BRPI0814787B1 - FILM FOR COVERAGE, FUMIGATION FILM, PROPAGATION FILM, PROPAGATION POTS, TRAYS FOR SOWS AND / OR TRAYS FOR HARVESTING OF POLYMERIC COMPOUND WITH BIOCIDAL FUNCTIONALITY, ITS PRODUCTION METHOD AND ITS USE - Google Patents

Description

Patent Descriptive Report for "COVER FILM, FUMIGATION FILM, SPREAD FILM, SPREAD JARS, SEED TRAYS AND / OR PO-LIMER COMPOUND TRAYS WITH BIOCID FUNCTIONALITY, ITS METHOD OF USE .

The present invention relates to biocidal functionality of polymeric compound materials, methods for producing such polymeric compound materials and their use, in particular for agriculture.

[002] A wide variety of polymeric materials such as biodegradable, weed growth reducing mulch films, or special biodegradable pots for horticulture are known and employed in the field of agriculture. An emphasis on the properties of these polymeric materials lies either in the task of stabilizing the material against the environment and chemical influences, or improving the biodegradability of the material. Examples of pesticide stabilized agricultural films with an additive can be found in Japanese Patent Application JP 631 75 072. European Patent Application EP 0214507 describes UV stabilizers that are used in outdoor agricultural films.

[003] An example of a material capable of thermal diffusion of an active ingredient is described in DE 28 19 515 A1. A multilayer composite material comprises a layer that is capable of raising the temperature of the material by exothermic chemical reaction so that a functional material may be released. However, the disclosed inorganic chemicals that are required for the exothermic reaction are harmful to the environment as well as unsuitable for the production, cultivation or transport of food and medicinal articles.

Another polymeric material incorporating inorganic biocidal substances is known from DE 696 29 891 T2. There, chlorine dioxide is supplied as an inorganic biocidal substance that acts as a disinfectant in food packaging films. However, handling and controlling the right amount for a given period of time is difficult, complex and costly. According to the disclosed material it involves different layers which should include a hydrophobic layer comprising a releasing substance and a neighboring hydrophilic layer comprising chloride ions.

Another approach to functionalizing agricultural or horticultural polymers is the incorporation of inorganic substances such as copper, copper salts, and finely powdered silver that act as disinfectants. However, detachment of the active substance is uncontrollable and usually involves the degradation or dissolution of the polymer.

All polymeric materials known hitherto in agriculture or horticulture have a problem that the life expectancy of the functionalized material is short. In addition, the function is usually based only on the protection of the polymer itself. However, a function is not conveniently given to agricultural products, such as those of a biocide, due to limitation to inorganic substances only, again involving degradable polymers or soluble polymers to release the inorganic substance. Thus, the required useful life of the functionalized polymeric material for a 12-month growth period, or in the case of reuse, of several years and / or several plantings, and harvest period is impossible. Over time the mechanical properties decrease with increasing biodegradation, and cause a reduction in polymer molecular weight. Decreasing molecular weight reduces desired polymer performance, such as the strength required to mitigate weather variations by agricultural films, or the protection of seed roots using seed pots and trays, for example.

It is therefore an object of the present invention to provide a composite polymeric material, preferably for use in agriculture and horticulture, which may have a variety of biocidal functionalities and which has a long shelf life.

Another object of the present invention is to provide a method for preparing such a polymeric composite material.

This object is solved by a biocidal functionality polymeric composite material, preferably for use in agriculture, comprising at least one base polymer compound and at least one biocidal active ingredient, wherein the biocidal active ingredient is an organic biocide which may be emitted by diffusion and / or osmosis material.

Under the term base polymer compound can be understood all polymeric compounds which show UV stability and sufficient time to withstand constant external exposure for at least 12 months and not react with the organic biocidal active ingredient and whose properties are not modified by the organic biocide. Since the flexibility of the polymeric material depends on the thickness of the material, under the term base polymer material flexible films are understood as well as inflexible molded articles.

Under the term biocidal active ingredient are meant all chemicals that are capable of killing different forms of living organisms and / or viruses used in fields such as medicine, agriculture and forestry.

In a preferred embodiment of the present invention the biocidal active ingredient or a combination of biocidal active ingredients is incorporated into the polymeric composite material as a molecular dispersion. In this way a homogeneous and defined distribution is obtained in the composite material.

In another preferred embodiment of the present invention the biocidal active ingredient is incorporated into a coating layer.

By this means, emission of the biocidal active ingredient by diffusion and / or osmosis can be facilitated and / or timed.

Coating materials are preferably applied in a thin film (dry coating layer thickness preferably below 0.5 mm) to the basic polymeric compounds. To achieve the desired thin film characteristics, the coating material formulation and the coating layer structure may be adjusted to the desired characteristics of the part, for example flexible films or molded rigid parts, to facilitate and / or time the coating. emission of the biocidal active ingredient. Coating materials may be formulated from a variety of chemicals and materials, or a combination of different chemicals, and applied as a single layer or multiple stacked layers. Coating materials of the present invention are preferably formulated through four components: binders, additives, biocidal active ingredients and the carrier.

Binders primarily function as an adhesive for the basic polymer. Binders are polymeric adhesive systems of varying molecular weights.

Molecules in the binder may be crosslinked during the curing stage to improve strength and create polymeric composite material.

In the preferred embodiment of the present invention, the coating material may be based on water soluble polymeric adhesive systems comprising binders that are crosslinkable and which are, after crosslinking, water insoluble but water swellable and capable of gel formation. by water absorption. The term "crosslinkable" according to the present invention indicates that the binders may form a mesh structure preferably initiated by heat, pressure, radiation and / or chemicals (hereinafter also referred to as hardeners). The term "gel former" according to the present invention refers to a co-loidal structure comprising at least 50%, at least 75% and typically at least 95% by weight of liquid, which is immobilized by surface tension between It is a macromolecular network of fibers constructed from a small amount of binders. In a preferred embodiment the gel liquid is water and the gel is a hydrogel in which water is the dispersion medium.

Binders are preferably selected from the group comprising gelatin, alginates, cellulose-based polymers such as methylcellulose, hydroxy methylcellulose, carboxy methylcellulose, cellulose acetate phthalate, and the like; starch-based polymers such as carboxymethyl starch, natural gums such as arabic gum, locust bean gum, carrageenan gum and xanthan gum; pectins; polymers formed from monomers with acid groups, such as poly (acrylates) (including (polyacrylic) acid, poly (methacrylic acid), and the like), poly (ethers), poly (acrylamides), poly (vinyl alcohol), beaker -amers of maleic anhydride, polyvinyl sulfonates, grafted hydrolyzed acryl nitriles starch, grafted acrylic acid starch, poly (N-vinyl pyrrolidone), poly (2-hydroxyethyl acrylate), poly (methacrylate) 2-hydroxyethyl), poly (sodium acrylate-coacrylic acid), poly (vinylsulfonic acid), poly (ethylene oxide), ethylene oxide block copolymers with polyamides, polyesters, and polyurethanes, and mixtures and copolymers in salt form of the groups mentioned above.

Particularly preferred binders comprise water-soluble (but insoluble after cross-linking) chemical and / or physical crosslinkable adhesive polymers such as polyvinyl alcohol, polyvinyl methyl ether; polyvinyl pyrrolidone; polyethylene oxide; cellulose derivatives such as dextrans and starches; polyacrylates such as polyacrylic acid, polyacrylamides, methyl cellulose, carboxy methyl cellulose, starch based polymers, gelatin, casein, hydroxyl ethyl cellulose hydroxy propyl cellulose and / or ethylene oxide block copolymer dispersions with polyurethane.

Illustrative examples of particularly useful water absorbing crosslinkable coating binders which are capable, under the most favorable conditions, of absorbing at least about 5, more preferably at least 10, even more preferably at least 15 and more preferably At least 25 times its weight in an aqueous solution containing 0.9 weight percent sodium chloride are preferably selected from the group comprising superabsorbents such as poly (acrylates) including poly (acrylic) acid, poly ( (methacrylic acid), and the like), maleic anhydride copolymers, poly (vinyl sulfonates), poly (sodium acrylic co-acid acrylate), poly (vinyl sulfonic acid), (such as, for example, described in US Patent 6,737. 491, US 6,849,685, US 6,887,961, US 7,115,321, US 6,964,803, US 6,808,801, US 7,205,259), gelatin and / or polyethylene oxide block copolymer dispersions.

A particularly useful coating material according to the present invention comprises the combination of at least two water absorbing crosslinkable polymeric binders, wherein one water absorbing crosslinkable polymeric binder is gelatin. In a particularly preferred embodiment, coating layers comprise the combination of a gelatin binder and a superabsorbent binder, such as a poly (acrylate) binder.

Gelatin has been surprisingly beneficial as it supports the binding of water absorbing crosslinkable polymers to the base polymer without substantially interfering with the properties of water absorbing crosslinkable polymers.

Any gelatin, such as photographic gelatin, food gelatin, edible gelatin, industrial gelatin, protein gelatin, may be used for such a preferred coating layer. By adding as a additive a hardener, gelatin is cross-linked due to a reaction of amino, imino and hydroxyl groups.

Additives are defined as insoluble pigments or low molecular weight chemicals in coating formulations that allow coatings to perform specific functions but do not contribute to biocidal function. Additives include but are not limited to pigments. Pigments are the typically dyeing portion of a coating material, but can also provide corrosion protection or stability to ultraviolet (UV) light. Additives also include but are not limited to non-pigments. Non-pigment additives include ultraviolet or heat block attack stabilizers, hardener to accelerate the cross-linking reaction, co-solvents to increase viscosity, or plasticizers to enhance uniform coating.

In another embodiment of the invention, a hardener, preferably formaldehyde, is employed as an additive to crosslink the coating layer material and to enhance the bonding of the layer material to the base polymer.

A particularly useful compound material refers to a base polymer wherein the coating materials comprise a combination of cross-linkable water absorbing polymers, preferably superabsorbers, more preferably polyacrylates, gelatin and a hardener, preferably formaldehyde.

The carrier is typically a liquid, such as an organic solvent or water. The vehicle allows coating materials to flow and to be applied by methods such as spraying, dipping, cascade molding and / or curtain. This component may be in the coating formulation prior to application, but evaporates thereafter to allow solid materials to immobilize and form the coating layer. The resulting polymeric composite material may optionally be dried.

The vehicle, therefore, may be completely absent, partially present or present in the final ready-to-use polymer composite material. In a preferred embodiment the carrier is absent or present only partially in the final ready-to-use polymer composite material. However, one skilled in the art recognizes that water or other liquid will be absorbed by the polymeric composite material during use and will play an important role in the functionality of the polymeric composite material.

In another preferred embodiment of the invention the organic solvent is ethanol, acetone, 1,4-dioxane, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl formamide, dimethyl sulfoxide, acetic acid, n-butanol, isopropanol, n-propanol, methanol, formic acid, other solvents known to those skilled in the art and / or aqueous solutions thereof.

Coating materials of the present invention comprise at least one biocidal active ingredient (hereinafter also referred to as a biocide).

Coating formulations vary widely, with different types and amounts of biocidal binders, additives, vehicles and active ingredients. Differences in coating formulations provide film characteristics specifically tailored to the part and its end use. Typically, one type of coating material cannot be formulated to provide all desired properties. Several layers of different coating materials may be applied to a base polymer to form the coating film.

The polymeric composite material according to another preferred embodiment of the present invention may be a multilayer coating structure and the biocidal active ingredient is incorporated into repeated coating layers or a coating layer.

By incorporating the biocidal active ingredient into repeated coating layers, a control of diffusion and / or osmosis rates is even better obtainable. Apart from this, different biocidal active ingredients may be incorporated into different layers. The present invention, however, also relates to an embodiment wherein a mixture of at least two biocidal active ingredients are incorporated into a coating layer. Depending on plant growth and possible seasonal change requirements in terms of pests, fungi, and the like, a tailored approach to biocidal treatment may be provided.

In a preferred embodiment of the invention, at least one biocidal active ingredient may be incorporated into the same coating layer as binders. One embodiment wherein the layer with at least one biocide comprises gelatin is preferred.

The organic biocide is preferably selected from the group consisting of pesticides, herbicides, insecticides, algicides, fungicides, molluscicides, miticides, and rodenticides. In addition, the organic biocide may be selected even more preferably from the group that antivirals consist of germicides, antibiotics, antibacterials, antifungals, antiseptics, antiprotozoans and antiparasitics.

In another preferred embodiment of the invention the organic biocide is selected from the group of antiseptics and / or disinfectants for medical and food use.

As regulations for chemicals considered safe for use in agriculture, food and medicine are constantly changing, such organic biocidal active ingredients are more preferred for the present invention, which comply with current official regulations for chemicals and especially for antiseptics. and disinfectants in those fields. Especially those substances which are listed in the "European the Biocidel Products Directive" (98/8 / EC) by the European Commission are preferably used as biocidal active ingredients according to the present invention.

In another preferred embodiment of the present invention the organic biocide is selected from the group comprising acetamides and anilide herbicides, thiocarbamate herbicides, chlorophenoxy herbicides, dipyridyl herbicides, dinitrocresolic herbicides, cyclohexyloxide herbicides, phosphonate herbicides, urea herbicide derivatives and / or mixtures thereof.

Particular herbicides according to the present invention are selected from the group comprising acetochlor, acibenzolar, acibenzolar-s-methyl, acifluorfen, sodium acifluorfen, aclonifene, alachlor, alidochlor, aloxidime, amethrin, amicarbazone, amidochlor, amidosulfurone, aminopyralide, amitrole, ammonium sulfamate, ancimidol, anilophos, asulam, atrazine, azafenidin, azimsul-furone, aziprotrin, BAH-043, BAS-140H, BAS-714H, BAS-762H, BAS-776H, BAS-800H, beflubutamide, benazoline, ethyl bezazoline, bencarbazone, benfluralin, benfuresate, bensulide, methyl bensulfurone, bentazone, benzofendizone, benzobicyclone, benzofenan, benzofluor, benzoylprop, bifenox, bilanafos, sodium bilanafos, sodium bilanafos bispiribac, bromacil, bromobutide, bromophenoxim, bro-moxinil, bromurone, buminafos, busoxinone, butachlor, butafenacil, bu-tamifos, butenachlor, butraline, butroxidime, butylate, cafenstrole, car-betamide, ethamfentrazone azone, clomethoxyfen, chlorine am-ben, chlorine azifop, chlorine butyl azifop, chlorine bromurone, chlorine bufam, chlorine fenac, chlorine fenac, chlorine fenprop, chlorine flurenol, chlorine methyl fluorine, chlorine idazone, chlorine imurone , chloro-mequat chloride, chlorine nitrofen, chlorophthalim, chlorothal dimethyl, chlorotolurone, chlorosulfurone, cinidone, ethyl cinidone, cinmethylin, cinosulfurone, cletodi-ma, propargyl clodinafop, clofencet, clomazone, clomepropam, clomepropam, methyl chloransulam, cumilurone, cyanamide, cyanazine, cyclanilide, cycloate, cyclosulfamurone, cycloxidime, cyclurone, cyhalofop, butyl cihalofop, cyperquat, cyprazine, cyprazole, 2,4-D, 2,4-DB, daimurone / dimrone, dalapone, daminozide, dazomet, n-decanol, desmedifam, desmethrin, detosyl pyrazolate (DTP), dialect, dicamba, diclobenyl, dichloro prop, p-dichloroprop, diclofop, methyl diclofop, p-methyl diclofop, diclosulam, dietatyl, diethyl, diphenoxurone, difenzoquat, difluf enican, diflufenzopyr, sodium diflufenzopyr, dimefurone, sodium dikegulac, dimefurone, dimepiperate, dimethachlor, dimetamethrin, dimethenamide, p-dimethenamide, dimethipine, dimethasulfurone, dinitramine, dinoseb, dinoterb, dihydrate, di-dimenathide dithiopyr, diurone, DNOC, ethyl eglinazine, endotal, eptc, esprocarb, etalfluralin, methyl etametsulfurone, ethephone, etidimurone, etiozine, etofumesate, ethoxyphene, ethyl ethoxyfen, ethoxysulfurone, ethoxy-benzanide, F-5-N33 chloro-4-fluoro-5- [4- (3-fluorpropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide, fenoprop, fenoxaprop, p-phenoxaprop , ethyl fenoxaprop, p-ethyl fenoxaprop, fentraza mida, fenurone, flamprop, m-isopropyl flamprop, m-methyl flamprop, flazasulfurone, florassulam, fluazifop, p-fluazifop, butyl fluazifop, p-butyl fluazifop, fluazolate, flucarbazone, sodium flucarbazone, flucetosulfurin, flucloraline, flufenacet (thiafluamide), flufenpir, ethyl flufenpir, flumethrelin, flumetsulam, flumiclorac, pentyl flumichlorac, flumioxazine, flumipropyn, fluometurone, fluordifen, fluorglicofen, ethyl fluorglycofen, flu-poxam, flupropacil, flupropanate, flupirsulfurone, methyl sodium flupirsulfu-rona, flurenur, flurenol, flurenol fluroxipyr, flurprimidol, flurtamone, flutiacet, methyl flutiacet, flutiamide, fomesafen, foramsulfurone, forchlorophenurone, fosamine, furyloxyphene, gibberelinate, l-glufosinate, ammonium l-glufosinate, ammonium glufosinate, glifosinate, glyphosinate, ammonium glufosinate -safen, halosulfurone, methyl halosulfurone, haloxyfen, p-haloxyfen, ethoxyethyl haloxyfen, p-ethoxyethyl haloxyfen, methyl haloxyfen, p-methyl haloxyfen, hexazinone, hnpc-9908, HOK-201, HW-02, imazamethane imazametabenzo, imazamox, imazapic, imazapyr, imazzaquin, imaze-tapir, imazosulfurone, inabenfeto, indanophane, indolacetic acid (IAA), 4-indol-3-yl-butanoic acid (IBA), iodosulfurone, methyl sodium iodosulfurone, ioxinyl, isocarbamide, isopropaline, isoproturone, isouron, isoxaben, isoxachlorotole, isoxaflutole, isoxapyrifop, HDI-100, KUH-043, KUH-071, carbutylate, ketospiradox, lactofenazide, lenacid, acid maleic acid, MCPA, MCPB, methyl MCPB, ethyl MCPB and sodium MCPB, mecoprop, sodium mecoprop, butotyl mecoprop, p-butotyl mecoprop, p-dimethyl ammonium mecoprop, ρ-2-ethyl hexyl mecoprop, mecoprop p-potassium, mefenacet, mefluidide , mepi-quat chloride, mesosulfurone, methyl mesosulfurone, mesotrione, metabenzo-thiazurone, metam, metamifop, metamachron, metazachlor, metazole, me-toxifenone, methyl-dimethyl, 1-methylcyclopropene, methylisothiocyanate, me-tobenzurone, metobenzurone, metobenzurone metolachlor, s-metolachlor, metosulam, methoxurone, metribuzine, metsulfurone, methyl metsulfurone, molinate, monalide, monocarbamide, monocarbamide dihydrogen sulfate, monolinurone, monosulfurone, monurone, MT 128, MT-5950 [i.e. chloro-4- (1-methylethyl ) -phenyl] -2-methyl pentanamide, NGGC-011, naproanilide, napropamide, naptalam, NC-310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole, nebu-rone, nicosulfurone , nipyraclofen, nitralin, nitrophen, sodium nitrophenolate (mixture of isomers), nitrofluorfen, nonanoic acid, norflura-zone, orbencarb, orthosulfamurone, oryzaline, oxadiargyl, oxadiazone, oxasulfurone, oxaziclomefone, oxyflatrazole, paclofluorene, paclofenatate pelargonic (nonanoic acid), pendimeta-lina, pendralina, penoxsulam, pentanochlor, pentoxazone, perfluidone, petoxamide, fenisofam, fenmedifam, ethyl fenmedifam, picloram, picoli-nafen, pinoxaden, piperophos, pirifenop, butyl-pyrifenopyridone, methyl primisulfurone, probenazole, profluazole, prociazine, prodiamine, prifluralin, prooxidime, prohexadione, prohexadione calcium, prohydrojasmona, prometone, promethrin, propachlor, propanizafop, propazine, profam, propisochlor, propoxy bazo-na, sodium propoxycarbazone, propyzamide, prosulfaline, prosulfocarb, prosulfurone, prinachlor, pyraclonyl, pyraflufen, ethyl pyraflufen, pyrasulfotol, pyrazolinate (pyrazolate), ethyl pyrazosulfurone, pyrazoxyphene, piribambenzo benzopyrimidazole, pyridate, pyriftalide, pyriminobac, methyl pyriminobac, pyrimisulfan, piritiobac, sodium piritiobac, pyroxasulfone, piroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, ethyl quizalofop, p-quizalofop, p-ethylsulfonate, p-ethylsulfone, setoxydima, sidurone, simazine, symmetrine, SN-106279, sulcotrione, sulfalate (cdec), sulfentrazone, sulfometurone, methyl sulfometurone, sulfosate (glyphosate-trimese), sulfosulfurone, SYN-523, SYP-249, SYP-298, SYP -300, tebutam, tebutiurone, technazene, tefuriltrione, tembotrione, tepraloxidime, terbacil, terbucarb, terbuclor, terbumetone, terbuthylazine, ter-butyl, th-547, tenylchlorine, thiafluamide, tiazaflur ona, thiazopyr, thidiazimin, thidiazurone, thienocarbazone, methyl thienocarbazone, thifensulfuronat methyl thifensulfurone, thiobencarb, thiocarbazil, topramezone, tralco-xidime, triallate, triassulfurone, triazurone acid, triazurone, triazifenate, triazifenate , triclopyr, tridifane, trietazine trifloxysulfurone, sodium trifoxysulfurone, trifluralin, triflussulfon, methyl triflussulfurone, trimethurone »trinexapac, ethyl trinexapac, tritosulfurone, tsitodef, uniconazole, p-uniconazole, Z-Z16, Z-J16-Z2 -0543, ZJ-0862, as well as the following compounds In another preferred embodiment of the present invention the organic biocide is selected from the group comprising antibiotic insecticides, cyclodene insecticides, insect growth regulators, carbamate insecticides, nicotenoid insecticides, pyridic herbicides, oxadiazine insecticides, organophosphorus insecticides and / or mixtures thereof.

The following insects may be mentioned as examples and as preferred, but without limitation: Beetles such as Hylotrupes bajulus, Clorophorus pilo-sis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pu-bescens, Trogoxilon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Hetero-bostrychus brunneus, Sinoxiion spec. Dinoderus minutus; Hymenopte-rons, such as Sirex juvencus, Urocerus gigas, Urocerus gigas tai-gnus, Urocerus augur; Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus; Bristletails, such as Lepisma saccharina.

Particular insecticides according to the present invention are selected from the group comprising acetylcholinesterase (AChE) inhibitors such as, for example, carbamates, for example alanicarb, aldicarb, aldoxycarb, alixicarb, aminocarb, bendiocarb, benfu- racarb, bufencarb, butacarb, butocarboxy, butoxycarboxyme, carbaryl, carbofuran, carbosulfan, cloetocarb, dimethylane, ethiofencarb, fe-nobucarb, phenothiocarb, formetanate, furatiocarb, isoprocarb, metamicarb, methicarbyl, methicarbyl promecarb, propoxur, thiodicarb, thiophanox, trimetacarb, XMC, and xylylcarb; or organo phosphates, for example, acetate, azametiphos, (methyl, ethyl) azinfos, ethyl bromophos, (methyl) bromophenvinphos, butathiophos, cadusaphos, carbophenothione, chloroethoxy, chlorophenvinphos, chloromephos, (methyl / ethyl) chlorophosphos, cyanophenphs, cyanophos, chlorine fenvinphos, S-methyl demetone, S-methyl sulfone demetone, dialiphos, diazinone, diclofentiona, dichloro / DDVP, dicrotophos, dimethoate, dimethylvinphos, dioxabenzophos, disulphotone, EPN, ethion, etoprofin famfur, fenamiphos, fenitrothione, fensulfothione, fentiona, flupirazofos, phonophos, formothione, fosmetilana, fostiazato, heptenofos, iodofenfos, iprobenfos, isazofos, iso-propyl, O-salicylate, methaphylate, iodation, meoflation metidationa, mevinfos, monocrotophos, naled, ometoate, methyl oxememone, (methyl / ethyl) parathion, phentate, phorate, fosalone, fos-met, phosphamidone, phosphocarb, foxima (methyl / ethyl), profenophos pyrimiphos, propaphos, propetamphos protiofos protoato piraclofos p iridafentiona, pyridationa, quinalfos, sebufos, sulfotep, sulprofos, tebupirimfos, temos-fos, terbufos, tetrachlorovinfos, thiometone, triazofos, trichlorophone, vami-dotiona, and imiciafos. GABA gate colorectal channel antagonists such as, for example, organochlorines, for example, camflor, chloro-dane, endosulfan, gamma-HCH, HCH, heptachlor, lindane, and methoxy-chlorine; or fiproles (phenylpyrazoles), for example acetoprol, etiprol, fipronil, pirafluprol, pyriprole, and vaniliprol. Sodium channel modulators / voltage-dependent sodium channel blockers such as, for example, pyrethroids, for example acrinatrine, (d-cis-trans, d-trans) alethrin, beta-cyfluthrin, bifentrin, bioalethrin, S-isomer -cyclopentyl bi-oalethrin, bioethanometrine, biopermethrin, bioresmethrin, clovaportrin, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocitrin, cycloprotrin, cyfluthrin, cyhalothrin, (alpha-, beta-, theta- cyrethine-cetrinetrine) , deltamethrin, empentrin (1R isomer), esfenvalerate, etofenprox, fenflutrin, fenpropatrin, fenpiritrin fenvalerate, flubrocitrinate, flucitrin-to, flufenprox, flumethrin, fluvalinate, fubfenprox, gamma-cyhalothrin, cadiothrothine, protothioprine metofluthrin, (cis-, trans-) permethrin, phenothrin (trans 1R isomer), pralethrin, proflutrin, protrifenbute, pyresmethrin, resmetrin, RU 15525, silafluofen, tau-fluvalinate, tefluthrin, teralethrin, () tetramethrin, atralometrine, tr ansflutrin, ZXI 8901, pyrethrin (pyretrum), efflusilanate; DDT; or methoxychlor. Nicotinergic acetylcholine receptor agonists / antagonists such as, for example chloronicotinyls, for example acetamipride, clotianidine, dino-tefuran, imidacloprid, imidaclotize, nitiazine, thiacloprid, thiamethoxam, AKD-1022, nicotap, bensot, sodium they think. Allosteric acetylcholine receptor modulators (agonists) such as, for example, spinosyns, for example, spinosad and spinetoram. Chloride channel activators such as, for example, mectins / macrolides, for example, abamectin, emamectin, emamectin benzoate, ivermectin, lepimectin, and milbemectin; or juvenile hormone analogs, for example, hydroprene, cinoprene, methoprene, epophenonane, triprene, phenoxycarb, pyriproxyfen, and diophenolane.

Active ingredients with unknown or non-specific mechanisms of action such as, for example, gassing agents, for example methyl bromide, chloropicrin and sulfuryluride; selective antifeedants, for example cryolide, pimetrozine, pyriflu-quinazone and flonicamid; or mite growth inhibitors, for example clofentezine, hexitiazox, ethoxazole. Oxidative phosphorylation inhibitors, for example, diafentiurone; organotin compounds, for example azocyclotine, cyhexatin and fenbutatin oxide; or propargite, tetradifone. Oxidative phosphorylation decouplers acting by interrupting the proton H gradient such as, for example, chlorine fenapir, binapacryl, dinobutone, dinocap and DNOC. Microbial interferences of the insect gut membrane such as, for example, Bacillus thuringiensis strains. Chitin biosynthesis synthesis inhibitors such as, for example, benzoylureas, for example bistriflu-rone, chlorine fluazurone, diflubenzurone, fluazurone, flucicloxurone, flu-phenoxurone, hexaflumurone, lufenurone, noviflumurone, penlururon, triflururon, triflururon, trifluronuron Buprofezin. Seedling switches such as, for example, cyromazines. Ecdisone agonists / switches such as, for example, diacylhydrazines, for example, chromafenozides, halofenozides, methoxyphenozides, tebufenozides, and JS-118; or azadiractin. Octopaminergic agonists such as, for example amitraz. Site III electron transport inhibitors / Site II electron transport inhibitors such as, for example, hydramethylnone; acequinocil; fluacripyrime; or cyflumetophen and cyienopyrophen. Electron transport inhibitors such as, for example, site I electron transport inhibitors, from the METI acaricide group, for example phenazaquine, fenpyroximate, pyrimidifen, pyridaben, tebufenpirad, tolfenpirad, and rotenone; or voltage-dependent sodium channel blockers, for example indoxacarb and metaflumizin. Fatty acid biosynthesis inhibitors such as, for example, tetronic acid derivatives, for example spirodiclofen and spiromesifen; or tetramic acid derivatives, for example spirotetramate. Neuronal inhibitors with unknown mechanism of action, eg bifenazate. Rhyanodine receptor effectors such as, for example, diamides, for example flubendiamide, (R), (S) -3-chloro-N1- {2-methyl-4- [1,2,2,2-tetrafluor-1- ( trifluoromethyl) ethyl] phenyl} -N2- (1-methyl-2-methylsulfonylethyl) phthalamide, chloro anthraniliprol (Rinaxipir), or Ciazipir. Other active ingredients with unknown mechanism of action such as amidoflumet, benclothiaz, benzoxime, bromopropylate, buprofezin, chinomethionate, chlorine dimeform, chlorobenzylate, clotiazo-beno, cycloprene, dicofol, dicyclanil, phenoxacrim, fentrifanil, flubenzine-flutubenzine, flubenzine-flutubin , gossiplure, japonilure, methoxyadiazone, petroleum, potassium oleate, pyridalyl, sulfluramide, tetrasul, triaratene or verbutin; or one of the following known active compounds 4 - {[(6-brompirid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115644), 4 - {[ (6-fluorpyrid-3-yl) methyl] (2,2-difluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115644), 4 - {[(2-chloro-1,3- thiazol-5-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115644), 4 - {[(6-chloropyrid-3-yl) methyl] (2- fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115644), 4 - {[(6-chloropyrid-3-yl) methyl] (2,2-difluoroethyl) amino} furan-2 (5H ) -one known from WO 2007/115644), 4 - {[(6-chloro-5-fluorpyrid-3-yl) methyl] (methyl) amino} furan-2 (5H) -one (known from WO 2007/115643 ), 4 - {[(5,6-Dichloropyrid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115646), 4- {[{6- chloro-5-fluoro-3-yl) methyl] (cyclopropyl) amino} furan-2 (5H) -one (known from WO 2007/115643), 4 - {[(6-chloro pyrid-3-one) yl) methyl] (cyclopropyl) amine} fu-2 (5H) -one (known from EP-A-0 539 588), 4 - {[{6-chloropyrid-3-yl) methyl] (methyl) amino} f uran-2 (5H) -one (known from EP-A-0 539 588), [(6-chloro pyridin-3-yl) methyl]] (methyl) oxyd-) I-denocated anamide (as known from WO 2007/149134), [1- (6-chloro pyridin-3-yl) ethyl] (methyl) oxide-λ4-suiphanylidenocyanamide (known from WO 2007/149134) and its diasteomers (A) and (B) (also known from WO 2007/149134), [(6-trifluoromethyl pyridin-3-yl) methyl] (methyl) oxide-14-sulfanylidenocyanamide (known from WO 2007 / 095229), or [1- (6-trifluoromethyl pyridin-3-yl) ethyl] (methyl) oxide-X4-sulfaphenylenene cyanamides (known from WO 2007/149134) and their (C) and (D) diastereomers ) (also known from WO 2007/149134), [0046] In another preferred embodiment of the present invention the organic biocide is selected from the group comprising acetamide and anilide fungicides, aliphatic nitrogen fungicides, aromatic fungicides, thio carbamate fungicides , oxazole fungicides, organophosphorus fungicides, phthalimide fungicides, strobilurin fungicides a, urea derivative fungicides, quaternary ammonium antiseptic compounds, quaternary ammonium antiseptic compounds such as chlorhexidine gluconate, polyhexamethylene biguanide hydrochloride, octenidine dihydrochloride and / or mixtures thereof.

Particular fungicides according to the present invention are selected from the group comprising nucleic acid synthesis inhibitors such as, for example, benalaxyl, benalaxyl-M, bupiri-mato, clozylacone, dimethirimol, etirimol, furalaxyl, himexazole, mefe- noxam, metalaxyl, metalaxyl-M, ofurace, oxadixyl and oxolinic acid. Mitosis and cell division inhibitors such as, for example, benomi-la, carbendazim, chlorofenazole, dietofencarb, etaboxam, fuberidazole, profenofos, pencicurone, thiabendazole, thiophanate, methyl thiophanate and zoxamide. Breathing inhibitors such as, for example, diflumeto-kidney as a Cl-breathing inhibitor; bixafen, boscalid, carboxin, fenfuram, flutolanil, fluopiram, furametpir, furmeciclox, mepronil, oxycarboxin, pentiopirad, tifluzamide as a C1l respiration inhibitor; amisulbromo, azoxystrobin, ciazofamide, dimoxystrobin, enestrobin, famoxadone, fenamidone, fluoxastrobin, methyl cresoxime, metominoestrobin, orisaestrobin, picoxyestrobin, piraclostrobin, piri-bencarb, trifloxytrobin respirator Compounds capable of acting as a decoupler such as for example dino-cap, fluazinam and meptildinocap. Inhibitors of ATP production such as, for example, fentin acetate, fentin chloride, fentin hydroxide and siltiofam. Amino acid and / or protein biosynthesis inhibitors such as, for example, andoprim, blasticidin-S, cyprodinil, casugamycin, casugamycin hydrochloride hydrate, mepanipyrim and pyrimethanil. Transduction signal inhibitors such as, for example, fenpiclonil, fludioxonil and quinoxyfen. Lipid and membrane synthesis inhibitors such as, for example, biphenyl, clozolinate, edifenphos, etridiazole, iodocarb, iprobenfos, iprodione, isoprothiolane, procimidone, propamocarb, propamocarb hydrochloride, pyrazophos, methyl tolclophos and vinclozoline. Ergosterol biosynthesis inhibitors such as, for example, aldimorf, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, diphenoconazole, diniconazole, diniconazole-M, dodemorf, dodemorf acetate, epoxiconazole, ethaconazole, fenarimol, fenbucidazole, fenbucidazole fenpropimorf, fluquinconazole, flurprimi-dol, flusilazole, flutriafol, furconazole, cis furconazole, hexaconazole, imaza-lil, imazalyl sulfate, imibenconazole, ipconazole, metconazole, miclobu-tanyl, naphthyphine, nuarimol, oxpoconazole, peflurazole, paclobutazole , piperine prochloraz, propiconazole, protioconazole, piributicarb, pirifenox, quinconazole, simeconazole, spiroxamine, tebuconazole, terbibaphin, tetraconazole, triadimephone, triadimenol, tridemorf, triflumizole, triforine, triticonazole, uniconazole, viniconazole. Cell wall synthesis inhibitors such as, for example, bentiavalicarb, dimetomorph, flumorf, iprovalicarb, mandipropamid, polyoxins, polyoxo-kidney, validamycin A, and valifenal. Melanin bisynthesis inhibitors such as, for example, carpropamide, diclocimet, phenoxanil, phthalide, pyrokylone and tricyclazole. Compounds capable of inducing a host defense such as, for example acibenzolar-S-methyl probenazole, and thiadinyl. Compounds capable of producing a multi-site action, such as, for example, the mixture Bordeaux, captafol, captan, chloro-talonyl, copper naphthenate, copper oxide, copper oxychloride, copper preparations such as copper hydroxide, copper sulphate, diclo-fluanide, dithianone, dodine, dodine free base, ferbam, fluorofolpet, follet, guazatin, guazatin acetate, iminoctadine, iminoctadine albesylate, mancobre, mancoziram, mazinc, mazinc, metham, copper oxine, propineb, sulfur and sulfur preparations including calcium polysulfide, thiram, tolylfluanide, zineb and ziram. Other compounds such as for example 3- (difluoromethyl) -1-methyl -N - [(9R) -9- (1-methylethyl) -1,2,3,4-tetrahydro-1,4-methanonaphthalene 5-yl] -1H-pyrazol-4-carboxamide, 3- (difluoromethyl) -1-methyl -N - [(9S) -9- (1-methylethyl) -1,2,3,4-tetramid hydro-1,4-methanonaphthalen-5-yl] -1H-pyrazol-4-carboxamide, 3- (difluoromethyl) -N- [4 '- (3,3-dimethyl but-1-yn-1-yl) biphenyl-2-yl] -1-methyl-1 H -pyrazol-4-carboxamide, 2-chloro-N- (4'-prop-1-yn-1-ylbiphenyl-2-yl) pyridin-3-carboxamide, 2-Chloro-N- [4 '- (3,3-dimethyl but-1-yn-1-yl) biphenyl-2-yl] pyridine-3-carboxamide, 5-fluoro-1,3-dimethyl-N- (4'-prop-1-yn-1-ylbiphenyl-2-yl) -1H-pyrazol-4-carboxamide, N- [4 '- (3,3-dimethyl but-1-yn-1-yl) biphenyl-2-yl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide, 3- (difluormethyl) -1-methyl -N- (4'-prop-1-yn-1-yl) ylbiphenyl-2-yl) -1H-pyrazol-4-carboxamide, 3- (difluoromethyl) -N- [4 '- (3-methoxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl ] -1-methyl-1H-pyrazol-4-carboxamide, N- (3-tert-butyl-2-ethenylphenyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-carboxa Mida, 1-methyl-N- [9- (1-methylethyl) -1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl] -3- (trifluoromethyl) -4, 5-dihydrolH-pyrazol-4-carboxamide, N- (4'-chloro biphenyl-2-yl) -1-methyl-3- (trifluoromethyl) -4,5-dihydro-1 H -pyrazol-4 -carboxamide, N- [9- (dichloromethylidene) -1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl] -3- (difluoromethyl) -1-methyl-1H-pyrazol-2-one 4-carboxamide, N- [4 '- (3-cyano-3-methylbut-1-yn-1-yl) biphenyl-2-yl] -3- (difluoromethyl) -1-methyl-1H-pyrazol-4 -carboxamide, rel-3- (difluoromethyl) -1-methyl-N - [(1R, 4S) -4- (1-methylethyl) -1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl] -1H-pyrazol-4-carboxamide, N- [9- (dibromomethylidene) -1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl] -3- (difluoromethyl) -1- methyl-1 H-pyrazol-4-carboxamide, rel-3- (difluormethyl) -1-methyl-N - [(1 R, 4S) -9-methylidene-1,2,3,4-tetrahydro-1 , 4-methanonaphthalen-5-yl] -1H-pyrazol-4-carboxamide, rel-3- (difluoromethyl) -1-methyl-N - [(1 R, 4S) -1,2,3,4-tetrahydro-1 , 4-methanonahalen-5-yl] -1H-pyrazol-4-carboxamide, 3- (difluoromethyl) -N- [9- (difluoromethylidene) - 1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl] -1-methyl-1H-pyrazol-4-carboxamide, N- [2- (1,3-dimethylbutyl) phenyl] -5-Fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide, N- {2- [1,1'-Cyclopropyl-1-yl] phenyl-S-hydroxymethyl) -! -methyl -1H-pyrazol-4-carboxamide (2E) -2- (2 - {[6- (3-chloro-2-methylphenoxy) -5-fluorpyrimidin-4-yl] oxy} phenyl) -2- ( methoxyimino) -N-methylethanamide, 2-chloro-N- (1,1,3-trimethyl -2,3-dihydro-1H-inden-4-yl) pyridine-3-carboxamide, N- (3 -ethyl-3,5,5-trimethyl cyclohexyl) -3- (formylamino) -2-hydroxybenzamide, 5-methoxy-2-methyl-4- (2 - {[({(1E) -1 - [3 - (trifluoromethyl) phenyl] ethylidene} amino) oxy] methyl} phenyl) -2,4-dihydro-3H-1,2,4-triazol-3-one, (2E) -2- (methoxy) imino) -N-methyl-2- (2 - {[({(1 E) -1- [3- (trifluoromethyl) phenyl] ethylidene} amino) oxy] methyl} phenyl) ethanamide, (2E) -2- ( methoxyimino) -N-methyl-2- {2 - [(E) - ({1- [3- (trifluoromethyl) phenyl] ethoxy} imino) methyl] phenyl} ethanamide, (2E) -2- {2- [({[(1E) -1- (3 - {[(E) -1-fluoro-2-phenylethenyl] oxy} phenyl) ethylidene] amino} oxy) methyl] phenyl} -2- (methoxyimino) - N-Methylethanamide, 1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol, methyl 1- (2,2-dimethyl-2,3-dihydro) hydro-1 H-inden-1-yl) -1 H -imidazol-5-carboxylate, N-ethyl-N-methyl -N '- {2-methyl -5- (trifluoromethyl) -4- [3- (trimethyl silyl) proposed xi] phenyl} imidoformamide, N-ethyl -N-methyl -N '- {2-methyl -5- (trifluoromethyl) -4- [3- (trimethylsilyl) propoxy] phenyljimidoformamide, N' - {5- (difluoromethyl) -2-methyl-4- [3- (trimethylsilyl) propoxy] phenyl} -N-ethyl-N-methyl imidoformamide, 0- {1 - [(4-methoxyphenoxy) methyl] -2,2-dimethylpropyl} 1H imidazol-1-carbothioate, N- [2- (4 - {[3- (4-chloro phenyl) prop-2-yn-1-yl] oxy} -3-methoxyphenyl) ethyl] -N2- (methylsulfonyl) valinamide , 5-chloro-6- (2,4,6-trifluorphenyl) -N - [(1 R) -1,2,2-trimethylpropyl] [1,2,4] triazolo [1,5-a] pyrimidine-1 7-amine, 5-chloro-N - [(1R) -1,2-dimethyl propyl] -6- (2,4,6-trifluorphenyl) [1,2,4] triazolo [1,5-a] pyrimidin -7-amine, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorphenyl) [1,2,4] triazola [1,5-a] pyrimidine, propamocarb -phosethyl, (2E) -2- {2 - [({[(1E) -1- (3 - {[(E) -1-fluoro-2-phenylenyl] oxy} genyl) ethylidene] amino} oxy ) methyl] phenyl} -2- (methoxyimino) -N-methylethanamide, 1 - [(4-methoxyphenoxy) methyl] -2,2-dimethylpropyl 1 H -imidazol-1-carboxylate, 1-methyl -N- [ 2- (1,1,2,2-tetrafluorooxy) phenyl] -3- (trifluoromethyl) -1H-pyraz ol-4-carboxamide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, 2-phenylphenol and salts, 3 - (difluoromethyl) -1-methyl-N- [2- (1,1,2,2-tetrafluorooxy) phenyl] -1H-pyrazol-4-carboxamide, 3,4,5-trichloropyridine-2,6-dicarbonitrile , 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine, 3-chloro-5- (4-chlorophenyl) -4- (2,6-difluorphenyl) -6-methylpyridazine, 4- (4-chlorophenyl) -5- (2,6-difluorphenyl) -3,6-dimethyl pyridazine, quinolin-8-ol, bentiazole, betoxazine, capsimycin, carvone, quinomethionate, cufraneb, ciflufenamide, cimoxanil, dazomet, debacarb , dichlorophen, dichlomezine, dichlorane, difenzoquat, difenzoquat methyl sulfate, diphenylamine, ecomato, ferimzone, flumetover, fluopi-collide, fluoroimide, flosulfamide, fosetyl calcium, fosetyl sodium, hexachlorobenzene, isulfonyl methanesulfonamide, methyl (2E) -2- {2 - [({cyclopropyl [(4-methoxyphenyl) imino] methyl} thio) methyl] phenyl} -3-methoxyacrylate, methyl isothiocyanate, metrafenone, mildiomycin, N- (4-chloro-2-nitrophenyl) -N-ethyl-4-methyl benzenesulfonamide, N- (4-chlorobenzyl) -3- [3-methoxy-4- (prop-2-yn-1-yloxy) phenyl ] propanamide, N - [(4-chlorophenyl) (cyano) methyl] -3- [3-methoxy-4- (prop-2-yn-1-yloxy) phenyl] propanamide, N - [(5-bromo-3 -chloropyridin-2-yl) methyl] -2,4-dichloropyridin-3-carboxamide, N- [1- (5-bromo-3-chloropyridin-2-yl) ethyl] -2,4-dichloropyridin-3 -carboxamide, N- [1- (5-bromo-3-chloropyridin-2-yl) ethyl] -2-fluoro-4-iodopyridine-3-carboxamide, N - {(Z) - [(cyclopropylmethoxy) imino] [ 6- (difluoromethoxy) -2,3-difluorphenyl] methyl} -2-phenylacetamide, N - {(E) - [(cyclopropylmethoxy) imino] [6- (difluoromethoxy) -2,3-difluorphenyl] methyl} -2- phenylacetamide, natamycin, nickel dimethyl dithiocarbamate, isopropyl nitrotal, octylinone, oxamocarb, oxyphentine, pentachlorophenol and salts, phosphorous acid and its salts, propanamine phosphate, sodium propanosine, proquinazide, pyrrolnitrin, 5-amino-5-amino S-Prop-2-en-1-yl (1-methyl-ethyl) -4- (2-methylphenyl) -3-oxo-2,3-dihydro-1H-pyrazol-1-carbothioate chlophthalam, technazene, triazoxide, triclamide, 6-chloro-N-phenyl-N'-prop-2-yn-1-ylthiophene-2-sulfonohydrazide and zarylamide, 8-hydroxyquinoline sulfate, 2,3-dibutyl-6-chloro -thieno [2,3-d] pyrimidin-4 (3H) one, chlororoneb, protiocarb, binapacryl, and cyprosulfamide.

Common names are used in accordance with the International Organization for Standardization (ISO) or chemical names, if appropriate together with a usual code number of the compounds, and always comprise all applicable forms such as acids, salts, esters or modifications. such as isomers, such as stereoisomers and optical isomers.

[0049] The biocidal active ingredients of the present invention may further have asymmetric carbons and therefore encompass optical isomers. Additionally, the biocidal active ingredients that may be used according to the invention may be present in different polymorphic forms or as a mixture of different polymorphic forms. Both pure polymorphs and polymorphic mixtures are suitable according to the invention.

The biocidal active ingredient which is suitable according to the invention may be formulated and / or applied with one or more additional biocidal active ingredient, compound or synergist. Such combinations can provide certain advantages such as, without limitation, exhibiting synergistic effects for increased insect pest control, reducing insecticide application rates thus minimizing any impact on the environment and worker safety, controlling a wider spectrum of insect pests, crop safety against phytotoxicity, and improved tolerance to non-pest species such as mammals and fish. Additional compounds include, without limitation, other pesticides, plant growth regulators, fertilizers, soil conditioners, or other agricultural chemicals. Synergists are compounds that enhance the action of the biocidal active ingredient without the added synergistic agent being itself active.

Some biocidal active ingredients which are suitable according to the invention act not only against plants, pests and stored hygiene products, but also in veterinary medicine in the sector against animal parasites (ectoparasites and endoparasites), such as hard tick, tick. moles, scabies mites, leaf mites, mosquitoes (biting and licking), parasitic fly larvae, lice, hair lice, feather lice, and fleas.

Some biocidal active ingredients which are suitable according to the invention also exhibit a strong insecticidal action against insects that destroy industrial materials. Industrial materials in the present context should be understood to mean non-living materials such as plastics, adhesives, sizes, paper and cardboard, leather, wood and processed wood products and coating compositions.

In another preferred embodiment the compound material of the present invention comprises at least one biocidal active ingredient which is effective in insecticidal action against base polymer-destroying insects.

[0054] Biocidal active ingredients which are suitable according to the invention may also be employed to protect composite materials that come into contact with seawater or brackish water, such as wraps, screens, nets, constructions, lockers and systems. signaling, against fouling.

In addition, some biocidal active ingredients which are suitable according to the invention alone or in combination with other active compounds may be employed as antifouling agent.

More preferably, the biocidal active ingredient of the present invention is a low volatile non-greasy non-liquid substance at room temperature where the substance may be solid or may be formulated as a substance in solid form. The choice of such substances improves detachment controllability and storage stability of the polymeric composite material.

Especially, essential oils should be avoided as biocidal active ingredients because of the difficulty of providing a stable dispersion in the basic polymeric compound or coating layer without biocidal exudation. In addition, the mechanical stability of the polymeric composite material could be inhibited in the production method due to bubble wrap and the like if high volatile liquids or substances are incorporated.

The base polymer compound according to the present invention may be selected from the group consisting of polyethylene terephthalate, polyvinyl chloride, polyolefins such as polyethylene (such as, for example LDPE, HDPE) and polypropylene, polystyrene, polyesters. -ter, polyether, polyacrylate, polycarbonate, polyamide and polyurethane which may optionally usually comprise used pigments, UV stabilizers, UV absorbers, IR absorbers and light diffusers. These materials show the resistance required for outdoor exposure and can be used in the form of flexible films as well as inflexible molded articles such as trays and pots.

According to another preferred embodiment of the invention the coating layer has a water absorption of at least 100% per given coating layer area. It is also possible to provide the mobility required for effective emission of organic biocide to the target pest or weed by diffusion and / or osmosis.

Preferably, the coating layer is based on a superabsorbent polymeric coating material.

Also, water absorption and time of water loss during outdoor exposure can be adjusted.

In another preferred embodiment of the invention, the base polymer is treated with Corona to increase the binding of the coating layer (s) to the base polymer.

Additive (s), binder (s) and at least one biocide may be incorporated into any base polymer coating layers. A particularly preferred embodiment of the present invention is a Corona-treated base polymer comprising at least one coating layer with a binder, preferably superabsorbers, and at least one coating layer with at least one biocidal active ingredient. In a preferred embodiment, the base polymer further comprises at least one coating layer with an additive, preferably a hardener (for closure). In another preferred embodiment at least one such coating layer further comprises gelatin. In another preferred embodiment of the invention all three layers further comprise gelatin.

Preferably the thickness of the entire binder coating layer (s), preferably superabsorbers and preferably also gelatin, is between 1-100 pm, preferably 5-40 pm, and particularly preferably 10-30 pm. . All coating layers may be produced by coating various coating layers, preferably superabsorbers and preferably also gelatin, for example with cascade casting or curtain casting. The thickness of the entire coating layer with at least one biocidal active ingredient and preferably also gelatin is 0.5 - 5 pm, preferably 1 - 4 pm, and particularly preferably 2-3 pm. The entire coating layer with biocide (s) and preferably also gelatin may be produced by coating several layers of the same or different biocide and preferably with gelatin, for example cascade or curtain casting. The thickness of the entire coating layer with the additive, preferably the hardener, is 0.2 - 5 pm, preferably 0.5 - 4 pm, even more preferably 2-3 pm. The entire coating layer with the additive, preferably hardener and preferably also gelatin, may be produced by coating several layers of the hardener and preferably gelatin, for example by cascade or curtain casting.

The base polymer has a thickness of 10 to 250 pm, preferably 10 to 150pm, more preferably 20 to 120pm, and even more preferred 20-50pm.

In another preferred embodiment of the invention, the base polymer is preferably Corona treated on both sides and has on both sides at least two layers comprising at least one binder coating layer (s) of preferably superabsorbers, and at least one coating layer with at least one biocide. In a preferred embodiment, the base polymer further comprises at least one coating layer with an additive, preferably a hardener (for closure). In another preferred embodiment at least one such coating layer further comprises gelatin. In an even more preferred embodiment of the invention all layers further comprise gelatin.

In another embodiment of the present invention the polymeric composite material can withstand at least 12 months of external exposure to sunlight and weather. This is independent of whether there is a coating layer present or not. Having a minimum of strength the polymeric compound is able to meet the requirements of intended use in agriculture as fumigation or cover film or as reusable seed production trays (sowing trays), for example.

Similarly, the polymeric composite material should not be biodegradable or water soluble. The function of polymeric composite material should be usable over a long period of time so that, for example, no weeds, pests or fungi can damage plants as they grow in a field under the protection of biocidal polymeric composite material. . In addition, articles of the intended use of films and trays should be usable for a longer period of time and should not degrade over a period of planting and crop cultivation, for example. Especially the mechanical stability of the films should be kept high because the film should preferably be field removable and reusable.

It is within the scope of the polymeric composite material of the invention that additional filler pigments, which are widely known to those skilled in the art, can be used.

Another object of the present invention is a method for producing a polymeric composite material according to the present invention including the steps of mixing at least one base polymer compound and at least one biocidal active ingredient such that biocidal active ingredient is incorporated in the form of a molecular dispersion, molding of the polymeric composite material into the desired shape by molding and / or film forming via extrusion or blow molding.

There are four basic methods for mixing plastics with the active biocidal ingredients: dry mixer, batch mixer, continuous mixer and helical mixer. Method selection is determined by the condition of the material, the volume of end product required and the sensitivity of biocidal active ingredients to shear stress and temperature of a polymer melt. The composting method includes two steps: (1) mixing the materials and (2) molding the mixture into pellets, laminates, sticks, or bubbles for further molding and / or film forming processing.

The present invention therefore comprises a polymeric composite material, wherein the biocidal active ingredient is incorporated into the polymeric composite material as a molecular dispersion.

Alternatively, a polymeric composite material according to the present invention may also be produced by a method for its production including the steps of mixing at least one coating compound and at least one biocidal active ingredient such that the ingredient Biocidal active is incorporated in the form of a molecular dispersion, coating the base polymer compound with the above mixture and curing the mixture to produce a coating layer.

The present invention therefore comprises a polymeric composite material in which the biocidal active ingredient is incorporated into a coating layer.

The term "coating compound" refers to any possible compound or compounds that may be used to incorporate at least one biocidal active ingredient in the base polymer. Particularly useful coating compounds according to the present invention are binders such as superabsorbers and / or gelatin. In a preferred embodiment of the invention, binders, preferably superabsorbents and gelatin and a hardener are employed as coating compounds. In another preferred embodiment, "coating compound" also comprises a carrier.

Coating compounds may be applied to the part made of the base polymer in a number of ways. Coating compounds may be sprayed on the part, or the part may be immersed in a tank of coating material. Other methods include spray-coated parts or roll-applied parts between large barrels to spread the coating.

Cascade casting or curtain casting advantageously allows the application of multiple layers, also of different thicknesses in the polymeric composite material in one working step.

The application of the coating layer is preferably carried out by curtain coating.

The curtain coating medium is well known in the field of photographic films and photographic papers and can be advantageously applied to the coating of the present invention. Improved curtain coating procedures that may be employed to produce the polymeric composite material of the present invention include such procedures as described in EP 1 023 949 A1, EP 938 935 A2, US 5,906,865, DE 195 00 402 , and EP 275,015 B1, which are therefore incorporated herein by reference.

In the curtain coating method, a base film or paper web is continuously moved by a transport device through a coating zone and is thus coated with one or more layers, either wholly or partially, by the curtain. totally or partially free-falling liquid.

In the photographic industry, this method is used, for example, to apply photosensitive and non-photosensitive coatings. Such coatings comprise most multilayers formed from aqueous coating solutions which are coated as liquid layer compounds at the base. The curtain in the curtain coating method may be wider or narrower than the base. The basis of photographic application is mostly a synthetic film or a paper web. Coating speeds may vary according to the base material and thickness and the thickness of the net curtain and its viscosity, for example. In so-called high speed coating applications photographic coating solutions can be applied at a base speed greater than 250 meters per minute. The coated base then passes through a drying device in which the coating solution is dried. The dry film web is wound. At this point the weft corners must be dry otherwise the individual layers of the roll will adhere.

With the advantageous possibility of producing the polymeric composite material of the present invention by curtain coating the base polymer compound with at least one coating layer comprising at least one biocide, binder (s), carrier and optionally additives, high production speed and low mass production costs are obtained.

In a preferred embodiment, a curtain coating is performed on a base polymer preferably treated with Corona with a first coating comprising a binder, preferably a superabsorbent and a carrier, and a second coating comprising at least one biocide. and a vehicle. In another preferred embodiment, the first binder coating further comprises gelatin and / or the second coating with at least one biocide comprises gelatin. In a preferred embodiment, a hardener as an additive is added, just prior to curtain coating, to one of the coatings. Another preferred curtain coating method is conducted with a third coating comprising a hardener as an additive and a carrier. In another preferred embodiment, the third coating comprises gelatin, carrier and a hardener as an additive, and the hardener is added to gelatin and the carrier just prior to the curtain coating.

Preferably, any of the methods according to the present invention comprise the subsequent step of coating both sides of the base polymer compound with a different mixture, each comprising at least biocidal active ingredient. It is also possible to incorporate different biocidal active ingredients, one for example for soil disinfection or plant root protection, and the other as pesticide and / or fungicide directed at the surface of the agricultural field.

As already briefly mentioned above, a polymeric composite material according to the present invention or a product obtained by a method according to the present invention may preferably be used in agriculture and / or horticulture.

Especially, it is preferred to use as cover film, fumigation film or as spread film.

Alternatively, a polymeric composite material according to the present invention or a product obtained by a method according to the present invention may be employed as propagation pots, sowing trays, and / or harvesting trays.

The invention also relates to cover film, fumigation film, spread film, spread pots, seed trays and / or crop trays comprising a polymer composite material as discussed herein.

Examples Example 1: Preparation of Propagation Films Propagation films were prepared by coating a polyethylene film with the following additional layers employing a curtain casting machine: Film 1: Base: low density polyethylene film ( 100PE-thick, Corona-treated polyethylene (LDPE) First layer: 9.36 g / m2 S1 superabsorbent (flexible absorber binder composed of: 20-40% by weight sodium polyacrylate (CAS- No .: 9003-04-7), 2-5% by weight polyethylene glycol (CAS-No .: 25322-68-3), water (CAS-No .: 7732-18-5) dissolved in 53.40 g of water Second layer: 9.36 g / m2 S1 superabsorbent dissolved in 53.40 g of water Third layer: 9.36 g / m2 S1 superabsorbent dissolved in 53.40 g of water [ 0092] Fourth layer: 9.36 g / m2 S1 superabsorbent dissolved in 53.40 g of water. Film 2: Base: 100pm thick, three-layer polyethylene (LDPE) film laced by Corona First layer: 9.36 g / m2 S1 superabsorbent and 3.12 g / m2 gelatin dissolved in 53.40 g water Second layer: 9.36 g / m2 S1 superabsorbent and 3.12 g / m2 gelatin dissolved in 53.40 g water Third layer: 9.36 g / m2 S1 superabsorbent and 3.12 g / m2 gelatin dissolved in 53 , 40 g water Fourth layer: 9.36 g / m 2 S1 superabsorbent and 3.12 g / m 2 gelatin dissolved in 53.40 g water Fifth layer: 2.34 g / m m2 gelatin dissolved in 27.53 g water Sixth layer: 1.20 g / m2 gelatin 1.33 g / m2 H1 hardener (formaldehyde, concentration: 10% in water; coating amount of 0.086 g H1 hardener per g gelatin). Gelatin and hardener are premixed immediately before curtain coating with 28.20 g of water. Film 3: Base: Corona-treated 100pm-thick low-density polyethylene (LDPE) film [00104] First layer: 9 36 g / m2 S1 superabsorbent and 3.12 g / m2 gelatin dissolved in 26.70 g of water Second layer: 9.36 g / m2 S1 superabsorbent and 3.12 g / m2 gelatin dissolved in 26.70 g water Third layer: 9.36 g / m2 superabsorbent S1 and 3.12 g / m2 gelatin dissolved in 26.70 g water Fourth layer: 9.36 g / m2 S1 superabsorbent and 3.12 g / m2 gelatin dissolved in 26.70 g of water Fifth layer: 2.34 g / m2 gelatin dissolved in 27, 53 g of water Sixth layer: 1.2 g / m 2 of gelatin, 1.33 g / m 2 of premixed H1 hardener just prior to curtain coating with 28.20 g of water.

After coating, the films were dried.

Example 2: Mechanical stability of the films Then, the films prepared according to Example 1 were rinsed for 10 minutes in distilled water. Subsequently, excess water was drained and mechanical stability was tested by washing the rinsed layers with warm flowing water. While superabsorbent layers S1 dissolve from the polyethylene layer in film 1, the additional layers in films 2 and 3 do not dissolve from the polyethylene layer.

Example 3: Preparation of Biocidal Fumigation Films According to similar methods as described in Example 1, the following six fumigation films were prepared to the following final thicknesses after drying. Base: Low Density Polyethylene (LDPE) Film 100pm thick and Corona-treated [00117] First layer: 6 pm superabsorbent binder [00118] Second layer: 6 pm superabsorbent binder [00119] Third layer: 6 pm superabsorbent binder [00120] Fourth layer: 6 pm superabsorbent binder Fifth layer: 3 pm of gelatin with herbicide Sixth layer: 3 pm of hard gelatin The following different herbicides were introduced in the fifth layer: placebo (film 1), aclonifen (150 mg / m2 ; film 2), ethoxysulfurone (6 mg / m2; film 3), isoxaflutol (10 mg / m2; film 4), benfure sate (150 mg / m2; film 5), glyphosate (200 mg / m2, film 6), halosulfuron methyl (5 mg / m2, film 7).

Example 4: Preparation of Biocidal Fumigation Films Low density polyethylenes were dry blended with 7 weight percent of a standard batch of commercial LDPE stabilizer with titanium dioxide pigments and UV HALS stabilizer, for example PLASTWITTE PE 7344 from Cabot Deutschland and the specified amount of the selected herbicide, extruded and perforated to form molded pellets. Molded pellets were placed in a standard blow molding apparatus and the thermoplastic composition was blown to form a film according to standard procedures at temperatures between 160 and 240 ° C depending on the decomposition and / or boiling temperature of the herbicide. selected. Sample cuts of various films of uniform surface area and uniform thickness of 100 pm were employed for all tests.

Films without herbicide (film 8), and with ethoxysulfurone (6 mg / m2; film 9) and benfuresate (150 mg / m2; film 10) were blow molded from the above mixtures and tested.

Table 1 indicates the physical properties of films according to examples 8, 9 and 10.

Table 1: Example 5: Enhanced Weed Control Soil-filled trays with a variety of weeds including the problematic key herbs from CYPES (Yellow Nut Sedge, Cyperus esculentus), and CONAR (Field Bindweed, Convolvulus arvensis) ) were employed in a greenhouse test with fumigation plastic films (comprising biocides) prepared according to example 4.

Soil was filled in plastic trays until it was approximately full and then the soil was lightly compressed. Uniform quantities of CYPES and CONAR herbal seeds were then sown in several sets of these trays and then the seeds were covered with soil until the trays were completely full. These filled trays were then covered with the different fumigation plastic films and an untreated placebo plastic film as a control. Light weights were placed on the plastic film to ensure that the film was not pushed up or away due to weed growth.

[00129] The full and covered trays were placed in a greenhouse with a 12 hour day and 12 hour night regime. Daytime temperatures were 24Ό and a relative humidity of 60%, and night temperatures were 16Ό also with 60% relative humidity. Light intensity was up to 60,000 Lux. The plants were irrigated by flood irrigation (water from below) daily so that good plant growth could be ensured. Plant growth was monitored by 2 representatives of each weed species that were not covered with a plastic film.

After 4 weeks the weights and plastic films were removed and a visual evaluation of the control weed was performed. Trays covered with treated plastic film were compared with trays covered with untreated plastic film. An average of the two representatives per treatment was taken and shown below in table 2. Values provided are in percent 0 = No effect; 100 = Complete death.

Table 2: Ό0131] All films comprising biocides showed medium to strong inhibition for both herbs over a period of at least 4 weeks.

Claims (10)

1. Covering film, fumigation film, spreading film, spreading pots, seed trays and / or harvesting trays, comprising a biocidal functional polymeric compound, comprising: (a) at least one base polymeric compound, and (b) at least one coating layer comprising at least one solid biocidal active ingredient, wherein at least one solid biocidal active ingredient comprises an organic biocide, wherein the solid biocidal active ingredient is incorporated into at least one coating layer; and wherein the at least one coating layer comprises at least one binder and at least one fluid carrier, characterized in that said binder is gelatin and a superabsorbent selected from the group consisting of poly (acrylamides), copolymers of maleic anhydride, poly (vinylsulfonic), poly (sodium acrylate-coacrylic acid), poly (vinyl sulfonic acid), and copolymer dispersions. block erosion of ethylene oxide with polyurethane; whereby a water absorbing capacity of at least one coating layer allows an emission of organic biocide from the polymeric composite material by diffusion and / or osmosis. Covering film, fumigation film, spreading film, spreading pots, seed trays and / or harvesting trays according to claim 1, characterized in that the polymeric composite material comprises different coating layers; wherein some layers comprise the same solid biocidal active ingredient or different solid biocidal active ingredients. Covering film, fumigation film, spreading film, spreading pots, seed trays and / or harvesting trays according to claim 1 or 2, characterized in that the organic biocide is selected from the group. consisting of pesticides, herbicides, insecticides, algicides, fungicides, molluscicides, miticides, rodenticides, germicides, antibiotics, antibacterials, antivirals, antifungals, antiseptics, antiparasites, disinfectants, and / or mixtures thereof. Covering film, fumigation film, spreading film, spreading pots, sowing trays and / or harvesting trays according to any one of claims 1 to 3, characterized in that at least one coating layer is provided. comprises at least one additive. Covering film, fumigation film, spreading film, spreading pots, seed trays and / or harvesting trays according to claim 4, characterized in that at least one additive comprises a hardener. Covering film, fumigation film, spreading film, spreading pots, seed trays and / or harvesting trays according to claim 5, characterized in that the hardener comprises formaldehyde. Covering film, fumigation film, spreading film, spreading pots, sowing trays and / or harvesting trays according to any one of claims 1 to 6, characterized in that at least one fluid carrier, is an organic solvent and / or water. Method for producing a covering film, fumigation film, spreading film, spreading pots, sowing trays and / or harvesting trays as defined in any one of claims 1 to 7, characterized in that comprising the steps of: - mixing at least one coating compound and at least one solid biocidal active ingredient, - wherein the biocidal active ingredient is incorporated as a molecular dispersion, and - coating the base polymeric compound with the above mixture and cure the mixture to provide a cover layer. A method according to claim 8, characterized in that it comprises the additional step of coating both sides of the base polymeric compound with a different mixture each comprising at least one solid biocidal active ingredient. Use of a covering film, fumigation film, spreading film, spreading pots, sowing trays and / or harvesting trays as defined in any one of claims 1 to 7, or a product obtainable by the method; as defined in claim 8 or 9, characterized in that it is in agriculture and / or horticulture.