EP2181186A1 - Solutions d'agents tensio-actifs stables au stockage pour blanchiment au peroxyde - Google Patents

Solutions d'agents tensio-actifs stables au stockage pour blanchiment au peroxyde

Info

Publication number
EP2181186A1
EP2181186A1 EP08708902A EP08708902A EP2181186A1 EP 2181186 A1 EP2181186 A1 EP 2181186A1 EP 08708902 A EP08708902 A EP 08708902A EP 08708902 A EP08708902 A EP 08708902A EP 2181186 A1 EP2181186 A1 EP 2181186A1
Authority
EP
European Patent Office
Prior art keywords
solutions
solutions according
manganese
complex
bleaching
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.)
Withdrawn
Application number
EP08708902A
Other languages
German (de)
English (en)
Inventor
Herbert Bachus
Christian Dörfler
Bernd Horrer
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.)
CHT Germany GmbH
Original Assignee
CHT R Beitlich GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CHT R Beitlich GmbH filed Critical CHT R Beitlich GmbH
Publication of EP2181186A1 publication Critical patent/EP2181186A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes

Definitions

  • the invention relates to the use of storage-stable surfactant solutions in bleaching processes with hydrogen peroxide, which use manganese complexes, in particular of triazacyclononanones, as catalyst.
  • Hydrogen peroxide is one of the most important bleaching agents today, which decomposes when used in water and oxygen. In contrast to chlorine-containing bleaching agents, there are no toxic or carcinogenic halogen-containing substances. Thus, it continues to gain ground in many industrial areas. Typical applications for hydrogen peroxide are the paper and pulp industry, the textile finishing or household detergents, where hydrogen peroxide forms on dissolving perborates or percarbonates. 2,200,000 tonnes of hydrogen peroxide are produced each year, 50% for paper and pulp and 10% for textile bleaching.
  • the first catalyst in a commercial household detergent was a binuclear manganese complex with one 1,4,7-trimethyl-1,4,7-triazacyclononanone (L) connected by three oxygen bridges:
  • the catalyst was first used by Wieghardt et al. (Lit. 29-32) describe and 0 C and pH ranges effectively 9-11 even at 4O, but was due to Fiber damage of the cellulosic material after a short time taken back from the market.
  • Me 4 dtne 1, 2-bis (4,7-dimethyl-l, 4,7-triazacyclonon-1-yl) ethane.
  • These catalysts can also lower while still providing the desired white effect treatment temperatures in the textile bleaching of 98 0 C or more, for example 8O 0 C.
  • pulp bleaching it is customary to sequester and / or remove the manganese ions for manganese removal prior to bleaching with hydrogen peroxide in precursors with EDTA or DTPA.
  • these two complexing agents are neither biodegradable nor are they eliminated in sewage treatment plants.
  • EDTA and DTPA still dominate complexing agent use in pulp bleaching.
  • These two complexing agents also allow for efficient bleaching with cat 1) because they bind the manganese liberated during the bleaching process from the catalyst and thereby reduce the peroxide decomposing and cotton damaging effect.
  • WO 2007/042192 A2 describes bleach compositions containing a defined Mn catalyst, an aminocarboxylate-based complexing agent, hydrogen peroxide and, in addition, a carbonate or borate buffer.
  • the buffer keeps the pH constant over a certain range and thus contributes to a further stabilization of the bleaching compositions and in particular of the Mn complexes contained therein.
  • the complexing agents used can be EDTA, HEDTA, NTA, N-hydroxyethylaminodiacetic acid, DTPA, MGDA or alanine-N, N-diacetic acid.
  • amines are also used for stabilizing bleach compositions, as described in DE 197 02 734 A1.
  • compositions described therein are biodegradable aliphatic or alicyclic amines having 1 to 12 C atoms; In addition, these amines, which contain only one N atom in each case, can additionally carry (also in each case several) hydroxyl groups.
  • complexing agents for example, aminocarboxylates are used in these compositions, especially those containing an N, N-diacetic acid grouping, such as EDTA, NTA, aspartic acid / glutamic acid or .beta.-alanine-N, N-diacetic acid, iminodiacetic acid.
  • a disadvantage of the previously known in the prior art method is that the catalyst is always mixed separately from the actual bleaching composition to be used, which not only has a higher equipment complexity by additional metering result. Moreover, at least with a dimension of the mass of the catalyst with an (analytical) balance, the risk of overdosing of the catalyst to be used only in small quantities increases. In addition to the catalyst, the actual bleaching agent is usually added separately.
  • the pH adjustment has an influence on the stability of the product. If the specified pH is not adjusted, no storage-stable product can be formulated.
  • the object of the present invention is accordingly to provide stable and, in particular, storage-stable compositions which can be used in peroxide bleaching and over which a bleach-active catalyst no longer has to be added separately. Such compositions would therefore already contain the catalyst in solution, which would make an additional separate metering or dissolution of a (catalyst) powder superfluous.
  • compositions except for the blending agent to be blended separately, should contain all the excipients and agents necessary for peroxide bleaching so that the amount of blending and / or metering operations can be minimized by the use of such compositions.
  • the invention relates to storage-stable surfactant solutions
  • At least one manganese-based metal complex of general formula I admixed with a surfactant as process auxiliary
  • L represents a ligand of an organic molecule having a number of nitrogen atoms which coordinate via its nitrogen atoms to the manganese center (centers); Mn for manganese in the oxidation state III or IV; n and m are each independently an integer of 1 to 3; X for a coordination or bridge species; p is an integer having a value of 0 to 4; z for a charge of the complex, which is a whole negative and positive
  • coordination species are understood in particular to be monodentate ligands.
  • bridge species summarizes those multidentate ligands which connect at least 2 metal atoms (bridging) to one another (for a more detailed explanation of these terms, see “Coordination Chemistry” by L. Gade, Wiley-VCH 1998).
  • the catalyst can be incorporated into existing auxiliaries, that is, for example, commercially available surfactant solutions / detergents, and the resulting compositions nevertheless have sufficient storage stability. Surprisingly, the solubility in the detergent is sufficient and the shelf life at 25 0 C is even several months. Because of these conditions, a large amount of (storage-stable) surfactant solution can be prepared directly, so that the error in the dimension of the amount of catalyst required for the admixture is reduced accordingly.
  • the surfactant solutions according to the invention may furthermore contain at least one biodegradable or at least bioeliminable complexing agent (b).
  • the solutions are characterized in that the
  • Me 4 dtne l, 2-bis (4,7-dimethyl-l, 4,7-triazacyclonon-1-yl) ethane.
  • EDTA and DTPA are commonly considered to be strongly binding complexing agents for a wide variety of metal cations. Due to the associated very high complex formation constants, the binding capacity is extremely strong. However, with the aid of the present invention it is preferred to use complexing agent with significantly lower complex formation constant, also in view of the associated improved environmental properties. Accordingly, it is particularly preferred for the purposes of the present invention if the complexing agents have a complex formation constant of less than or equal to 12, in particular less than or equal to 10.
  • aminocarboxylic acids are suitable as complexing agents, examples being:
  • Biodegradable complexing agents according to OECD 302 B Carboxymethylated polyethylenimine (Trilon P ® )
  • biodegradability in the sense of the present invention is defined and measured as follows:
  • the degradation is determined by periodic measurements of DOC (Dissolved Organic Carbon), CO 2 or O 2 .
  • DOC Dissolved Organic Carbon
  • O 2 Organic 2
  • the criterion for easy biodegradability is the achievement of 70% DOC elimination and 60% oxygen consumption or production of carbon dioxide within 10 days after exceeding the degree of degradation of 10%.
  • OECD 302 methods :
  • DOC, CO 2 and O 2 are measured at periodic intervals and set in relation to the DOC and TOC at the beginning of the test.
  • the percentage degradation rate calculated in this way gives the degradation curve plotted against time.
  • the criterion for a potential biodegradability is the achievement of> 20% DOC decrease or oxygen consumption after 28 days. Complete biodegradability (elimination) is assumed to be> 70% after 28 days.
  • the product is readily biodegradable according to OECD criteria.
  • the actual bleaching agent used in each of the further sections of the description and the patent claims is a 35% strength by weight aqueous solution of hydrogen peroxide.
  • component (a) and (b) may be preferred in various proportions in the mixtures according to the invention. However, for the purposes of the present invention, preference is given to adjusting the weight ratio of component (a) to component (b) in the range from 20: 1 to 500: 1, more preferably within a range from 80: 1 to 300: 1 with the advantages of higher whiteness with acceptable fiber damage.
  • solutions according to the invention need not contain any buffer substances, in particular no buffer substances based on borates and / or carbonates, for stabilizing the manganese complexes contained in these solutions.
  • the effectiveness of the bleaching mixtures can be substantially increased by an additional component (c) in the form of sodium hydroxide and / or potassium hydroxide. Accordingly, it is particularly preferred that the mixtures according to the invention contain these additional alkaline substances.
  • the additional component (c) in the form of sodium and / or potassium hydroxide solution is not incorporated into the formulation / blend but is added to the treatment liquor see, for example, series of experiments 1.
  • the addition of the liquor to the treatment liquor is necessary around the optimum pH range for to adjust the bleaching with the catalyst.
  • Another embodiment of the present invention is the use of the solutions as defined above for the peroxide bleaching of cellulosic substrates.
  • cotton or shredded wood material is particularly preferably bleached, for example in textile finishing, household washing, pulp bleaching or paper bleaching.
  • a commercially available liquid detergent Felosan ® NFG were, for the examples and comparative examples and the following sodium salt solutions of complexing agents used:
  • Comparative Example 1 shows a non-catalyzed bleach. The residual peroxide is over 90% very high, the bleach was consumed little and the whiteness is only 59 Berger units. Comparative Example 2 shows the effect of cat 1) without addition of further complexing agents. Whiteness increases by 3 points, but the damage factor also increases to 0.3.
  • Comparative Example 5 demonstrates that even a good heavy metal complexing agent such as DTPMP has little positive effect in such an all-in process.
  • Inventive Examples 1 to 4 show all fiber damage factors ⁇ 0.2 and the same final whiteness as EDTA or DTPA. Phosphonates such as DTPMP are less effective and phosphonates are not sufficiently eliminated by OECD 301 or OECD 302 methods.
  • the catalyst is stirred into the detergent and adjusted to the desired pH with acetic acid or formic acid. It produces intense red-colored, clear solutions that are stable at temperatures below 25 0 C for months.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne l'emploi de solutions d'agents tensio-actifs stables au stockage dans des procédés de blanchiment au peroxyde d'hydrogène utilisant comme catalyseur, un complexe de manganèse, en particulier de triazacyclononanones.
EP08708902A 2007-02-13 2008-02-12 Solutions d'agents tensio-actifs stables au stockage pour blanchiment au peroxyde Withdrawn EP2181186A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007006908A DE102007006908A1 (de) 2007-02-13 2007-02-13 Katalysierte Peroxidbleiche ("Katalysator-Bleiche")
PCT/EP2008/051664 WO2008098921A1 (fr) 2007-02-13 2008-02-12 Solutions d'agents tensio-actifs stables au stockage pour blanchiment au peroxyde

Publications (1)

Publication Number Publication Date
EP2181186A1 true EP2181186A1 (fr) 2010-05-05

Family

ID=39271167

Family Applications (2)

Application Number Title Priority Date Filing Date
EP08708902A Withdrawn EP2181186A1 (fr) 2007-02-13 2008-02-12 Solutions d'agents tensio-actifs stables au stockage pour blanchiment au peroxyde
EP08101523A Withdrawn EP1967577A1 (fr) 2007-02-13 2008-02-12 Blanchiment peroxyde catalysé (blanchiment à catalyseur)

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP08101523A Withdrawn EP1967577A1 (fr) 2007-02-13 2008-02-12 Blanchiment peroxyde catalysé (blanchiment à catalyseur)

Country Status (3)

Country Link
EP (2) EP2181186A1 (fr)
DE (1) DE102007006908A1 (fr)
WO (1) WO2008098921A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5401034B2 (ja) 2007-12-19 2014-01-29 ライオン株式会社 漂白助剤、および該漂白助剤を含有する漂白助剤粒子
EP2103604A1 (fr) 2008-03-17 2009-09-23 Evonik Degussa GmbH Procédé de fabrication d'épichlorhydrine
DE102008034231A1 (de) * 2008-07-23 2010-01-28 Cht R. Beitlich Gmbh Katalysierte Peroxidbleiche ("Katalysator-Bleiche-Variante 3: All-in-one")
CN106111254B (zh) * 2016-08-26 2019-07-05 江苏新业重工股份有限公司 一种辊压机的压辊

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5480575A (en) * 1992-12-03 1996-01-02 Lever Brothers, Division Of Conopco, Inc. Adjuncts dissolved in molecular solid solutions
GB9305598D0 (en) * 1993-03-18 1993-05-05 Unilever Plc Bleach catalyst composition
US5429769A (en) * 1993-07-26 1995-07-04 Lever Brothers Company, Division Of Conopco, Inc. Peroxycarboxylic acids and manganese complex catalysts
GB9523654D0 (en) * 1995-11-18 1996-01-17 Ciba Geigy Ag Fabric bleaching composition
DE19638569A1 (de) * 1996-09-20 1998-04-02 Bayer Ag Bleichregulatoren und Bleichverfahren damit
DE19702734A1 (de) * 1997-01-27 1998-07-30 Basf Ag Wasch- und Reinigungsmittel-Formulierung mit einem Bleichsystem sowie einer Mischung aus Aminen und Komplexbildnern
ATE315627T1 (de) * 1999-07-14 2006-02-15 Ciba Sc Holding Ag Metallkomplexe von tripodalenliganden
FR2813896A1 (fr) * 2000-09-14 2002-03-15 Atofina Procede de delignification et blanchiment par un oxydant et un catalyseur d'oxydoreduction
US20040048763A1 (en) * 2002-08-27 2004-03-11 The Procter & Gamble Co. Bleach compositions
DK1433839T4 (da) * 2002-12-24 2015-06-15 Dalli Werke Gmbh & Co Kg Optimeret vaske- og rengøringsmiddelsystem med henblik på forbedret blegevirkning ved lave temperaturer
DE10301535A1 (de) * 2003-01-17 2004-07-29 Cht R. Beitlich Gmbh Verfahren zur Veredlung von textilem Fasermaterial
DE102004044411A1 (de) * 2004-09-14 2006-03-30 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophob modifizierte Polycarboxylate
PL1741774T3 (pl) * 2005-07-08 2009-01-30 Unilever Nv Kompozycje przeznaczone do automatycznego zmywania naczyń
CA2624846C (fr) * 2005-10-12 2014-02-11 Unilever Plc Blanchiment catalytique de substrats industriels

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008098921A1 *

Also Published As

Publication number Publication date
WO2008098921A1 (fr) 2008-08-21
DE102007006908A1 (de) 2008-08-14
EP1967577A1 (fr) 2008-09-10

Similar Documents

Publication Publication Date Title
DE2226784C3 (de) Mittel zum Stabilisieren von Peroxyverbindungen in wäßrig-alkalischer Lösung und seine Verwendung
EP0713882B1 (fr) Chitosanes phosphonométhylées
EP0628655B1 (fr) Adjuvants de blanchiment
DE2609039B2 (de) Verfahren zum Herstellen von beständigem Natriumpercarbonat
EP2181186A1 (fr) Solutions d'agents tensio-actifs stables au stockage pour blanchiment au peroxyde
DE2500428C2 (de) Aminomethylphosphonsäurederivate, Verfahren zu deren Herstellung und deren Verwendung als Sequestriermittel
DE1617161A1 (de) Verstaerkungsmittel fuer synthetische Detergentien
DE2910403A1 (de) Bleichmittel
DE2326467C3 (fr)
DE102008034231A1 (de) Katalysierte Peroxidbleiche ("Katalysator-Bleiche-Variante 3: All-in-one")
DE3002271A1 (de) Bleichmittel
EP0510331A1 (fr) Protéine comme stabilisateur biodégradable pour le blanchiment à l'oxygène utilisé dans le lavage du linge
EP1583861B1 (fr) Procede pour le finissage de matieres fibreuses textiles
EP0315848B1 (fr) Procédé pour le prétraitement de matériaux textiles
DD141844B1 (de) Bleichmittel
DE19638569A1 (de) Bleichregulatoren und Bleichverfahren damit
DE3009473A1 (de) Natriumhydrosulfitzusammensetzung
CH676256A5 (fr)
EP1634990A1 (fr) Adjuvant liquide pour l'ennoblissement de produits textiles.
DE19614628A1 (de) Vorbehandlung von Textilien
EP1634991A2 (fr) Adjuvant liquide pour le traitement et l'ennoblissement de produits textiles.
EP1528147B1 (fr) Adjuvant de teinture
DE1695089C3 (de) 2-(3'-Halogen-2-suIfo-4-stilbyl-) -naphtho [1,2 zu d] triazole Verfahren zu ihrer Herstellung und deren Verwendung
EP0086898A1 (fr) Suspensions aqueuses de péroxodisulfate et leur usage comme agent de désencollage pour des textiles imprégnees d'amidon
EP0775226B2 (fr) Utilisation d'un concentre d'agents stabilisants pour solutions aqueuses de blanchiment et de traitement a base de peroxyde d'hydrogene et/ou d'autres composes peroxo organiques et/ou inorganiques

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: 20091221

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 MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: HORRER, BERND

Inventor name: DOERFLER, CHRISTIAN

Inventor name: BACHUS, HERBERT

17Q First examination report despatched

Effective date: 20110426

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20121116