C9- n-alcohol with 7 EO, C-ms-alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -i8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as
  • Levels of ethoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank 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 containing EO and PO groups together in the molecule can also be used according to the invention.
  • the detergent contains a Ci 2 -i 8 -fatty alcohol with 7 EO or a Ci 3 .i 5 -oxo-alcohol with 7 EO as nonionic surfactant.
  • the content of nonionic surfactants is in the detergent preferably 1 to 17 wt .-%, preferably 2 to 12 wt .-% and in particular 3 to 10 wt .-%, each based on the total detergent.
  • the detergent in addition to the anionic surfactant and the hydrophobically-modified cationic polymer, contains from 0.02 to 5% by weight, based on the total detergent, of a polyalkylene glycol.
  • polyalkylene glycols for example, polyethylene glycols, polypropylene glycols or mixtures of polyethylene glycols and
  • Polypropylene glycols are used.
  • polyethylene glycols having an average molecular weight between 200 and 400 can be used.
  • hydrophobic-modified, cationic polymers, in particular hydrophobically-modified, cationic cellulose compounds can be dissolved only with difficulty and only in low concentrations in water. As a result, these polymers are difficult, stable to incorporate into aqueous detergents.
  • a mixture of the hydrophobically-modified, cationic polymer and a polyethylene glycol having an average molecular weight between 200 and 400 leads to a flowable slurry which can readily be incorporated into an aqueous detergent.
  • the resulting aqueous detergent has an increased stability.
  • the amount of hydrophobically-modified cationic polymer to polyalkylene glycol is preferably in the range of 1: 2 to 1: 5, and more preferably in the range of 1: 2.5 to 1: 3.5.
  • the detergents may contain other ingredients containing the
  • preferred laundry detergents additionally contain one or more substances from the group of builders, bleaches, bleach activators, bleach catalysts, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, Soil-release polymers optical brighteners, grayness inhibitors, anti-crease agents,
  • the detergents particularly preferably comprise, as further ingredients, builders, electrolytes, nonaqueous solvents, perfume, dyes, foam inhibitors,
  • the detergent is preferably liquid.
  • the liquid detergent contains water as the main solvent.
  • the detergents according to the invention can be used for cleaning and / or conditioning textile fabrics, in particular textile fabrics of wool and / or silk.
  • the detergents according to the invention can furthermore be used to improve the elasticity, in particular to reduce the residual elongation, of textile fabrics, in particular textile fabrics of wool and / or silk.
  • the detergents and cleaners according to the invention can be used to reduce the shrinkage tendency during the cleaning and / or conditioning of textile fabrics, in particular textile fabrics of wool and / or silk.
  • liquid detergents are carried out by means of customary and known methods and processes in which, for example, the constituents are simply mixed in stirred kettles, whereby water, non-aqueous solvents and surfactants are expediently initially introduced.
  • the fatty acid is added and the saponification of the fatty acid portion and the neutralization of the anionic surfactants, which are used in the acid form.
  • the other ingredients except the hydrophobically modified cationic polymer are added in portions.
  • the hydrophobically-modified cationic polymer is added either in the form of an aqueous solution with a pH of 8.0 ⁇ 0.2 or in the form of a slurries with polyalkylene glycol.
  • Table 1 shows the compositions of two inventive detergents E1 and E2 and of two comparative examples V1 and V2 (data in% by weight of active substance).
  • Detergents E1 and E2 according to the invention were stable on storage for several weeks and did not show any undesired changes.
  • samples of the detergent were stored in electronically controlled heating chambers at different temperatures (0 ° C, 23 ° C and 40 °) for several weeks (up to 12 weeks). During this period, visual, physical and olfactory assessments of the detergent were made.
  • washing tests were carried out with the detergents E1, E2, V1 and V2.
  • Wool detergent (the surfactant block comprised 13% by weight of nonionic surfactants, 0.5% by weight of anionic surfactants and 2.5% by weight of esterquat) with the wool program of
  • the fabrics were divided into two groups.
  • the first group was washed six times with 90 ml each of the detergent V2 and the second group was washed six times with 90 ml each of the detergent E2.
  • the same amount of SBL-2004 dirt load wipes from WFK Testgewebe GmbH was additionally present in each wash cycle. After hanging drying of the textile fabrics, the residual elongation was determined according to DIN 53 835, Part 13.
  • the fabrics washed with E2 showed a lower tendency to shrink during washing than the fabrics treated with the detergent V2.
  • the detergent E2 imparted to the textile fabrics treated therewith a pleasant soft feel.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un agent détergent renfermant : a) 5 à 15 % en poids d'un agent tensio-actif anionique et b) 0,01 à 1% en poids d'un polymère cationique, modifié hydrophobe. L'invention a pour objet un agent détergent qui nettoie, en particulier des textiles délicats en laine et/ou en soie, leur confère de la souplesse, améliore leur élasticité et réduit la tendance au retrait des textiles lors du lavage.
EP11711356.3A 2010-03-31 2011-03-31 Agent détergent pour textiles délicats Not-in-force EP2553077B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL11711356T PL2553077T3 (pl) 2010-03-31 2011-03-31 Środek piorący do wrażliwych tekstyliów

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE201010003535 DE102010003535A1 (de) 2010-03-31 2010-03-31 Waschmittel für empfindliche Textilien
DE201110006147 DE102011006147A1 (de) 2011-03-25 2011-03-25 Waschmittel für empfindliche Textilien II
PCT/EP2011/055008 WO2011121073A1 (fr) 2010-03-31 2011-03-31 Agent détergent pour textiles délicats

Publications (2)

Publication Number Publication Date
EP2553077A1 true EP2553077A1 (fr) 2013-02-06
EP2553077B1 EP2553077B1 (fr) 2015-10-14

Family

ID=44201984

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11711356.3A Not-in-force EP2553077B1 (fr) 2010-03-31 2011-03-31 Agent détergent pour textiles délicats

Country Status (4)

Country Link
EP (1) EP2553077B1 (fr)
ES (1) ES2552066T3 (fr)
PL (1) PL2553077T3 (fr)
WO (1) WO2011121073A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017102874A1 (fr) * 2015-12-18 2017-06-22 Henkel Ag & Co. Kgaa Composition de détergent liquide
KR20180107265A (ko) * 2016-02-15 2018-10-01 허큘레스 엘엘씨 홈케어 조성물
EP3722329A4 (fr) 2017-12-06 2021-09-08 Kao Corporation Dérivé de polysaccharide
US11655434B2 (en) 2017-12-06 2023-05-23 Kao Corporation Composition
CN111448348B (zh) 2017-12-06 2023-06-02 花王株式会社 布帛处理组合物
AU2018381370A1 (en) * 2017-12-06 2020-06-25 Kao Corporation Soil release agent

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69937745T2 (de) 1998-10-13 2008-11-27 The Procter & Gamble Company, Cincinnati Reinigungsmittelzusammensetzungen oder waschmittelkomponente
DE10027636A1 (de) * 2000-06-06 2001-12-13 Basf Ag Verwendung von kationisch modifizierten, teilchenförmigen, hydrophoben Polymeren als Zusatz zu Spül-, Pflege-, Wasch- und Reinigungsmitteln
US20030226212A1 (en) * 2002-04-16 2003-12-11 Jiping Wang Textile mill applications of cellulosic based polymers to provide appearance and integrity benefits to fabrics during laundering and in-wear
WO2004069979A2 (fr) 2003-02-03 2004-08-19 Unilever Plc Compositions de nettoyage et de conditionnement pour blanchisserie
MX319376B (es) 2006-03-22 2014-04-11 Procter & Gamble Composicion liquida de tratamiento.
US7723453B2 (en) * 2006-05-04 2010-05-25 Conopco, Inc. Hydrophobically modified cationic polymers
GB0618542D0 (en) 2006-09-21 2006-11-01 Unilever Plc Laundry compositions
DE102006059465A1 (de) * 2006-12-14 2008-06-19 Henkel Kgaa Moisturizing-Duschbad mit optimierten Schaumeigenschaften

Non-Patent Citations (1)

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Title
See references of WO2011121073A1 *

Also Published As

Publication number Publication date
EP2553077B1 (fr) 2015-10-14
WO2011121073A1 (fr) 2011-10-06
PL2553077T3 (pl) 2016-03-31
ES2552066T3 (es) 2015-11-25

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