Patent Application
20110082037
The present invention is related to the area of agriculture and refers to new adjuvant compositions comprising two types of non-ionic surfactants.
The crop protection market represents a total value of around 22 billion/year. By far the largest single biocides are glyphosate-based compositions, which account for approximately 15% of the total market. In the past four years, with the extended cultivation of GMO crops, glyphosate-based product sales have grown by 12%/year and they reached a value of
3.4 billion in 2005. It has been calculated that around 250,000 tons of various glyphosate formulations are sprayed on crops every year. Most glyphosate-based herbicides are formulated with adjuvants (also known as potentiators) to maximise their efficacy by fulfilling several functions. An adjuvant must provide good wetting of the leaf surface, facilitate the foliar penetration of the biocide under a wide range of climatic conditions and enhance, or at least not inhibit, translocation of the biocide, in particular the herbicide into the plant. In addition, it must not produce phytotoxic effects when used on specific resistant crops. Tallow amine ethoxylates are most frequently used as adjuvants with biocides, in particular as adjuvants for glyphosates. These are mixtures of ethoxylated long-chain alkyl amines derived from fatty acids. The amounts of biocides and tallow amine ethoxylates used have changed little over the last few years and, despite concerns over eye irritation and eco-toxicity label ratings (“WARNING” or “DANGER”), they continue to be used. Alternative adjuvant chemistries, such as phosphate esters, are available.
European patent EP 0688165 B1 (KVK Agro) relates to a stable concentrated herbicide suspension containing high amounts of electrolytes and herbicide in finely divided form, which dissolves easily on dilution for spray. The compositions may contain alkoxylated alkyloligoglycosides. European patent EP 1063883 B1 (Dow Agrosciences) refers to the use of alkoxylated alkyl oligoglycosides in compositions comprising pesticides which are insoluble or very little soluble in water. The use of alkyl polyglucosides containing EO-units as adjuvants for pesticides is also known from U.S. Pat. No. 6,746,988 (Syngenta), however, these compounds are obtained by acetalisation of ethoxylated fatty alcohols with glucose, thus the polyether chain links the fatty alcohol and the glucose part of the molecule. International patent application WO 05/087785 A1 (Cognis) discloses an improved process for making ethoxylates of alkyl oligoglycosides and their use as adjuvants, in particular for glyphosate-based herbicides.
Nevertheless, the alternatives known from the state of the art do not achieve the level of weed control obtained with tallow amine ethoxylates in terms of price and performance and/or are very difficult to handle because of their physical properties, such as foam generation, low temperature behaviour, miscibility in cold water, gel formation and flocculation. It has therefore been the object of the present invention developing new adjuvants for biocides, in particular for glyphosate-based compositions showing improved performance, especially compared with tallow amine ethoxylates and—ethoxylated—alkyl oligoglycosides.
The present invention refers to adjuvant compositions, comprising
Surprisingly it has been observed that the mixtures according to the present invention improves the activity of biocides in general and glyphosate in particular when compared with standard adjuvants like tallow amine ethoxylates, alkyl oligoglycosides or ethoxylated alkyl oligoglycosides alone. The mixtures also exhibit an improved cold water miscibility, cold temperature viscosity and reduced foaming.
Alkoxylation products of alkyl and alkenyl oligoglycosides are well known from the state of the art. For example, an improved process for obtaining these non-ionic surfactant is disclosed in WO 05/087785 A1 (Cognis), which is hereby incorporated by reference. Patent literature very often refers to “APG ethoxylates”, however, these products usually represent acetalisation products of glucose and fatty alcohol ethoxylates, thus the polyether chain links the sugar and the fatty part of the molecule. It is explicitely stated that these types of surfactants are not covered by the phrase “Alk(en)yl oligoglycoside alkoxylates”, since it is essential for the success of the technical teaching associated with the present invention, that alkoxylation takes place at the free hydroxyl groups of the sugar moiety in order to provide the beneficial effects within the blend. Therefore, compound (a) truly represent adducts of alkylene oxides to alk(en)yl oligoglycosides, and more particular adducts of ethylene oxide and/or propylene oxide to alk(en)yl oligoglycosides.
As far as the glycoside part of the molecule is concerned it may be derived from aldoses or ketoses containing 5 or 6 carbon atoms, preferably glucose. Accordingly, the preferred alkyl and/or alkenyl oligoglycosides (alkoxylates) are alkyl or alkenyl oligoglucoside (alkoxylate)s. The alk(en)yl oligoglycoside part according to the invention corresponds to formula (I):
R1O[G]p (I)
wherein R1 is an alkyl or alkenyl radical having from 6 to 22 carbon atoms, G is a sugar unit having 5 or 6 carbon atoms and p is a number from 1 to 10. The index p in general formula (I) indicates the degree of oligomerisation (DP degree), i.e. the distribution of mono- and oligoglycosides, and is a number of 1 to 10. Whereas p in a given compound must always be an integer and, above all, may assume a value of 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined calculated quantity which is mostly a broken number. Alk(en)yl oligoglycosides having an average degree of oligomerisation p of 1.1 to 3.0 are preferably used. Alk(en)yl oligoglycosides having a degree of oligomerisation below 1.7 and, more particularly, between 1.2 and 1.4 are preferred from the applicational point of view. The alkyl or alkenyl radical R1 may be derived from primary alcohols containing 4 to 22 and preferably 8 to 16 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof such as are formed, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Alkyl oligoglucosides based on hydrogenated C8-C16 coconut oil alcohol having a DP of 1 to 3 are preferred.
In a preferred embodiment of the present invention said alk(en)yl oligoglycoside alkoxylates represent adducts of on average 1 to 20, preferably 1 to 5 Moles ethylene oxide and/or propylene oxide to alk(en)yl oligoglucosides, preferably alkyl oligoglucosides. More particularly the alk(en)yl oligoglycoside alkoxylates represent adducts of on average 2 to 10 Moles ethylene oxide and 1 to 3 Moles propylene oxide to C8-C10 and/or C12-C14 alkyl oligoglucosides.
Primary alcohol alkoxylates, forming compound (b), are well known as non-ionic surfactants derived from alkoxylation of long-chain petrochemical or oleochemical alcohols. Typically the compounds follow general formula (II),
R2O(CH2CHR3O)nH (II)
in which R2 stands for a linear or branched, saturated or unsaturated hydrocarbon radical having 4 to 22, preferably 12 to 22 and more preferably 16 to 18 carbon atoms and 0 or 1 to 3 double bonds, R3 represents either hydrogen or a methyl group and n stands for a number of 1 to 20, preferably 2 to 10. Typical examples are adducts of 1 to 20, preferably 2 to 10 Moles ethylene oxide and/or propylene oxide to butanol, pentanol, capryl alcohol, caprylyl alcohol, caprinyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linolyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures, like cocoyl alcohol or tallowyl alcohol. Also useful are petrochemical-based alcohols with odd carbon numbers, like for example the Dobanol types (Shell). The preferred primary alcohol alkoxylates represent adducts of on average 1 to 20 Moles ethylene oxide and/or propylene oxide to saturated or unsaturated fatty alcohols having 16 to 22 carbon atoms, and more particularly adducts of 5 to 15 Moles ethylene oxide to unsaturated alcohols having 16 to 22 carbon atoms. A typical example is oleyl alcohol+10 EO.
The compositions according to the present inventions may contain compounds (a) and (b) in weight ratios of 10:90 to 90:10, preferably 25:75 to 75:25 and more preferably 40:60 to 60:40. Usually these compositions represent aqueous solutions or pastes showing water contents of 10 to 90% b.w., depending whether they should deal for making diluted or concentrated products. The composition may also contain organic co-solvents, like glycerol or propylene glycol in amounts up to 25% b.w. The most preferred composition is a mixture consisting of about 55 to 65% b.w. ethoxylated alkyl oligoglucosides, about 15 to 25% b.w. oleyl alcohol+10EO and about 15 to 25% b.w. glycerol under the condition that the amounts add to 100% b.w.
Another object of the present invention is directed to the use of compositions comprising
in agriculture, in particular the invention covers also the use of said compositions as adjuvants and/or emulsifiers for biocides.
Finally, the invention also refers to a method for improving the growth of plants by applying a composition comprising at least one biocide and an adjuvant mixture, comprising
For preparing the end-composition, the blends according to the present invention are usually mixed with the respective biocide under vigorous stirring and optionally at elevated temperature. The nature of the biocides is not critical since it fully depends on the proposed application. The preferred biocides, however, are herbicides and among this group preferably glyphosates and glufosinates. Nevertheless, in the following various types of biocides are compiled which in general are all useful for the preparation of agricultural compositions, especially for crop protection:
A biocide (component b) is a chemical substance capable of killing different forms of living organisms used in fields such as medicine, agriculture, forestry, and mosquito control. Usually, biocides are divided into two sub-groups:
Biocides can also be added to other materials (typically liquids) to protect the material from biological infestation and growth. For example, certain types of quaternary ammonium compounds (quats) can be added to pool water or industrial water systems to act as an algicide, protecting the water from infestation and growth of algae.
The U.S Environmental Protection Agency (EPA) defines a pesticide as “any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest”.[1] A pesticide may be a chemical substance or biological agent (such as a virus or bacteria) used against pests including insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms) and microbes that compete with humans for food, destroy property, spread disease or are a nuisance. In the following examples, pesticides suitable for the agrochemical compositions according to the present invention are given:
Fungicides
A fungicide is one of three main methods of pest control—the chemical control of fungi in this case. Fungicides are chemical compounds used to prevent the spread of fungi in gardens and crops. Fungicides are also used to fight fungal infections. Fungicides can either be contact or systemic. A contact fungicide kills fungi when sprayed on its surface. A systemic fungicide has to be absorbed by the fungus before the fungus dies. Examples for suitable fungicides, according to the present invention, encompass the following species: (3-ethoxypropyl)mercury bromide, 2-methoxyethylmercury chloride, 2-phenylphenol, 8-hydroxyquinoline sulfate, 8-phenylmercurioxyquinoline, acibenzolar, acylamino acid fungicides, acypetacs, aldimorph, aliphatic nitrogen fungicides, allyl alcohol, amide fungicides, ampropylfos, anilazine, anilide fungicides, antibiotic fungicides, aromatic fungicides, aureofungin, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxy,l benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb, benzalkonium chloride, benzamacril, benzamide fungicides, benzamorf, benzanilide fungicides, benzimidazole fungicides, benzimidazole precursor fungicides, benzimidazolylcarbamate fungicides, benzohydroxamic acid, benzothiazole fungicides, bethoxazin, binapacryl, biphenyl, bitertanol, bithionol, blasticidin-S, Bordeaux mixture, boscalid, bridged diphenyl fungicides, bromuconazole, bupirimate, Burgundy mixture, buthiobate, butylamine, calcium polysulfide, captafol, captan, carbamate fungicides, carbamorph, carbanilate fungicides, carbendazim, carboxin, carpropamid, carvone, Cheshunt mixture, chinomethionat, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin, chlorothalonil, chlorquinox, chlozolinate, ciclopirox, climbazole, clotrimazole, conazole fungicides, conazole fungicides (imidazoles), conazole fungicides (triazoles), copper(II) acetate, copper(II) carbonate, basic, copper fungicides, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper(II) sulfate, copper sulfate, basic, copper zinc chromate, cresol, cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cyclic dithiocarbamate fungicides, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet, DBCP, debacarb, decafentin, dehydroacetic acid, dicarboximide fungicides, dichlofluanid, dichlone, dichlorophen, dichlorophenyl, dicarboximide fungicides, dichlozoline, diclobutrazol, diclocymet, diclomezine, dicloran, diethofencarb, diethyl pyrocarbonate, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinitrophenol fungicides, dinobuton, dinocap, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, dithiocarbamate fungicides, DNOC, dodemorph, dodicin, dodine, DONATODINE, drazoxolon, edifenphos, epoxiconazole, etaconazole,etem, ethaboxam, ethirimol, ethoxyquin, ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, formaldehyde, fosetyl, fuberidazole, furalaxyl, furametpyr, furamide fungicides, furanilide fungicides, furcarbanil, furconazole, furconazole-cis, furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, hydrargaphen, hymexazol, imazalil, imibenconazole, imidazole fungicides, iminoctadine, inorganic fungicides, inorganic mercury fungicides, iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isovaledione, kasugamycin, kresoxim-methyl, lime sulphur, mancopper, mancozeb, maneb, mebenil, mecarbinzid, mepanipyrim, mepronil, mercuric chloride, mercuric oxide, mercurous chloride, mercury fungicides, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, metiram, metominostrobin, metrafenone, metsulfovax, milneb, morpholine fungicides, myclobutanil, myclozolin, N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin, nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace, organomercury fungicides, organophosphorus fungicides, organotin fungicides, orysastrobin, oxadixyl, oxathiin fungicides, oxazole fungicides, oxine copper, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury nitrate, phenylmercury salicylate, phenylsulfamide fungicides, phosdiphen, phthalide, phthalimide fungicides, picoxystrobin, piperalin, polycarbamate, polymeric dithiocarbamate fungicides, polyoxins, polyoxorim, polysulfide fungicides, potassium azide, potassium polysulfide, potassium thiocyanate, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyracarbolid, pyraclostrobin, pyrazole fungicides, pyrazophos, pyridine fungicides, pyridinitril, pyrifenox, pyrimethanil, pyrimidine fungicides, pyroquilon, pyroxychlor, pyroxyfur, pyrrole fungicides, quinacetol, quinazamid, quinconazole, quinoline fungicides, quinone fungicides, quinoxaline fungicides, quinoxyfen, quintozene, rabenzazole, salicylanilide, silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, spiroxamine, streptomycin, strobilurin fungicides, sulfonanilide fungicides, sulfur, sultropen, TCMTB, tebuconazole, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thiazole fungicides, thicyofen, thifluzamide, thiocarbamate fungicides, thiochlorfenphim, thiomersal, thiophanate, thiophanate-methyl, thiophene fungicides, thioquinox, thiram, tiadinil, tioxymid, tivedo, tolclofos-methyl, tolnaftate, tolylfluanid, tolylmercury acetate, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazine fungicides, triazole fungicides, triazoxide, tributyltin oxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, unclassified fungicides, undecylenic acid, uniconazole, urea fungicides, validamycin, valinamide fungicides, vinclozolin, zarilamid, zinc naphthenate, zineb, ziram, zoxamide and their mixtures.
Herbicides
An herbicide is a pesticide used to kill unwanted plants. Selective herbicides kill specific targets while leaving the desired crop relatively unharmed. Some of these act by interfering with the growth of the weed and are often based on plant hormones. Herbicides used to clear waste ground are nonselective and kill all plant material with which they come into contact. Herbicides are widely used in agriculture and in landscape turf management. They are applied in total vegetation control (TVC) programs for maintenance of highways and railroads. Smaller quantities are used in forestry, pasture systems, and management of areas set aside as wildlife habitat. In the following, a number of suitable herbicides are compiled:
Insecticides
An insecticide is a pesticide used against insects in all developmental forms. They include ovicides and larvicides used against the eggs and larvae of insects. Insecticides are used in agriculture, medicine, industry and the household. In the following, suitable insecticides are mentioned:
Rodenticides
Rodenticides are a category of pest control chemicals intended to kill rodents. Rodents are difficult to kill with poisons because their feeding habits reflect their place as scavengers. They would eat a small bit of something and wait, and if they do not get sick, they would continue eating. An effective rodenticide must be tasteless and odorless in lethal concentrations, and have a delayed effect. In the following, examples for suitable rodenticides are given:
Miticides, Moluscicides and Nematicides
Antimicrobials
In the following examples, antimicrobials suitable for agrochemical compositions according to the present invention are given. Bactericidal disinfectants mostly used are those applying
As antiseptics (i.e., germicide agents that can be used on human or animal body, skin, mucoses, wounds and the like), few of the above mentioned disinfectants can be used under proper conditions (mainly concentration, pH, temperature and toxicity toward man/animal). Among them, important are
Bactericidal antibiotics kill bacteria; bacteriostatic antibiotics only slow down their growth or reproduction. Penicillin is a bactericide, as are cephalosporins. Aminoglycosidic antibiotics can act in both a bactericidic manner (by disrupting cell wall precursor leading to lysis) or bacteriostatic manner (by connecting to 30 s ribosomal subunit and reducing translation fidelity leading to inaccurate protein synthesis). Other bactericidal antibiotics according to the present invention include the fluoroquinolones, nitrofurans, vancomycin, monobactams, co-trimoxazole, and metronidazole.
Greenhouse experiments were conducted to investigate the potency of the mixtures of alkoxylated oligoglycosides and alkoxylated primary alcohols as adjuvants for glyphosate. Winter wheat (Triticum aestivum) was used as a model for difficult-to-wet grasses and black night-shade (Solanum nigrum) was used as a model plant with an easy-to-wet, but difficult-to-penetrate, leaf surface. Both were grown in a growth chamber under 14 hours of light, at 18/12(±0.5)° C. (day/night) temperature, and in 70/80(±5)% (day/night) relative humidity. Light was provided by high-pressure mercury lamps and fluorescent tubes to give 70 W/m2 (PAR) at leaf level. The plants were grown in 11 cm diameter plastic pots filled with a mixture of sand and humic potting soil (1:2 by volume). The pots were placed on sub-irrigation matting which was wetted daily with half-strength nutrient solution. After emergence, the wheat seedlings were thinned to six plants/pot for the efficacy experiments. Black nightshade seedlings were thinned to one plant/pot. Black nightshade and wheat were treated at the three- and the four-leaf stage, respectively. The fresh weights of the plants were measured 14 days after treatment (DAT) for black nightshade and 21 DAT for wheat. The glyphosate solutions were applied with an air-pressured laboratory track sprayer with 1.2-mm nozzles fitted with a perforated (0.6 mm) whirling pin and delivering 200 L/ha at 303 kPa. Table 1 lists the adjuvants tested. These were added to the unformulated monoisopropylamine salt of glyphosate [MON 8717 (glyphosate IPA salt 648 gai/litre=2.84 M without adjuvant)] at a concentration of 0.25% (w/v). Demineralised water was used as the carrier.
A sub-optimal rate of glyphosate, giving (ideally) a 0-20% growth reduction without adjuvant, was used to demonstrate the adjuvants' effects. Based on previous work, these rates were 77.8 gae/hectare (equivalent to 2.3 mM at 200 litres/hectare) on wheat and 30.4 gae/hectare (equivalent to 0.9 mM) on black nightshade. The experiments were conducted as a randomised complete block with four replicates. Two separate experiments were conducted for each of the two plant species. The data was subjected to analysis of variance using the Genstat statistical package (Release 6.1 from Rothamsted Experimental Station). The fresh weight data is shown in Tables 2 and 3. The performance of the products on both species was expressed as a percentage of the FW of untreated plants. Examples 1 to 8 are according to the invention, examples C1 to C12 serve as comparison.
aGly = unformulated isopropylamine salt of glyphosate.
bEach adjuvant was included at 0.25% w/v (2.5 g/L).
cTrial 1 = 0.9 mM glyphosate (equivalent to 30.4 g a.e./ha at 200 L/ha)
dTrial 2 = 0.6 mM glyphosate (equivalent to 20.3 g a.e./ha at 200 L/ha);
1Gly = unformulated isopropylamine salt of glyphosate 2.3 mM (equivalent to 77.8 ga.e./ha at 200 L/ha)
2Each adjuvant was included at 0.25% w/v (2.5 g/L)
The examples and comparative examples demonstrate that mixtures of alkoxylated alkyl oligoglucosides and primary alcohol alkoxylates show superior performance in all trials compared to state of the art adjuvant like tallow amine ethoxylates, alkyl oligoglycosides or even alkoxylated alkyl oligoglycosides taken alone.
Apart from biological efficacy, there are physical properties that make certain chemistries more desirable in glyphosate formulations. These properties include cold water miscibility, cold temperature viscosity and low foaming. The cold water miscibility of the potentiators was observed by agitating 400 ml of cold water (0° C.) with a 25 mm stir bar to create a 1 cm vortex. 40 grams of each surfactant were added at one go. The surfactant behaviour was observed and the time at which no striations remained was recorded in seconds.
Among the candidates ethoxylated tallow amine exhibits the poorest cold water miscibility (Table 4). All of the tallow amine ethoxylate introduced into the stirring water immediately collapsed onto itself, forming several large gelatinous masses. These masses broke up very slowly and tended to stick to the beaker walls rather than disperse.
To overcome this deficiency, ethoxylated tallow amine must be formulated with anti-gelling agents. None of the other chemistries were observed to form gels, yet the APG and the 8-10 phosphate ester did show slight clinging to the bottom of the beaker. Both, the alkoxylated APG and the blend with oleyl alcohol+3EO dispersed immediately and never touched the glass surface in its concentrated form.
| Number | Date | Country | Kind |
|---|---|---|---|
| 08005236 | Mar 2008 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2009/001716 | 3/11/2009 | WO | 00 | 9/20/2010 |
