• 专利附录
  • 专利说明
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  • 类似技术
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    • 专利摘要:
    The present invention relates to the use for the treatment of soils by fumigating a fumigant barrier film having, on at least a part of its external surface or on at least a part of its internal surface or on at least a part of its external and internal surfaces, at least one continuous self-adhesive or self-adhesive or tackifying zone. The present invention also relates to the method of sealing a floor for fumigation treatment or during treatment by fumigation or which has been fumigated, by covering said floor with a self-adhesive fumigant barrier film, and a fumigation treatment kit comprising at least one fumigant and self-adhesive barrier film and at least one fumigant.
    公开号:FR3028148A1
    申请号:FR1460834
    申请日:2014-11-10
    公开日:2016-05-13
    发明作者:Thierry Fouillet
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of fumigation of soils, that is to say the treatment of soil or plant substrates (potting soil, peat, rockwool. . . ), especially agricultural substrates, to control nematodes, pathogenic fungi, weeds, pests or bacteria.  The fumigation technique is now widely used for the disinfection of soil or plant substrates, including those for intensive agriculture and especially those for arboriculture, horticulture and market gardening.  This fumigation technique uses at least one fumigant, generally a volatile pesticide compound, which is introduced into the soil or the substrate to be treated, according to various techniques known to those skilled in the art, for example using coulters, or injection nozzles in the ground ("shank application" in English), or drip ("drip" in English).  This fumigation technique also comprises the use of at least one fumigant in the form of gas or mist, above the soil or plant substrate to be treated.  The fumigant diffuses into the soil or more generally into the substrate to be disinfected, but also rises to the surface and can dissipate into the atmosphere.  Large amounts of fumigant can be lost, resulting in a loss of effectiveness of the product used.  In addition, the fumigant and dissipated in the atmosphere can be embarrassing, or even toxic for farmers and the environment in the immediate vicinity of crops and fields treated.  To overcome this drawback, it is common to cover the fumigated floor with a polymer film impervious to fumigant vapors, as described for example in EP0766913.  This plastic tarpaulin, impermeable to gases, prevents said fumigant from dispersing in the air above the soil or substrate to be treated.  In this way, there is a gap between the soil or substrate and the polymer film, in which the fumigant vapors are concentrated, thus enhancing the efficiency of said fumigant.  Different types of films, such as polyethylene films, or SIF ("semi-waterproof film" in English), VIF ("virtually waterproof film" in English), or TIF ("totally waterproof film" in English) , are today used during the treatment of soils or substrates by fumigation.  The films for the disinfection of agricultural soils can be classified into two categories according to the duration of use: a) Category 1: "simple" protection: These films are kept in place for the duration of the - 2 - disinfection required of the substrate to be treated and then removed before culturing.  This category includes two sub-categories, depending on whether the films are assembled together or not by gluing: i) films set up without gluing, film on film ii) films whose surface condition allows the assembly of the strips by gluing in if you ; b) Category 2: Protection and mulching: Films in this category first provide protection during disinfection and are then held in place as mulch film.  In the present invention we are interested rather in the first category where the films are assembled together, but also in the second category, where the films can also be assembled together.  [0008] The polymer films are advantageously deposited on the soil or the substrate, before or after the fumigation treatment, and left in place for the time necessary to allow effective control of the nematodes, phytopathogenic fungi, bad weeds, harmful insects and other bacteria.  After this period of treatment, the duration of which depends largely on the soil or substrates to be treated, climatic conditions, the type of culture envisaged, and others, the polymer films may be, if necessary, removed or simply perforated, in order to allow the planting crops.  [0009] The use of polymer films in the fields has other advantages such as the increase of the soil temperature especially in the early spring, the reduction of the problems related to the emergence of weeds, the conservation moisture, reducing the number of certain insect pests, higher yields and more efficient use of soil nutrients.  [0010] Most mulch films are generally black for weeding, white for cooling, or clear for short-term disinfection or for soil heating.  The temperature of the soil under a plastic mulch depends on the thermal properties (reflection, absorption or transmission) of the particular material constituting the film, with respect to the incoming solar radiation.  For example, black mulch retains moisture and heat while preserving weed infestation.  Black, the dominant color used in vegetable production, is an opaque absorber and a radiator.  Black mulch absorbs most ultraviolet (UV), visible and infrared (IR) wavelengths from incident solar radiation and emits a portion of the absorbed energy again as thermal or infrared radiation.  Much of the solar energy absorbed by the black plastic mulch is lost to the atmosphere by radiation and forced convection.  On the other hand, transparent polymer films do not absorb solar radiation, but transmit 85% to 95% of said radiation, with relative transmission depending on the thickness and degree of opacity of the film.  The surface beneath these polymer mulches is usually covered with condensed water droplets.  This water is transparent to the incoming shortwave radiation, but is opaque to outgoing infrared heat radiation, heat lost to the atmosphere from a bare ground by infrared radiation but which is retained by the transparent polymer mulch.  White films, meanwhile, may cause a slight decrease in soil temperature compared to a bare soil, because they reflect, in the plant cover, most of the incident solar radiation.  These mulches can be used to establish a crop when soil temperatures are high, such as in very sunny areas and where any reduction in soil temperature is beneficial.  [0014] There is thus today a large quantity of polymer films already widely used in agriculture, some of them combining photocatalytic properties, as described for example in application WO2013030513, and which are particularly suitable for fumigation of soils.  One of the difficulties, however, related to the use of these so-called fumigation films is that they need to be positioned, or even repositioned, on the floors so as to ensure the most perfect seal possible in order to retain all or at least the largest part of fumigant gases, avoiding as much as possible fumigant leakage into the atmosphere, the health authorities of many countries now requiring that a waterproof film be applied to any fumigated soil.  Thus, to completely cover a previously fumigated soil, it is common to distribute on the ground parallel film strips and to seal between said film strips, by gluing edge to edge between them.  Bonding the strips together is a technique now widely known and used especially for fumigation treatment with methyl bromide, and is now extended to fumigation treatments with other fumigants.  [0017] It is thus known today to lay the plastic films by overlapping them slightly one on the other, by joining or gluing according to several different techniques (cf.  for example US4050972), and which implement various types of adhesives among which may be mentioned: - Adhesives diluted in a solvent, such as for example rosin-based adhesives in dichloromethane; these types of solvent-based adhesives, however, impose the additional difficulty of subsequently removing said solvent, the so-called "hot melt" adhesives, as described for example in US Pat. No. 5,535,461, but which require a heat treatment and therefore additional operations costly and involving a significant additional workforce.  All these known techniques for completely sealing a floor covered by fumigated film strips therefore require one or more additional operations that are most often delicate or difficult to implement, and which generate additional costs and often prohibitive for the farmer who has to comply with the norms and authorities of regulation of the culture by fumigation.  [0019] There remains therefore a need for fumigation films that are easy to use and in particular that the installation on fields and soils of culture in general, is facilitated in particular so that the sealing between the strips of movies are easily made.  The invention proposed here solves, in whole or at least in part, the disadvantages known from the prior art and in particular the difficulties encountered in achieving the sealing of fumigation films.  Still other objects are achieved by the present invention which is now detailed in the description which follows.  Thus, and according to a first subject, the present invention relates to the use for fumigant soil treatment of a fumigant barrier film having on at least part of its external surface or at least a portion of its surface. internal surface or at least a portion of its outer and inner surfaces, at least one self-sticking or self-adhesive continuous zone or "tackifying".  The present invention thus proposes the use for fumigating the soil of at least one barrier film, that is to say, vapor-proof fumigant, and having a tackifying power on the inner face and / or external of the film, so as to create at least one self-adhesive continuous zone, generally continuous and parallel to the greatest length of the film, so that the film strips laid parallel to each other on the floors provide a fumigant seal .  According to one embodiment of the invention, the entire external or internal surface of the film constitutes the self-adhesive area of the film.  The use according to the present invention makes it possible to dispense with the additional step or steps of sealing by bonding and / or welding together film strips for fumigation.  The so-called "self-adhesive" films used in the present invention can be laid according to the conventional techniques for laying conventional so-called fumigation films and the fumigant seal is ensured by virtue of the properties of the "self-adhesive" or "self-adhesive" film. adhesive ".  It is also possible, in order to ensure perfect sealing and perfect bonding of the strips to one another, to apply pressure to the self-adhesive continuous zone, this pressure being able to be especially achieved during the laying of the fumigation film, by all means known to those skilled in the art, and for example, and without limitation, via a pressure roller or pressure roller.  According to a preferred embodiment, the invention relates to the use of a self-adhesive film that can be applied according to at least one of the following techniques: a) laying a film of barrier film fumigant and self-adhesive, overlapping another of said self-adhesive fumigant barrier film, optionally pressing on the overlap area, simultaneously or after application of the self-adhesive fumigant barrier film (s), b Simultaneous application of a conventional (ie, non-self-adhesive) barrier film web and a small strip of self-adhesive, fumigant barrier film between two barrier film webs with conventional gas, that is to say non-adhesive, optionally pressing the small strip of self-adhesive film, simultaneously or after the laying of the fumigant barrier film or sheets, c) alternating laying of a film of barrier film to the fumigant and sticker overlapping a conventional fumigant barrier film (i.e., non-self-adhesive), optionally pressing on the overlap area simultaneously or after the fumigant barrier film webs have been applied.  The invention also relates to the method of sealing a floor for fumigation treatment or during fumigation treatment or that has been treated by fumigation, said method consisting in covering all or at least a portion of said soil of a fumigant barrier film having at least one continuous self-adhesive zone.  Preferably, the method for sealing a soil according to the invention comprises one of the three techniques previously described under a), b) or c).  By "fumigant barrier film" is meant a fumigant impermeable film, wherein the impermeability is defined according to NF T54-195-2: 2014.  It has been discovered quite surprisingly that it is possible to combine, in the same fumigation film, the properties of fumigant impermeability and self-adhesive properties.  Indeed, it should be understood that the more or less important self-adhesive area, or even completely self-adhesive especially for reasons of simplicity of implementation of the film, must also have the character "fumigant barrier" required for all fumigation film.  Thus, the use according to the present invention is characterized by the use of a fumigant barrier film containing at least one continuous self-adhesive zone, continuous and parallel to the greatest length of the film, on at least a portion of its surface. outer surface or its inner surface or on its outer and inner surfaces.  [0029] Self-adhesive or self-adhesive films are already known and commercially available, some of which are used today for the manufacture of stretchable films, especially stretchable polyethylene films, especially for food packaging. , for the protection of pallet loads, for silage, and others. . . , as described for example in the application WO2013061264.  The self-adhesive properties of these films are most often obtained by adding in the polymers that make up these films an effective amount of one or more tackifiers or "tackifying" agents.  All the tackifying agents known today can be used and, among these, it is advantageous to mention the rosin derivatives, the polyterpenes, low molecular weight hydrocarbon tackifying resins, for example poly (iso-butene), also known by his acronym Pl B.  Among the known manufacturing processes, there may be mentioned those using a master-batch (or master-batch in English) based on polyolefin comprising a tackifier, for example based on polyethylene (PE) containing Pl B, the masterbatch may represent from 1% to 20% by weight, preferably from 1% to 15% by weight, relative to the total weight of the tackifier film.  Pl B is for example commonly used today for the manufacture of self-adhesive films such as those listed above for the manufacture of stretchable films, for food packaging, for the protection of pallet loads, for silage, etc.  The tackifying agents which can be used for the preparation of films adapted to the needs of the present invention are known and readily available, generally in liquid form, but also and advantageously in the form of a masterbatch (or "master batch"). In English), that is to say diluted in a polymer matrix, for example in a polyethylene matrix.  The tackifying agent is thus advantageously introduced in its master-batch form into the polymer during the manufacture of the plastic film.  The films used in the context of the present invention may consist of one or more layers.  At least one layer is a layer containing a suitable amount of tackifier, that is, one or more of the layers each capable of containing a suitable amount of tackifier.  By suitable amount is meant an amount allowing effective adhesion of the film on itself or on any other plastic film barrier to the fumigant gas, while permitting to take off [0035] According to one embodiment of the invention, the film for fumigation comprises at least one layer comprising a polymer chosen from polyolefins, polyamides and polyesters, and preferably polyolefins, polyamides and biosourced and / or biodegradable polyesters.  For the purposes of the present invention, the term "polyolefin" is intended to mean a random or block polymer or copolymer resulting from the polymerization or copolymerization, respectively, of monomers which are olefins, preferably chosen from ethylene, propylene, 1-butene, and the like, as well as mixtures thereof.  By way of examples of polyolefins, mention may be made of: propylene-based polymers, such as propylene homopolymers, copolymers of propylene with ethylene and / or an olefin comprising from 4 to 10 carbon atoms ( ex.  butene, pentene, hexene, and the like), heterophasic polypropylenes or mixtures thereof, these polymers being obtainable by any process known to those skilled in the art, for example in suspension or in the gas phase with Ziegler-Natta type catalysts or metallocene; polyethylenes chosen from homopolymers of ethylene or copolymers comprising at least 50 mol% of ethylene and one or more other comonomers.  According to a preferred embodiment, a polyolefin which can be used is polyethylene obtained by polymerization, preferably homopolymerization of ethylene, but also by copolymerization with an α-olefin, and in particular an α-olefin having from 2 to 30 carbon atoms. carbon.  As α-olefin, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3- Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene , 1-hexacocene, 1-octacocene, and 1-triacontene.  As other co-monomers of the copolymers with the polyolefins described above, mention may also be made of: dienes, such as, for example, 1,4-hexadiene, ethylidene norbornene, butadiene, esters, unsaturated carboxylic acids such as, for example, alkyl acrylates or alkyl methacrylates grouped under the term "alkyl (meth) acrylates", the alkyl chains of these (meth) acrylates having up to 30 atoms; carbon, with alkyl chains as examples: methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, methyl (meth) acrylates, ethyl and butyls being pr - unsaturated carboxylic acids and their salts, for example acrylic acid or methacrylic acid and the salts of these same acids, vinyl esters of carboxylic acids, among which mention may be made of vinyl acetate, vinyl versatate, vinyl propionate, vinyl butyrate, vinyl maleate, vinyl acetate being most preferred.  Among the polyesters that can be used for fumigation films, mention may be made of biosourced or biodegradable polyesters, and more preferably those chosen from: polylactides: for example, polymers and copolymers of acid lactic acid (PLA) or polymers and copolymers of glycolic acid (PGA); poly (hydroxyalkanoates), homo- or co-polymers (or PHA): for example, poly (hydroxybutyrates) (PHB), hydroxybutyrate-valerate (PHBV) copolymers, for example poly (3-hydroxybutyrate) poly (3-hydroxyvalerate), hydroxybutyrate-hexanoate copolymers (PHBHx), and hydroxybutyrate-hexanoate (PHBO) copolymers; poly (alkylene) succinates (PAS), such as for example poly (ethylene) succinate or PES, and poly (butylene) succinate or PBS; other polymers such as poly (butylene) succinate-adipate or PBSA, poly (butylene) adipateterephthalate or PBAT, poly (caprolactone) or PCL, poly (trimethylene terephthalate) or PTT.  The term "biobased" or "renewable" applies to a natural resource / 5 whose stock can be reconstituted over a short period on a human scale, the resource must renew itself as quickly as it is consumed.  In the context of the present invention, the bio-sourced materials correspond to organic materials whose carbon atoms come from non-fossil resources (cf.  ASTM 6866: "Biobased Materials - organic materials in which carbon corns from contemporaty (non-fossil) zo biological sources").  The term "biodegradable" applies to a material that can be degraded by microorganisms.  The result of this degradation is mainly the formation of water, carbon dioxide and / or methane, as well as possibly by-products (residues, new biomass), which are not toxic for the environment.  For the purposes of the present invention, the polyolefins chosen from polypropylene, polyethylene, copolymers of ethylene and an α-olefin, and ethylene / alkyl (meth) acrylate copolymers are advantageously used. ethylene / vinyl ester copolymers of carboxylic acids.  The polymer layer including a polyolefin and more particularly polyethylene 30 is preferably the main constituent, and advantageously the single component, comprises at least one tackifier or tackifying resin, as indicated above.  [0044] In a variant, the fumigation films that can be used in the context of the present invention may comprise one or more other polymer layers, or consist of one or more other polymers containing at least one tackifying agent or a tackifying resin, said polymers which can then be chosen from nitrogen polar and / or oxygenated resins, for example from polyamides, copolyamides, ethylene-vinyl acetate copolymers (EVOH), polyesters and copolyesters, for example polyglycolic acid (PGA) thermoplastic starches and mixtures of two or more of them in all proportions.  For the purposes of the present invention, the term "polyamide" is intended to mean a polymer or copolymer comprising the condensation products of: - one or more amino acids, such as aminocaproic, amino-7-heptanoic or amino acids; 11-undecandic and / or amino-12-dodecandic; one or more lactams, such as caprolactam, oanantholactam and / or lauryllactam; one or more diamines, optionally in the form of salts, such as hexamethylenediamine, dodecamethylenediamine, metaxylylenediamine, bis-para-aminocyclohexylmethane and / or trimethylhexamethylenediamine with one or more diacids, for example chosen among isophthalic, terephthalic, adipic, azelaic, suberic, sebacic and dodecanedicarboxylic acids; or mixtures of these monomers leading to copolyamides.  It is possible to use mixtures of polyamide and / or copolyamides.  According to a preferred embodiment, the fumigation film that can be used in the present invention comprises a polymer chosen from polyamide-6, polyamide-6,6, and ethylene-vinyl acetate copolymers, in particular saponified copolymers. vinyl acetate and ethylene (EVOH), as well as mixtures thereof.  The films which can be used according to the present invention must furthermore have a mechanical strength which is suitable for handling in the field, a mechanical strength which results in much easier handling.  In particular, the films do not break and tear, even when the film placed on the ground is trampled by the feet of the users, handlers, farmers and others, but also during the laying of the film strips on the ground. to be protected by machinery and apparatus intended for that purpose.  According to yet another variant, the films that may be used in the context of the present invention may comprise or may comprise one or more other polymers, and in particular so-called compatibility polymers that are generally used to make the polymers compatible with one another or two layers of polymers together, to be assembled as a two-layer or multi-layer film.  It is known that some polymers of different natures are only slightly compatible with each other, and make them integral is often difficult.  This is particularly the case of two-layer or multi-layer films comprising a layer based on polyolefin (s) and a layer based on polyamide (s) (PA) or on EVOH, such as for example the films 35 PA / EVOH or PA / EVOH / PA.  The compatibilization between the polymers and / or the polymer layers with one another is described for example in the applications FR 2 291 225, EP 0 342 066 and WO2013030513, and the polymers which can be used. for this purpose are advantageously chosen from: - propylene-based polymers, such as homopolymeric propylenes, copolymers of propylene with ethylene or a monomer comprising from 4 to 10 carbon atoms (for example butene, pentene, hexene, and others), heterophasic polypropylenes or mixtures thereof, the synthesis of these polymers can be carried out by any method known to those skilled in the art (for example in suspension, or in the gas phase with catalysts of the Ziegler Natta or metallocene type) ; polyethylenes chosen from homopolymers of ethylene or copolymers comprising at least 50 mol% of ethylene and one or more other comonomers, when the comonomer of the copolymer is an α-olefin, α-olefins having 2 to 30 carbon atoms, it being understood that, as second monomer, mention may be made of those chosen from: - dienes, for example 1,4-hexadiene, ethylidene norbornene, butadiene, - unsaturated carboxylic acid esters such as, for example, alkyl acrylates or alkyl methacrylates, grouped under the term alkyl (meth) acrylates, the alkyl chains of these (meth) acrylates having up to 30 atoms of carbon, and among these alkyl chains may be mentioned methyl, ethyl, propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetrad alkyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, the preferred unsaturated carboxylic acid esters being methyl (meth) acrylates, ethyl and butyl; and vinyl esters of carboxylic acids, among which mention may be made of vinyl acetate, vinyl versatate, vinyl propionate, vinyl butyrate, or vinyl maleate, preferably vinyl acetate, polyethylene, polypropylene, ethylene / α-olefin copolymers, for example ethylene / propylene copolymers, ethylene / butene copolymers, all these products being grafted with anhydrides of unsaturated carboxylic acids such as, for example, maleic anhydride; or glycidyl methacrylate, ethylene / alkyl (meth) acrylate / maleic anhydride copolymers, maleic anhydride being grafted or copolymerized, ethylene / vinyl acetate / maleic anhydride copolymers, maleic anhydride being grafted or copolymerized copolymers, ethylene / alkyl (meth) acrylate / glycidyl methacrylate copolymers, the glycidyl methacrylate being grafted or copolymerized, the copolymers ethylene / vinyl acetate / glycidyl methacrylate, the glycidyl methacrylate being grafted or copolymerized, ethylene / (meth) acrylic acid copolymers, optionally their salts, polyethylene, propylene or ethylene / propylene copolymers, these polymers being grafted with a product having a site reactive with amines, such as for example maleic anhydride, epoxy, and the like, these graft copolymers being then condensed with polyamides or polyamide oligomers having a single amine end, for example with mono-oligomers. caprolactam amines, as described, for example, in US Pat. Nos. 5,070,145 and EP 0 564,338; mixtures of one or more of these polymers and / or copolymers.  As indicated above one or more layers, in the case of multi-layer films, the fumigant film used in the context of the present invention may contain at least one tackifying agent or tackifying resin, incorporated (s) according to techniques known to those skilled in the art.  Indeed, and as indicated above, the fumigation films that can be used in the context of the present invention are known and commercially available or easily prepared according to techniques well known to those skilled in the art, and for example according to the techniques used. conventional extrusion, coextrusion of sheaths, extrusion and coextrusion of cast-films, extrusion blow molding and the like, using one or more extruders, or by polymer blends according to the usual techniques of melt blending (twin screw, Buss, single screw), and other methods well known to those skilled in the art.  The various polymers and / or copolymers constituting the multi-layer films according to the invention may also contain one or more additives known to those skilled in the art chosen from antioxidants, protective agents U. V. , agents for use, agents for preventing extrusion defects, anti-fogging agents, antiblocking agents, antistatic agents, nucleating agents and dyes.  These agents may be added in one or more of the constituent layers of the films of the present invention, according to techniques and in mass proportions also well known to those skilled in the art.  In particular, the films used in the context of the present invention may comprise one or more agents, organic and / or inorganic, protection against ultraviolet radiation.  Indeed, the films of the invention are intended to be exposed for long periods of solar radiation and are thus likely to be degraded under the effect of ultraviolet (UV) radiation.  If they are not protected, this degradation results in a plastic film becoming opaque and friable.  According to a preferred embodiment, the films useful in the present invention may also comprise at least one protective agent against degradation due to UV radiation.  Such protective agents are well known to those skilled in the art and can be chosen from the benzophenone or benzotriazole type molecules, the molecules known under the name of "HALS" (acronym for "Hindered Amine Light Stabilizers" in English), as well as than the mineral anti-UV, such as, for example, TiO 2 in its non-photocatalytic form.  According to another variant of the invention, fumigation films useful in the context of the present invention may also comprise one or more and / or one or more polymer layers called "reinforcement", interposed (s) or not between the constituent polymeric layers of said film.  These reinforcement layers further strengthen the structure of the fumigation film.  The nature of these reinforcing layers may be of any type known to those skilled in the art, and these layers may in particular comprise one or more of the polymers defined for the polymer layers defined above.  It should be understood that the adhesion of the reinforcing layer (s) can be improved by incorporation in said layer (s) of at least one compatibilizer, or else be co-extruded with a polymer. compatibility, as previously described.  According to yet another variant, the invention relates to the use of fumigation films as just described and further comprising one or more colored layers.  Indeed, plastic films or tarpaulins commonly used on soils or culture substrates may need to be colored, depending on whether one wishes to benefit from the temperature of the air or the soil, to preserve a certain degree of humidity or others.  The films of the present invention may thus consist of, or comprise, an additional layer colored, white, black, or any other color defined according to needs and climatic and edaphic conditions.  Such colored layers can be obtained according to techniques well known to those skilled in the art and for example, and without limitation, from masterbatches in the English language based on polyethylene (PE ) containing one or more pigments intended to provide the color, for example carbon black for the black color, pigmentary titanium dioxide for the white color, etc.  The colored layer may comprise, like the other possible constituent layers of the film, at least one tackifying agent or at least one tackifying resin, as indicated above.  On the other hand, in the case where the colored layer and the adjacent layer are not compatible with each other, it is possible to improve the adhesion between these two layers by using a compatibilizing agent or a compatibility layer, as previously described.  The thickness of the fumigated film that can be used in the context of the present invention, which comprises one or more polymer layers, can vary in large proportions.  However, the various polymer layers assembled must confer an acceptable mechanical strength to the film, and their respective thicknesses must not be too large so as not to stiffen said film which must remain easily manipulated.  Thus, and by way of nonlimiting example, the thickness of each of the polymer layers is generally between about 5 μm and about 100 μm, preferably between 5 μm and 75 μm, preferably between 5 μm and 60 μm. more preferably between 5 pm and 50 pm.  As a rule, the total thickness of the self-adhesive film used in the context of the present invention is between 5 μm and about 100 μm, preferably between 5 μm and 75 μm, preferably between 5 μm and 60 μm. more preferably between 5 pm and 50 pm.  The fumigation films as just described can be placed on the ground either before proceeding to the injection of fumigant (s), or immediately after this injection.  The tackifying properties of the fumigation films described above make it possible to ensure, in a particularly easy and effective way, a seal against the vapors of the fumigant, for example by superposition and gluing of the strips (or strips) of films, but also by burial in the earth. film borders, and / or any other techniques known to those skilled in the art.  Thus, the sealing method according to the present invention also comprises a step of injecting at least one fumigant immediately before the laying of the film, or after the laying of the film.  When the fumigant is injected before the laying of the film, the injection is preferably carried out in the soil, according to all techniques well known to those skilled in the art and for example using coulters.  When the fumigant is injected after the laying of the film, the fumigant is injected by any method known to those skilled in the art and for example by drip injection on the floor.  The fumigation films that may be used in the present invention may be photocatalytic films as described, for example, in the patent application JP 9-263502 or the application WO2013030513.  Thanks to the presence of photocatalyst, the fumigation films have, in addition to good mechanical strength and gas barrier properties, the ability to photocatalyst the fumigant which is trapped between the ground and said film.  This photocatalysis makes it possible, by means of ultra-violet radiation, for example from the sun, lamps used in greenhouses and the like, the decomposition of the often toxic and / or malodorous organic compounds which are used for the fumigation of said soils.  With fumigation films having tackifying properties and thus ensuring excellent sealing of the floors covered by said films, it is possible to use any type of fumigants known to those skilled in the art, chosen from nematocides. , herbicides, fungicides, insecticides, and bactericides, for example those listed in "Pesticide Manual," 10th edition, Ed.  Clive Tomlin.  By "fumigant" in the present invention is meant any type of phytosanitary compound that fulfills at least the two following essential conditions: (i) it does not present, at the doses at which it is active, any phytotoxicity on the cultures put in place after treatment and (ii) possess the essential and rare property of not being completely absorbed in the soils or substrates of culture and of diffusing rapidly, in the gas form, in the thickness of the soil to be treated, the organisms plant pathogens often at least 50 centimeters below the surface of said soil or said substrate.  In addition, for obvious reasons of productivity, as well as to limit the risk of new infestation, the treatment time during which the fumigant acts should be as short as possible.  As non-limiting examples of fumigants, mention may be made of methyl bromide, methyl iodide, methyl isothiocyanate (MITC), allyl isothiocyanate (AITC), 20 1, 3-dichloropropene, chloropicrin, ethanedinitrile (EDN), sulfuryl fluoride (SO2F2), phosphine, tetrathiocarbonate or other MITC-generating compounds, such as metam sodium and metam potassium, as well as tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2-thione (better known as Dazomet), as well as certain sulfur-containing compounds, such as alkyl sulfides, dialkyl disulfides, polysulfides and the like. dialkyl, thiosulfinates and the like, as well as mixtures of two or more of them in all proportions.  All these fumigant compounds are known and widely described in the literature.  The international application WO2002074083 describes, in particular, fumigants based on sulfur-containing compounds, and in particular the compounds corresponding to the general formula (I) RS (O), -Sx-R '(I) in which R is chosen from radicals alkyl and alkenyl containing 1 to 4 carbon atoms, n is 0, 1 or 2, x is 0 to 4 inclusive, and R 'is selected from alkyl and alkenyl containing from 1 to 4 carbon atoms or, only when n = x = 0, R 'may represent a hydrogen atom or an alkali metal atom.  The fumigants mentioned above, alone or in mixtures, and in particular those of formula (I) above, are particularly suitable for the fumigation of sols or substrates, in joint use with the fumigants mentioned above. fumigation films usable in the context of the present invention and described above because they fulfill three essential conditions to be used practically in disinfecting soils or substrates: they exhibit global pesticidal properties (nematocides, fungicides, herbicides, insecticides, bactericides) ; they are able to spread rapidly in the thickness of the soil to be treated; and they lead to a concentration of gas sufficient to kill the phytopathogenic organisms present.  Among the fumigants known today, it is preferred for the purposes of the present invention those of formula (I) above.  Indeed, as substitutes for methyl bromide, the compounds of formula (I) are all the more interesting that some are already present in nature from the natural degradation of cruciferous and alliums.  In particular, the thiosulfinates, included in the general formula (I), are products naturally emitted when alliums are ground and, as such, can be used in organic farming.  On the other hand, the compounds of formula (I) do not contain halogen-generating halogen radicals responsible for the catalytic destruction of stratospheric ozone, the compounds of formula (I) are harmless. for the ozone layer.  Nonlimiting examples of R and R 'radicals include methyl, propyl, allyl and 1-propenyl radicals.  Among the compounds of formula (I), those for which n = 0, that is to say the compounds corresponding to formula (I '), are preferred: RS-Sx-R' (r) in wherein R and R ', which are identical or different, preferably identical, are each independently of one another an alkyl or alkenyl radical, preferably alkyl, containing from 1 to 4 carbon atoms, and x represents 1, 2 , 3 or 4.  Other preferred compounds are disulfides (n = 0, x = 1) and more particularly dimethyl disulfide (DMDS).  The fumigants described above, and in particular the compounds of formula (I), described above can be used in pure form or in various forms, for example in emulsions, in microemulsions, aqueous, organic or hydro-organic, in the form of emulsifiable concentrate, in the form of microencapsulated products, nano-encapsulated or supported by a solid, in aqueous solutions, organic, or hydro-organic, or in admixture with one or more products having a activity for the treatment of soils or substrates.  [0076] All the formulations defined above can be carried out according to methods that are well known to those skilled in the art.  Thus, for example, aqueous emulsions and microemulsions can be obtained by adding one or more surfactants to the fumigant compound, and then adding to the resulting mixture a certain amount of water so as to obtain a stable emulsion or microemulsion.  Are more particularly suitable for the preparation of aqueous emulsions or microemulsions surfactants of predominantly hydrophilic nature, that is to say those having a HLB ("Hydrophilic Lipophilic Balance") greater than or equal to 8, which may be of anionic, cationic, nonionic or amphoteric nature.  As non-limiting examples of anionic surfactants include alkali metal salts, alkaline earth metal, ammonium or triethanolamine alkyl-, aryl- or alkylaryl-sulfonic acids, fatty acids at basic pH. , sulfosuccinic acid or alkyl, dialkyl, alkylaryl or polyoxyethylene alkylaryl esters of sulfosuccinic acid.  Mention may also be made of alkali metal or alkaline earth metal salts of sulfuric acid, phosphoric acid, phosphonic acid or sulphoacetic acid esters and of saturated or unsaturated fatty alcohol esters, as well as their alkoxylated derivatives.  Still other surfactants are represented by the alkali metal or alkaline earth metal salts of alkylarylsulphuric, alkylarylphosphoric and alkylarylsulphoacetic acids, as well as their alkoxylated derivatives.  The cationic surfactants that can be used are, for example, those of the family of quaternary alkylammoniums, sulphoniums or fatty amines with an acidic pH, as well as their alkoxylated derivatives. As non-limiting examples of nonionic surfactants, mention may be made of alkoxylated alkyl phenols, alkoxylated alcohols, alkoxylated fatty acids, glycerol fatty esters or sugar derivatives of sugar.  The amphoteric surfactants that can be used are, for example, alkyl betaines or alkyl taurines.  Preferred surfactants for the preparation of aqueous emulsions and microemulsions are alkyl benzene sulfonate and alkoxylated alkyl phenol compounds.  For the fumigant formulations in the form of a solution, the organic solvents which can be used are hydrocarbons, alcohols, ethers, ketones, esters, halogenated solvents, mineral oils, natural oils and their derivatives. as well as aprotic polar solvents such as dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone.  Biodegradable solvents, more particularly the methyl esters of rapeseed oils, are particularly suitable.  According to a variant of the present invention, two or more fumigants may be used, jointly, in a mixture, alternately or sequentially.  In particular may be used two or more fumigants having complementary or synergistic activities selected from 1,3-dichloropropene, EDN, sulfuryl fluoride (502F2), phosphine, methyl iodide, chloropicrin (CI3C- NO2), metam sodium (CH3-NHCS2Na), metam potassium (CH3-NHCS2K), sodium tetrathiocarbonate (Na2CS4), MITC (CH3-NCS), AITC, Dazomet (generator of MITC), and the compounds of formula (I), and in particular dialkyl disulfides, for example DMDS.  In the context of the present invention, that is to say in combination with the fumigating films with tackifying properties described above, the fumigants and the compositions containing them can be applied according to any of the conventional methods of the invention. introduction of pesticides into the soil, such as, for example, coulter injection which allows the product to be introduced in depth, spraying on the ground, drip irrigation by a conventional irrigation system or spraying of the type " sprinkler ".  After the fumigant (s) have been introduced into the soil or the cultivation substrate, it is possible to carry out a distribution, for example by roto-spades in the case of an injection into the soil.  The doses of fumigant (s) generally applied to obtain the desired effect are generally between 150 g / ha and 1000 kg / ha, preferably between 1 kg / ha and 750 kg / ha and depend on the nature of the or fumigants used, the degree of soil infestation, the nature of pests and plant pathogens, the type of crop and soil or substrate, and methods of application.  At the doses indicated above, the desired general pesticidal effect (both nematocidal, fungicidal, herbicidal, insecticidal and bactericidal) is observed and no phytotoxic or negligible effect.  It is not beyond the scope of the present invention by combining the treatment with a compound of formula (I) with a treatment (simultaneous or not) with one or more other pesticides, insecticides and / or fungicides and / or with a fertilizer.  The present invention also relates to the use of fumigation films with tackifying properties as just described, in the fumigation processes of soils or substrates intended for cultivation, in particular for vegetable and horticultural crops, such as that, for example and without limitation, strawberries, salads, tomatoes, melons, cucumbers, aubergines, carrots, potatoes, banana, pineapple, ornamental flowers, but also arboriculture and vine, and others.  The films that can be used in the context of the present invention can also be used on soils, substrates or, more simply, articles that are not necessarily intended for cultivation, but which undergo fungal infestations, and / or infestations. insects, nematodes, and other insects, larvae, slow, harmful.  Possible uses are, for example, in the fields of wood storage, hay, straw, cereals, in addition generally any foodstuff or not and liable to be degraded by fungi, insects, larvae, nematodes and others.  The invention also relates to a fumigation treatment kit comprising at least one fumigant barrier film and self-adhesive (tackifier) as described above, and at least one fumigant, preferably at least one volatile organic sulfur compound, preferably of formula (I) or formula (I '), more preferably said fumigant comprising dimethyl disulfide.  Another object of the present invention relates to the method of fumigating a soil, a cultivable substrate or an article, comprising at least the following steps: a) application in said soil, substrate or article, and or at the surface of said soil, substrate or article, at least one fumigant, as just defined, and / ob) total coverage of said soil, substrate or article by a tackifying film, as defined above , before or after step a).  In a preferred embodiment, the fumigation method according to the invention comprises at least the following steps: a) application in said soil, substrate or article, and / or on the surface of said soil, substrate or article at least one fumigant, as just defined,; b) total coverage of said soil, substrate or article by a tackifying film, as defined above, before or after step a); c) fumigation treatment by allowing said fumigant to act by itself under said film, for a duration that can vary from a few days to several weeks; and zo d) total or partial withdrawal, or simple perforation, of said film.  In the process described above, the term "tackifying film" refers to the fumigation film described above in the present description.  As indicated above, said tackifying film may comprise at least one tackifying agent and / or at least one tackifying resin.  At least a portion of the film may comprise said at least one tackifier and / or said at least one tackifying resin.  As a variant, the entire film is a tackifying film, that is to say that said at least one tackifying agent and / or said at least one tackifying resin and distributed uniformly in said tackifying film.  As indicated above, the tackifying film, in whole or at least in part, may be distributed over all or at least part of the soil, substrate or article, as indicated above, provided that all of said soil, substrate or article, is covered in a sealed manner by a film for fumigation, the sealing being provided completely or at least partially by a tackifying film as defined above.  In the process described above, it is thus envisaged the possibility of injecting at least one fumigant between the film and the substrate.  The injection into the soil of the fumigant or fumigants can be carried out according to any technique known to those skilled in the art, and for example as described above.  After the fumigation step, the fumigation tackifying film used in the process of the invention may be removed, when it is considered that the fumigant (s) has (have) filled its (their role.  The withdrawal can be total or partial, or even stay in place.  In the latter case, the film can be perforated in one or more predefined places, where crops will be planted, such as transplants for example.  The advantage of using a tackifying film as just defined is that it can be deposited on the soil, substrate or article, before or after the so-called fumigation step, for example by simple unwinding of the film on said soil, substrate or article, sealing being ensured, by contact, possibly accompanied by a more or less strong pressure, strips (or strips) of films between them, preferably on their zones overlap (or overlap), to prevent leakage of the fumigant into the atmosphere, the fumigant to be retained during the required period of fumigation between the soil, substrate or article and the fumigation film.  When the fumigated film used is a photocatalytic effect film, as indicated above, the photocatalytic action is provided by exposure to ultraviolet radiation, for example direct sunlight or by means of fluorescent lamps. ultraviolet radiation, used for example in greenhouse crops.  The ultraviolet radiation has the effect photocatalytic action of the photocatalyst particles (s) present in all or part of the fumigation film, which photocatalyst degrades the vapors or fumigants that emerge from the soil or treated substrate.  After photocatalytic destruction of the fumigant vapors, the plastic films can be removed in whole or in part from the soils or substrates to allow the planting of the crops in soils treated by fumigation.  According to yet another aspect, the invention relates to a fumigation treatment kit of a sol comprising at least one tackifying film for fumigation as defined above, and at least one fumigant, preferably at least one volatile organic compound. sulfur, preferably of formula (I) or formula (I ') as defined above, and more preferably said fumigant is dimethyl disulfide or DMDS.  The examples below illustrate the invention without however limiting the scope defined by the appended claims.  Manufacture of the film, PE or barrier, stretchable and tacky [0100] Among the known plastic films and in particular those used in the fields of food packaging, the protection of elements stored on pallets or silage, for example, films are often so-called "stretchable" films with tackifying properties.  More particularly, an extremely stretchable and self-adhesive film (tackifier, tacky) can then be used up to 180% of its initial length.  In order for the film to be optimized for stretching and gluing, it may, for example, consist of two or more polymer layers, at least one of which may contain an elastomer, and at least one, identical or different, which may contain a tackifier, such as Pl B.  Other examples of fumigation films and having tackifying properties are shown below: Film No. 1a: conventional gas barrier film prepared by extrusion blow molding, and containing three layers as follows: Polyethylene EVOH Polyethylene / o Film No. 1b: conventional gas barrier film prepared by extrusion blow molding, including a tackifying layer: Polyethylene EVOH Polyethylene + Pl B Film No. 1c: conventional gas barrier film prepared by extrusion blow molding, containing four layers including a tackifying layer : Polyethylene EVOH Polyethylene Polyethylene + Pl B 15 Film No. 2a: transparent photocatalytic gas barrier film prepared by extrusion blow molding, containing three layers as follows: Polyethylene EVOH Polyethylene + TiO2 photocatalytic Film No. 2b: gas barrier film, photocatalytic and transparent, with tackifying layer, prepared by extrusion blow molding, and containing four layers as follows: Pol yethylene EVOH Polyethylene + TiO2 Photocatalytic Polyethylene + Pl B - 21 - Film No. 3a: gas barrier film, colored photocatalytic, prepared by extrusion blow molding, and containing four layers as follows: Polyethylene EVOH Polyethylene + TiO2 Photocatalytic Polyethylene + Carbon Black Film No. 3b: gas barrier film, colored photocatalytic, with tackifying layer, prepared by extrusion blow molding, and containing four layers as follows: Polyethylene EVOH Polyethylene + TiO2 photocatalytic Polyethylene + carbon black + PIB Film No. 3c: barrier film with gas, colored photocatalytic, with tackifying layer, prepared by extrusion blow molding, and containing five layers as follows: Polyethylene EVOH Polyethylene + TiO2 photocatalytic Polyethylene + carbon black Polyethylene + Pl B Example of application of a gas barrier film sticker "[0102] For this test, tackifying films (or self-adhesive), corresponding to the f No. 1b above, with three layers of total thickness 30 μm, width 2.5 m and length 100 m, are used.  Two series of films are obtained by the so-called "extrusion-blowing" technique, which is well known to those skilled in the art, by using: for the first series: a tackifying masterbatch Polyethylene (PE) / PIB type PVV 60 sold by the company Polytechs at a rate of 5%, 10% and 15% (ie 3 films) by weight of tackifying masterbatch relative to the total weight of the film, and - for the second series: a tackifying masterbatch Polyethylene (PE) / PIB type PVV 70, sold by the company Polytechs, at a rate of 5%, 10% and 15% (ie 3 films) by weight tackifying masterbatch relative to the total weight of the film.  Many techniques can be envisaged to extend a film and cover a floor to be fumigated with a fumigant vapor-tight film.  Among these techniques, the following three techniques can be mentioned by way of illustration: - 22 - Technique No. 1 [0104] The laying of the film is carried out in a conventional manner with a "film-forming" machine, for example a machine that is commonly used used for treatment with fumigation with methyl bromide and using a translucent solvent or hot melt adhesive.  The operation includes laying a first tape (or tape) of sticker film and fumigant barrier, then gluing a second film web onto a portion of this first film strip, with an overlap width of about 10 cm to 30 cm.  Technique No. 2 [0105] With an existing film-forming machine, of the type described for example in application WO2001 / 0119167, a first gas barrier film strip (conventional, non-tackifying) and a second strip, in leaving a space of width about 5 cm to 20 cm between these two strips.  Then, while placing the third strip, sticking the self-adhesive gas barrier film strip (width about 10 cm to 50 cm, typically 40 cm) between the two strips previously laid, by simple pressure.
    [0002] Technique No. 3 [0106] With film-forming machine of Technique 1 and / or of Technique 2, alternating laying of strips of non-adhesive barrier film (non-tackifying) and self-adhesive barrier film (tackifier), with widths generally around 3 meters.
    [0003] Example of Application of a Film According to Technique No. 1 [0107] The application of the various films was carried out according to technique No. 1, namely from the film machine used for the fumigation treatment with methyl bromide. . A first strip of self-adhesive barrier film (film 1b) is placed, then a second strip of self-adhesive barrier film (film 1b) is adhered to the edge of this first strip of film, by simple pressure. , and so on, so as to cover the entire width of the field. The area of overlap is about 20 cm. All tackifying and fumigating barrier films as described in the present invention have a tackifying power satisfactory for use in fumigating the soil, while ensuring a perfect seal and thus retain the fumigant vapors under the film, more precisely between the ground and the film, so that no fumigant vapor, or only very small amounts of fumigant escapes into the atmosphere. The use according to the present invention of a self-adhesive fumigation film thus has many advantages, among which may be mentioned: - possibility of bonding-take-off, type "PostitTM" so easy to remove and to reposition. The uncovering is also made easier, - 23 - - possibility of using the same recycling path as for the conventional fumigation film, - ease of use of the film without any management of the adhesive during the fumigation the adhesive agent (or tackifier) is added to the film during its manufacture, it is therefore not necessary to add an adhesive (hot-melt type or solvent-based adhesive) to the film strips already positioned on the field, maintaining the number of operators identical to that observed during the laying of conventional fumigation films, lower final cost (material and time), in comparison with the techniques for bonding conventional film strips.
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. Use for fumigating barrier soil treatment with at least a portion of its outer surface or at least a portion of its internal surface or at least a portion of its external and internal surfaces thereof at minus a continuous self-adhesive or self-adhesive or tackifying zone. / o
    [0002]
    2. Use according to claim 1, wherein the self-adhesive continuous zone of the film is a continuous zone and parallel to the greatest length of the film.
    [0003]
    Use according to claim 1 or claim 2, wherein the film comprises at least one layer comprising a polymer selected from polyolefins, polyamides and polyesters, and at least one tackifier or tackifying resin.
    [0004]
    4. Use according to any one of claims 1 to 3, wherein the thickness of the fumigant barrier film and sticker is between 5 pm and about 100 pm, preferably between 5 pm and 75 pm, preferably between 5 pm and 60 μm, more preferably between 5 μm and 50 μm.
    [0005]
    5. Use according to any one of claims 1 to 4, wherein fumigated soils are soils or substrates for market gardening and horticulture, arboriculture, vine, and others. 25
    [0006]
    6. A method of sealing a floor for fumigation treatment or during fumigation treatment or that has been fumigated, said method of covering all or at least a portion of said soil of a film Fumigant barrier having on at least a portion of its outer surface or at least a portion of its inner surface or at least a portion of its outer and inner surfaces, at least one continuous self-adhesive zone.
    [0007]
    The process according to claim 6, wherein the self-adhesive fumigant barrier film can be applied by at least one of the following techniques: a) laying a fumigant barrier film web and self-adhesive, overlapping another leg of said fumigant barrier film and self-adhesive, optionally pressing on the overlap zone, simultaneously or after application of the fumigant barrier film and self-adhesive, b) laying simultaneously a conventional (i.e. non-sticky) fumigant barrier film web and a small strip of self-adhesive fumigant barrier film between two conventional gas barrier film webs; that is to say non-adhesive, possibly by pressing on the small band of self-adhesive film, simultaneously or after the laying of the film (s) of the fumigant barrier film, c) alternating laying of a barrier film strip at fumigant and sticker riding a movie ba back to the conventional fumigant (i.e., non-self-adhesive), optionally pressing on the overlapping area simultaneously or after the fumigant barrier film webs have been applied.
    [0008]
    8. A method according to claim 6 or claim 7, comprising a step of injecting at least one fumigant immediately before the film is applied, or after the film has been applied.
    [0009]
    9. Process according to any one of claims 6 to 8, wherein the fumigant is selected from methyl bromide, methyl iodide, methyl isothiocyanate, allyl isothiocyanate, dichloropropene, chloropicrin, ethanedinitrile, sulfuryl fluoride, phosphine, tetrathiocarbonate, metam sodium, metam potassium, tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2- thione, alkyl sulfides, dialkyl disulfides, dialkyl polysulfides, thiosulfinates and the like, as well as mixtures of two or more of them in all proportions. 25
    [0010]
    10. Fumigation treatment kit of a soil comprising at least one fumigant barrier film and self-adhesive and at least one fumigant, preferably at least one sulfur-containing volatile organic compound, more preferably said fumigant comprises dimethyl disulfide.
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    同族专利:
    公开号 | 公开日
    AR102541A1|2017-03-08|
    EP3217788B1|2018-12-26|
    AU2015344899A1|2017-05-25|
    IL251835D0|2017-06-29|
    JP2017536115A|2017-12-07|
    US20170332617A1|2017-11-23|
    CN106998673A|2017-08-01|
    KR20170077179A|2017-07-05|
    MX2017005966A|2017-06-29|
    AU2015344899B2|2019-06-13|
    WO2016075392A1|2016-05-19|
    ES2712848T3|2019-05-16|
    PL3217788T3|2019-05-31|
    FR3028148B1|2017-05-19|
    EP3217788A1|2017-09-20|
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    2021-08-06| ST| Notification of lapse|Effective date: 20210705 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1460834A|FR3028148B1|2014-11-10|2014-11-10|SELF-ADHESIVE FILM FOR SOIL FUMIGATION|FR1460834A| FR3028148B1|2014-11-10|2014-11-10|SELF-ADHESIVE FILM FOR SOIL FUMIGATION|
    JP2017525008A| JP2017536115A|2014-11-10|2015-11-05|Self-adhesive film for soil fumigation|
    EP15808710.6A| EP3217788B1|2014-11-10|2015-11-05|Self-adhesive film for soil fumigation|
    MX2017005966A| MX2017005966A|2014-11-10|2015-11-05|Self-adhesive film for soil fumigation.|
    PL15808710T| PL3217788T3|2014-11-10|2015-11-05|Self-adhesive film for soil fumigation|
    US15/525,170| US20170332617A1|2014-11-10|2015-11-05|Self-adhesive film for soil fumigation|
    CN201580063107.3A| CN106998673A|2014-11-10|2015-11-05|Self-adhesive film for soil-fumigating|
    PCT/FR2015/052988| WO2016075392A1|2014-11-10|2015-11-05|Self-adhesive film for soil fumigation|
    ES15808710T| ES2712848T3|2014-11-10|2015-11-05|Self-adhesive film for soil fumigation|
    KR1020177014212A| KR20170077179A|2014-11-10|2015-11-05|Self-adhesive film for soil fumigation|
    AU2015344899A| AU2015344899B2|2014-11-10|2015-11-05|Self-adhesive film for soil fumigation|
    ARP150103587A| AR102541A1|2014-11-10|2015-11-05|SELF-ADHESIVE FILM FOR SOIL FUMIGATION|
    IL251835A| IL251835D0|2014-11-10|2017-04-20|Self-adhesive film for soil fumigation|
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