EP2854527A1

EP2854527A1 - Storage aids comprising plant protectants and their use

Info

Publication number: EP2854527A1
Application number: EP13752938.4A
Authority: EP
Inventors: Karin Rauch; Jens SCHÖNEWERK; Tilo Wachs
Original assignee: se ma Gesellschaft fur Innovationen mbH; RKW SE
Current assignee: SE MA GESELLSCHAFT fur INNOVATIONEN MBH
Priority date: 2012-05-22
Filing date: 2013-07-22
Publication date: 2015-04-08
Also published as: WO2013175461A1; CA2874251C; RU2014150664A; DE102012009965B4; UA114324C2; CN104470357A; RU2601054C2; CA2874251A1; PE20150117A1; BR112014029039A2; US20150144521A1; DE102012009965A1; JP2015527051A; JP6129303B2; ZA201407919B

Abstract

The invention relates to a storage aid which is finished with a plant protectant so as to extend the shelf-life of agricultural produce, and to the use of said storage aid. The storage aid comprises at least: a. a carrier film and/or a carrier paper, b. a permeable cover layer, the carrier film and the cover layer being joined together by an adhesive layer, the adhesive layer comprising between 0.1 and 70% by weight of a plant protectant.

Description

Storage aids with plant protectants and their use

The present invention relates to a storage aid, which is equipped to extend the storage life of agricultural products with a Pflanzenprotektivum and use of these storage aids.

It is known that the germination of crops of all cereals, such as oats, barley, corn, rice and rye, but also of other agricultural products, such as. Potato, sugar beet, tomato, pea, leek, asparagus, forage grass and fodder clover during Storage may be inhibited or prevented by treatment with gamma radiation or by hot fogging with chemicals such as prophy (IPC) or chlorprompham (CIPC).

In the known methods of germ inhibition, however, there are concerns about possible health damage. Thus, for example, potatoes may not be consumed until at least 42 days after the treatment after conventional treatment by means of hot fogging of the growth regulator CIPC.

Rhodes et al. (Research 1950, 3, 189-190) for the use of isopropyl N- (m-chlorophenyl) -carbamate (CIPC) (Ia) as a highly effective inhibitor of shoot formation in Solanum tuberosum.

Examples of typical growth regulators are carbamates having the general formula (I):

where Ar is an aryl or hetaryl radical, R is an alkyl radical and X is oxygen or sulfur. In the case of the defined structure (Ia), Ar is a phenyl radical, R is an isopropyl radical and X is oxygen.

Parochetti et al. {Weeds 1966, 14, 281-285) discloses the influence of temperature, soil moisture, soil type and air flow on the volatility of isopropyl N-phenyl-carbamate (IPC) and isopropyl N- (m-chlorophenyl) -carbamate (CIPC). , The observed volatility of IPC and CIPC from an air-dried soil (<1 / jg / cm2) is very low. Liebmann et al. {Chemische Technik 1964, 16 (4), 236-237) discloses for CIPC at a temperature of 20 ° C an extrapolated vapor pressure of 0.13 mPa. This means that under ideal conditions of vapor pressure saturation at a temperature of 20 ° C only a Cl PC concentration of 1, 26 ppb or about 1 1 / jg / m3 is achieved.

There are numerous other growth regulators such as Tecnazene and maleic hydrazide, which are similarly effective as isopropyl N- (m-chlorophenyl) carbamate, but could not be used in Germany. In the case of maleic hydrazide, the restriction on outdoor use has been relaxed because production-related admixtures of free hydrazine have been drastically reduced. The use of isopropyl-N- (m-chlorophenyl) carbamate has also been restricted in the private sector since 2001. The dilemma on the one hand the disadvantages of not insignificant storage and quality losses and on the other hand as far as possible residue-free food to bring into agreement, can only be solved by primarily the application rate is drastically reduced and false applications are excluded with absolute certainty. These misuses can not be ruled out with certainty in the conventional methods of distributing the growth regulator. The particularly disadvantageous variant of applying the preparation in solid form to the potatoes is largely due to the Sprühbzw. Hot mist method (DE 199 13 591 A1; US 2009/0203527 A1) has been replaced. But even here there may be significant concentration differences in the stored goods. Direct wetting with the concentrated preparation also occurs in practice, such as investigations on residues (J. Environm., Science a. Health 44B (2009) 1 -6; Acta Chim. Slov. 57 (2010) 972-979) Active substance lsopropyl-N- (m-chlorophenyl) carbamate in potatoes suggest.

There are a number of nature-identical active ingredients (Potato Res. 24 (1981) 61-76.), Which are to act similarly growth-regulating. In reality, the disadvantages which arise in connection with the characteristic olfactory properties and the marked exceedance of the odor threshold at the required concentrations, a possible reason why these substances are not yet used. An application of 2001 (DE 694 27 407 T2) describes an enhancement of the individual effects of carbene and menthol when used in a mixture. However, the application of this combination could not prevail.

DE 103 29 275 A1 discloses a three-layer composite of a transferable adhesive layer and a carrier film, which are not permanently connected to each other, wherein the adhesive layer may contain volatile ingredients.

EP 0 142 658 A1 discloses supports in the form of films, nonwoven and woven fabric of organic material with integrated active ingredients, wherein in the polymeric matrix of the carrier an active ingredient is integrated. The integrated drug is able to slowly migrate out of the polymeric matrix.

DE 691 22 525 T2 discloses the production of multilayer films comprising more than three layers, the multilayer films comprising a core layer, a corresponding further layer laminated to each side of the core layer, and an additive. The multilayer film is produced by an extrusion process of all layers, wherein in a first step of the manufacturing process an additive is encapsulated in a thermoplastic resin to obtain pellets which are mixed in a second step with a second thermoplastic resin having a melting point lower than that first resin has.

It is therefore an object of the present invention to provide a protective storage aid for the preservation and germ inhibition of stored goods, which reliably prevent the direct contamination of the stored material with a Pflanzenprotektivum while maintaining a constant concentration of Pflanzenprotektivums in the ambient air over the entire storage period of the stored crop and other agricultural products guarantee.

According to the invention the object is achieved by a storage aid comprising at least: a) a carrier film and / or a backing paper and

b) a permeable cover layer,

wherein the carrier film and the cover layer are connected by an adhesive layer, wherein the adhesive layer is between 0.1 and 70 mass%, preferably between 0.5 and 60 mass%, particularly preferred between 0.5 and 50 mass% of a plant protivivum.

Surprisingly, it has been found that when incorporating a preferably low-volatility plant protivative into the adhesive layer of a storage aid according to the invention, the adhesive layer serves as a long-term depot for an active substance (ie plant protivivum) and thus includes it. Advantageously, the direct contact of an active ingredient incorporated in the adhesive layer with the stored product is excluded by the inventive storage aid. In addition, the construction according to the invention of a storage aid for the user and the end user represents a contact protection against a plant protection substance. Previous and subsequent references are only to the extent that it is necessary for the understanding of the invention to those skilled in the art.

For the purposes of the invention, a storage aid is a flexible and permanent multilayer composite material or a laminate which consists of at least one carrier film and / or a carrier paper and at least one permeable cover layer, wherein between the carrier film and / or the carrier paper and the cover layer in each case an adhesive layer, wherein the adhesive layer contains a plant protection agent, preferably a low-volatile active substance selected from the group of growth regulators and fungicides, particularly preferably selected from the group carbamates and benzimidazoles.

A permeable cover layer is preferably a perforated cover film (for example made of PE, PP, PS, PET, PVC, polylactide or coated cellglass and blends) or a nonwoven (for example made of PE, PP, polyester, viscose or polyamide) or a perforated paper ,

The carrier films and / or the perforated cover films are flexible, band-shaped films, which preferably consist of a non-adhesive material, the type of carrier films used and / or perforated cover films being subject in principle to no restriction. Commercially available plastics, such as PE, PP, PS, PET, PVC, polyester, cellophane, cellulose, polyvinylidene chloride, styrene-butadiene block copolymers, ethylene-vinyl acetate copolymers, are preferably used as suitable materials for the carrier film and / or cover films (EVA), ethylene-vinyl alcohol copolymers (EVOH), ethylene-propylene terpolymers, polyacrylonitrile, polyacrylates, polyamides (PA), polylactide, cellglass (also known as cellulose hydrate or cellophane) and blends (ie composites of these materials) in question, which are known to the skilled person with their properties and are commercially available in a great variety.

For economic reasons, carrier films and cover films made of PE, PP, PS, PET, PVC, polylactide or coated cellglass and blends are generally particularly preferred.

The carrier film and / or the cover film preferably has a basis weight between 5 and 200 g / m ² , more preferably between 10 and 120 g / m ² , very particularly preferably between 25 and 100 g / m ² . The basis weight is defined as the weight of material per material area in g / m ² . Preferably, the carrier paper is a sulphate or sulphite kraft paper having a basis weight between 60 and 140 g / m ² , more preferably between 70 and 90 g / m ² .

The perforated cover film and / or the carrier film, in particular the perforated cover film are preferably finely perforated or perforated, whereby the film is permeable to gases, and so a controlled and uniform release of active ingredient is guaranteed to the ambient air.

A perforated carrier film or cover film preferably has between 10 and 500, particularly preferably between 20 and 400, very particularly preferably between 200 and 350 holes per cm ^{2 of} the film, the free surface of a film resulting from the holes having between 1 and 25 surface areas. % is. The holes of the carrier film and / or the cover film are not connected to one another and have a diameter of 50 μm to 3 mm, in particular from 0.1 to 2 mm, very particularly preferably from 0.2 to 1 mm. Advantageously, by the size of the holes in the carrier film and / or the cover sheet a uniform distribution of active ingredient by convection in the case of thicker compact storage aids favors.

Alternatively, the permeable cover layer is a non-woven of PE, PP, polyester, viscose or polyamide or a paper.

A fleece is a fiber composite that consists of loosely connected fibers, wherein the fibers are not yet connected to each other. In order to be able to process and use the nonwoven, it is usually consolidated, for which various methods known to those skilled in the art can be used. The length of the fibers of a nonwoven used is not subject to any particular limitation, i. Fibers can be used both so-called short and / or long fibers as well as fiber fragments. Short and / or long fibers having an average length of between 5 and 150 mm, preferably between 10 and 120 mm, very particularly preferably between 20 and 100 mm, have proven to be particularly preferred.

Preferably, the paper of the permeable cover layer is a perforated or needled sulphate or sulphite kraft paper having a basis weight between 60 and 140 g / m ² , more preferably between 70 and 90 g / m ² , with 2 to 10, preferably 2 to 5 holes per cm ² paper. The object of the carrier film and / or the backing paper and / or the permeable cover layer is to protect the permanent adhesive layer against undesired contact with foreign objects and to ensure a uniform release of the incorporated therein Pflanzenprotektivums.

The adhesive layer of the storage aid of the invention preferably consists of an elastic adhesive having a permanent adhesive action and a low polarity (which is matched to the growth regulator), which advantageously facilitates the diffusion of the incorporated growth regulator.

The adhesive of an adhesive layer is preferably selected from the group of polyolefin, polyurethane adhesives, plastisols, acrylate resins, PSA pressure-sensitive adhesives, natural adhesives or a mixture of these adhesives.

A particularly rapid release of active ingredient is naturally achieved by a low interaction between adhesive matrix and growth regulator, which is why the adhesive is particularly preferably polyisobutylene, a 1 or 2-component (K) polyurethane system, PVC plastisol or a mixture of these adhesives.

Preferred is a natural adhesive selected from starch and modified starch (eg, amylopectin and maltodextrin), cellulose esters and / or ethers (eg, methyl and acetyl cellulose), lignin products (eg, lignosulfonates, organosolv lignin ), Glutin glue (bone glue) and / or resins (eg rosin).

For optimal contact protection, a homogeneous distribution of the growth regulator in the adhesive layer is optimal, the polarity differences between growth regulator and adhesive having a great influence on the release of active ingredient. In the case of particularly low-volatility polar growth regulators, the release from a nonpolar adhesive layer containing polyisobutylene is advantageously much faster than from an adhesive layer containing a 1K or 2K polyurethane system or cyanoacrylate adhesive.

At the same time, an adhesion-reducing high concentration of the growth regulator can be advantageously achieved by selecting high molecular weight polyisobutylene, preferably having a molecular weight between 10,000 and 5,000,000 g / mol, more preferably between 10,000 and 1,000,000 g / mol, most preferably between 10,000 and 500,000 g / mol to be compensated, whereby the depot effect of the storage aid according to the invention is increased and its duration of use is extended. The corresponding compositions for 1K and 2K polyurethane systems are well known to the person skilled in the art or can be found, for example, in the handbook "Polyurethane" (Ulrich Meier-Westhues, Vincentz Network GmbH & Co KG, 2007). and 2-component polyurethane systems are described in DE 103 08 106 A1, EP 0 996 655 A1 and EP 2 143 337 A1 Examples of commercially available adhesives based on 1K and 2K polyurethane systems are the Körapur type (from KVT -Fastening AG), Bayhydrol® (Bayer AG), Bayhydur® (Bayer AG), Desmocap (Bayer AG) and Desmodur® (Bayer AG), Kleiberit 1K PUR502.9 (Klebchemie GmbH & Co. KG).

Examples of PSA adhesives include Duro-Tak adhesives (Henkel), Scotch-Weld ™ adhesives (3M).

A plastisol is a suspension of a powdered thermoplastic polymer and a plasticizer and optionally fillers, blowing agents and other additives. PVC plastisol is also known as soft PVC, hot melt vinyl.

The thickness of the adhesive layer connecting the multilayer composite is preferably selected between 1 and 50 μm, particularly preferably between 5 and 40 μm, very particularly preferably between 10 and 30 μm. Thinner adhesive layers tend to form the adhesive layer poorly, while thicker adhesive layers in addition to excessive adhesive consumption can lead to delamination of the multilayer composite.

Advantageously, by adjusting the thickness of the adhesive layer connecting the multilayer composite, a cushioning contact protection for the stored product can be achieved, whereby, for example, the formation of undesired pressure points during storage, rearrangement and / or transport is minimized.

By introducing small amounts by weight of the active substance into an adhesive layer of less than 50% by weight, the thickness of the adhesive layer connecting the storage aid as a multilayer composite can preferably be varied.

Preferably, the adhesive layer of a storage aid according to the invention serves as a depot for a plant protivivum incorporated into the adhesive layer, wherein the low polarity and the high hydrophobicity of the adhesive of an adhesive layer allow direct contact between the plant protector and the environment (eg water, aqueous solutions, Steam) is prevented. Advantageously, this minimizes chemical decomposition of the plant protivivum, for example by alkaline or acidic hydrolysis, to form inactive and / or toxic decomposition processes. Particularly good properties has a storage aid of a carrier film made of PE and a perforated cover sheet of PE, where as active ingredient-containing intermediate layer (ie adhesive layer) polyisobutylene (PI B) was used. Polyisobutylene is particularly well suited because it facilitates the diffusion of the active ingredient due to its low polarity and without solvents as toxicologically completely harmless adhesive permanently and elastically connects many different materials together. For bonding other adhesive systems are in principle suitable, as far as they allow the homogeneous distribution of the active ingredient. This composition of the storage aid is intended to guarantee that the active ingredient only passes into the gas phase and can not escape from the film by segregation and contaminates the stored product in liquid or solid form. Particularly easy is the processing of polyisobutylene, which is mixed with up to 10% isopropyl-N- (m-chlorophenyl) - carbamate and at 50 to 80 ° C as an adhesive layer on the substrate (PE, PP, PS, PET, PVC or coated cellophane and similar materials). The cover film used is a perforated PE or PP film or a nonwoven. Other adhesives which can also be used are 1K and 2K polyurethane systems.

For the purposes of the invention, plant protectants (or else active ingredients) are preferably growth regulators or fungicides which are known to the person skilled in the art, for example from Weed Research 26, 441-445 (1986) or "The Pesticide Manua" (10th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 1994) and literature cited therein.

The plant protivivum is particularly preferably a carbamate of the general formula 1

(1) where:

R ¹ and R ^{2 are} independently an optionally substituted and / or branched Ci to Cio-alkyl radical or optionally substituted aryl or hetaryl radical and

X is oxygen or sulfur, preferably oxygen,

or a benzimidazole.

As a plant-protecting agents known from the literature, which moreover can preferably be used in a storage aid according to the invention, the carbamates of the general formula 1 are preferably selected from the group Barbane, prophyne, chloropropham, (1S) -1 - {[(1R) -1- (6-fluoro-1,3-benzothiazol-2-yl) ethyl] carbamoyl} -2-methylpropyl] carbamic acid (Benthiavalicarb) , Methylbenzimidazol-2-ylcarbamate (carbendazim), 2-methyl-1 - [1- (4-methylphenyl) ethylcarbonyl] -propyl} -carbamic acid isopropyl ester (iprovalicarb), propyl [3- (dimethylamino) propyl] carbamate (propamocarb), Ethyl 2- (4-phenoxyphenoxy) ethylcarbamate (fenoxycarb), 3,5-dimethyl-4-methylmercaptophenyl-N-methylcarbamate (methiocarb), 5,6-dimethyl-2-dimethylaminopyrimidin-4-yl-N, N-dimethyl carbamate (pirimicarb), ethyl 3-phenylcarbamoyloxyphenylcarbamate (Desmedipham) and methyl 3- (3-methylcarbaniloyloxy) carbanilate (Phenmedipham).

The benzimidazole is preferably 2- (4-thiazolyl) -1H-benzimidazole (thiabendazole).

Preferably, the Pflanzenprotektivum (or the active ingredient) of the storage aid according to the invention is low volatility, d. h., That the relative volatility, as a dimensionless index that describes the evaporation of a substance is preferably greater than 25, more preferably greater than 30.

Preferably, the low-volatility Pflanzenprotektivum of the storage aid according to the invention at a temperature of 20 ° C has a vapor pressure less than 10 Pa, more preferably less than 10 mPa, most preferably less than 1 mPa.

An active substance is particularly preferably a growth regulator of the general formula 2

where Ar is an aryl or hetaryl radical or a substituted phenyl or naphthyl radical, R is an optionally substituted and / or branched alkyl radical and X is oxygen or sulfur, preferably oxygen.

The aryl or hetaryl radical of the growth regulator of the formula 2 is particularly preferably phenyl, tolyl, naphthyl, pyridyl, thienyl or isoxazolyl, very particularly preferably phenyl, tolyl, naphthyl, pyridyl, thienyl and R is isopropyl.

Particularly preferred is a growth regulator of formula 2 selected from the group isopropyl-N-phenyl-carbamate (CAS: 122-42-9) with a vapor pressure of 0.144 mbar at 25 ° C; isopropyl N- (m-chlorophenyl) carbamate (CAS: 101-21-3) with a vapor pressure of 0.144 mbar at 20 ° C, ethyl 2-pyridylcarbamate (CAS: 5255-67-4) with a vapor pressure of 0.1 mbar at 25 ° C or trifluoromethyl-2-thienylcarbamate (CAS: 89564-08-9) with a vapor pressure of 5.5 mbar at 25 ° C.

Particularly preferred is the growth regulator according to the formula 2 isopropyl-N- (m-chlorophenyl) carbamate.

In order to minimize the potential health hazards, the application of the active ingredient was investigated and found that obviously, the previously used amounts of active ingredient only had to be so large because under the selected storage conditions, no depot is present, which ensures a uniform release of active ingredient to the ambient air , The vapor pressure of isopropyl N- (m-chlorophenyl) carbamate (Amer Potato Jour 29 (1952) 268-272) is very low, but unexpectedly the drug release was from a film less than 0.5 g Active ingredient per m ² contained so large that even the cover of a relatively large storage volume with this film was completely sufficient to prevent sprouting.

FIG. 1 shows that when using the nonvolatile growth regulator, isopropyl N- (m-chlorophenyl) carbamate (CIPC), the evaporation losses at a temperature of 30 ° C. after 30 days are only 0.03%.

In order to ensure a sufficient circulation between the stored goods (for example potatoes), it is advantageous if the film including its carrier layer itself has a coarser additional perforation.

In a preferred embodiment of the invention, the storage aid according to the invention has a continuous perforation, preferably a coarser additional perforation additional coarser punch holes or a coarser continuous perforation.

In a preferred embodiment of the invention, the storage aid is a three-layer composite, so that the storage aid comprises only a carrier film and / or a carrier paper and a cover layer, wherein the carrier film and the cover layer are connected by a permanent adhesive layer.

Alternatively, a storage aid is a five-layer composite, wherein an additional second permeable cover layer is applied to the rear side of a carrier film and / or a carrier paper of a three-layer composite described above (ie the outer side of the carrier film and / or the carrier paper facing away from the adhesive layer). closes, wherein the additional second cover layer and the carrier film and / or the backing paper are connected by an additional second permanent adhesive layer. Advantageously, but not necessarily, in a five-layer composite, the materials of both cover layers differ from one another and / or the two adhesive layers from one another. The two outer layers can comprise both films and nonwovens. Advantageously, the active ingredients included in an adhesive layer may be the same or different in the five-layer composite according to the invention for the respective adhesive layer.

It should be noted that the embodiments according to the invention can be combined with each other in any arrangement.

Preferably, the preparation of the storage aid according to the invention is carried out by a spray coating or laminating method, wherein a single-stage or multi-stage coating of the surface of the carrier film and / or the backing paper and / or the permeable cover layer is carried out with an adhesive layer. For example, in the case of reactive adhesives, the growth regulator can be metered into the adhesive immediately prior to application by means of a static mixer (spiral mixer, X-element or V-element mixer) or the solution of the growth regulator in the adhesive which is stable in unlimited storage.

The operations of a spray coating or laminating process are known in the art and include, for example:

a) single-stage or multi-stage coating of the surface of the carrier film and / or the backing paper and / or the permeable cover layer with an adhesive layer containing the plant protection agent, at a temperature between 20 to 100 ° C, preferably between 30 and 90 ° C, more preferably between 40 and 80 ° C.

b) placing the carrier film and / or the carrier paper and / or the permeable cover layer on the surface of the film coated under a),

c) smoothing the film composite,

d) cooling,

e) peel off.

Before winding up a composite produced by spray-coating or laminating, the process can optionally be repeated several times, whereby a storage aid in the form of a multilayer composite with more than three layers is obtained. The incorporation of a Pflanzenprotektivums in the storage aid according to the invention is not carried out with an extrusion process (eg extrusion lamination, Schneckenextrusi- on), at high temperatures of 140 to 240 ° C and a high pressure of 250 to 400 bar. By dispensing with an extrusion process for producing a storage aid according to the invention, the decomposition of the plant protivivium at high temperatures is particularly advantageously avoided. At the same time advantageously high investment costs can be avoided.

The fine perforation of the carrier film and / or the cover film with holes, which have a diameter of 50 μm to 3 mm, preferably takes place before the coating, for example by means of needle or vacuum perforation.

Preferably, the coarser additional perforation of a storage aid with holes, which have a diameter of greater than 3 mm, more preferably between 3 and 5 mm, by hot-needle, flame, punching, laser perforation and laser scribing. These methods are known to the person skilled in the art. A coarser additional perforation preferably has between 1 and 5, more preferably between 1 and 2 holes per cm ^{2 of} the storage aid according to the invention.

The invention also encompasses a composite material that consists entirely or at least partially (that is, not completely) of a storage aid according to the invention, wherein the composite material may, for example, be composed of: B. in the form of a tarp or flexible web, preferably for storage and / or transport of stored goods. Preferably, a composite material, the storage aid according to the invention in the form of a multi-layer composite, consisting of at least one carrier film and / or a carrier paper and a permeable cover layer, which are connected by a permanent adhesive layer with incorporated plant protection.

The subject of the invention is also a container, such as e.g. a pallet hood, bag or bag which consists entirely or at least partially (that is to say not completely) of a storage aid according to the invention, the container serving as packaging of stored goods for storage and / or transport thereof. A container preferably has the storage aid according to the invention in the form of a film composite, consisting of a carrier and a cover film.

For the purposes of the invention, bags and pouches are hollow, deformable, preferably single-layered storage and transport containers, which have a normally closable opening for filling or Have emptying with a stored goods. Preference containers are, for example. In the form of a rectangular or funnel-shaped, bag, bag or sack.

Containers that are at least partially constructed from a storage aid are preferably paper, plastic or plastic bags or bags made of a biodegradable material (eg. Sisal, flax, cotton) with at least one continuous, superficial material recess, wherein in the at least one Material recess an inventive storage aid is integrated.

Preferably, the main component of the paper is a paper bag of pulp (cellulose). Further preferably, the paper of a paper bag is unbleached and / or bleached sulphate and / or sulphite paper. It has been found that paper with a basis weight between 150 g / m ² and above 10 g / m ^{2 is} particularly well suited for a container.

The storage aid according to the invention is preferably used for storage and / or transport of the stored product, preferably crop (for example cereals) and other agricultural products (for example potatoes).

The invention also encompasses the use of the storage aids according to the invention as a multilayer composite for the packaging and storage of stored goods, in particular crops (for example cereals) and / or agricultural products (for example potatoes).

The application of the multilayer composite produced therefrom can be done in various ways. In order to ensure a sufficient circulation between the stored goods (for example potatoes), it is advantageous if the film, including its carrier film itself, has a coarser additional perforation. With this film, the areas of the storage room are loaded (i.e., lined, covered) or the material is used for the production of packaging for storage, transport and distribution.

Advantageously, the storage aid according to the invention can be used at a temperature between -20 and 60 ° C, more preferably between -10 and 50 ° C, most preferably between 0 and 40 ° C for the storage and transport of stored goods.

In a preferred embodiment of the invention, the storage aid is placed in a storage room, where it is suspended for example on trusses and thereby in the Storage area and / or in the movement space of the storage room is sufficient. The storage of stored goods preferably takes place in an actively conditioned storage space (ie in a closed warehouse with internal cooling), so that advantageously the air circulation is conducted through the storage space and through the storage aid according to the invention. It should be noted, however, that active air conditioning is not necessary for the practicability of the invention.

Preference is given to packaging, the adhesive layer having a high adhesive effect between a carrier film and a cover film, as a result of which the stability of the inventive storage aid as a permanent film composite is increased.

Particularly preferred are packaging, wherein the thickness of the adhesive layer connecting the film composite between 5 and 100 μηη, most preferably 15 and 80 μηη, preferably selected between 20 and 60 μηη, thereby advantageously a cushioning contact protection for the stored material is achieved, so that, for example the formation of undesired pressure points during storage, rearrangement and / or transport is minimized.

Reference to the following figures and embodiments, the invention will be explained in more detail, without limiting the invention to these.

Fig. 1: Evaporation losses of isopropyl N- (m-chlorophenyl) carbamate.

Fig. 2: Germ inhibition experiment in the laboratory.

Fig. 3: Time-dependent concentration curve of CIPC in large-scale experiment.

Fig. 4: Continued storage without storage aids.

Fig. 5: Continued storage after Heißvernebelungsbehandlung.

Example 1 - Film combination with isopropyl N- (m-chlorophenyl) carbamate as a plant protective agent

A mixture of 288 mg of polyisobutylene and 25 mg of isopropyl N- (m-chlorophenyl) -carbamate (CIPC) is applied at 55 ° C. on a PE support film of 0.25 m × 0.25 m and with an appropriately sized perforated PE -Deckfolie glued. For comparison, a corresponding film was prepared using 300 mg of polyisobutylene (PIB) without the active ingredient. Two adequate containers with numerous round vents were filled with 2.5 kg potatoes each and covered with one of these foils.

At a storage temperature of 20 ° C and about 50% relative humidity 100% shoot formation over 2 cm in length was observed after four weeks in the drug-free sample. The sample containing the active ingredient-containing film after this time showed sprouting only in 12% of the samples, these were not longer than 5 mm and were evenly distributed over the entire sample volume.

Figure 2 shows two different samples of organic potatoes. The left sample in Figure 2 was stored in the presence of the storage aid (0.25 mx 0.25 m) consisting of the PE carrier film and the PE cover film. In the comparative sample (FIG. 2, right), the organic potatoes were stored in the presence of a reference film of analogous structure without CIPC. Both samples were stored in the dark over a period of 70 days at a temperature of 22 ° C and a relative humidity of 54%. Annex 6 can be clearly seen that by the use of a storage aid according to the invention (Figure 2, left) the germ inhibition is visibly prevented. The samples in the presence of the reference film without CIPC (Figure 2, right) show a pronounced dark nucleation.

Example 2 - Film combination with isopropyl N- (m-chlorophenyl) carbamate as plant protective agent

At room temperature (RT), a mixture of 250 mg of a 1 K polyurethane adhesive (Kleiberit PUR502.9) and 22 mg of isopropyl N- (m-chlorophenyl) carbamate is applied to a PE support film of 0.25 m × 0.25 m applied and glued with a perforated PE cover foil. The comparison sample without active substance contains 380 mg of the adhesive. The two o. G. Containers equipped with numerous round vents were again populated with 2.5 kg potatoes each and covered with one of these foils. Both containers were stored in the dark for a period of 14 days at a temperature of 22 ° C and a relative humidity of 54%.

After two weeks, a 100% shoot formation up to 0.5 cm in length was observed in the container containing the drug-free sample. The sample containing the drug-containing film after this time showed sprout formation only in 4% of the samples, which were just visible and distributed over the entire sample volume.

Example 3 - Film composite with a nonwoven as cover layer

A mixture of 300 mg of polyisobutylene and 28 mg of isopropyl N- (m-chlorophenyl) carbamate is applied to a PE support film of 0.25 m × 0.25 m at 55 ° C. and bonded to a PE nonwoven. For comparison purposes, a corresponding film was prepared using 300 mg PIB without the active ingredient. The two containers were each loaded with 2.5 kg of potatoes and covered with one of these films.

At a storage temperature of 20 ° C and about 50% relative humidity 100% shoot formation over 2 cm in length was observed after four weeks in the drug-free sample. The sample containing the drug-containing film after this time showed shoot formation only in 5% of the samples, these were not longer than 5 mm and were distributed over the entire sample volume.

Example 4 - Large-scale application of a storage aid

At RT, a mixture of 4.32 kg of a 1 K polyurethane adhesive based on diphenylmethane diisocyanate and 480 g of isopropyl N- (m-) is applied to a PE substrate film of 200 mx 1.6 m. Chlorophenyl) carbamate (CIPC) was applied and bonded with a perforated PE cover sheet (250 holes / cm ² ).

The storage aid was successfully tested in large-scale industrial application in a commercial refrigerated storage room with a potato capacity of 700 t at a storage temperature between 6 and 8 ° C and a relative humidity between 85 and 95% over a test period of 90 days.

FIG. 3 shows a diagram in which the concentration of CIPC (in mg per kg of potato) is shown as a function of the test time for two different stored goods.

The upper graph in FIG. 3 (circles) shows the time-dependent concentration course on CIPC of a stored material treated by conventional methods, wherein the potatoes were treated once by intensive hot-atomization with the growth regulator CIPC. In practice, 3 to 4 re-treatments of the stored material take place at regular intervals.

The lower graph in FIG. 3 (squares) depicts the time-dependent concentration profile of CIPC in a stored product in the presence of the above-described storage aid. For this purpose, the bearing aid described was mounted in tracks on trusses in the movement space of the hall.

The sampling of the respective storage room took place weekly from the middle of a storage box. The determination of the concentration of CIPC in the individual samples was carried out in parallel by two certified analysis laboratories.

The determined concentration of CIPC in the potatoes of a storage product stored in the presence of a suspended storage aid according to the invention (lower graph in FIG. 3) never exceeded the value of 1 mg per kg potato during the entire experimental period. Thus, the concentration of CIPC was only about 1/10 of the maximum permitted concentration. At the same time, even after a period of 90 days, the concentration of CIPC was well below the concentration of CIPC in a stored matter treated by a single hotverneeration (red graph).

Surprisingly, it has been found that germination takes place in the potatoes in the storage room with the storage aid after removal of the storage aid. Figure 4 shows potatoes, after storage in the presence of the above-described storage aid, this was removed after a period of 100 days and storage was continued for another 50 days. Surprisingly, these potatoes are removed after removal of storage aid germination. For this reason, a storage aid is also suitable for the temporarily limited germ inhibition of seed potatoes.

For potatoes obtained by the conventional method, i. H. When the intensive hot spray was treated with the growth regulator CIPC (see Figure 5), the ability to nucleate is completely eliminated. Therefore, seed potatoes should never be treated directly with a growth regulator.

Example 5 - Large-scale application of a storage aid

At RT, a mixture of 1.8 kg of a 1 K polyurethane adhesive based on diphenylmethane diisocyanate (Kleiberit PUR502.9) and 1.8 kg of isopropyl N- (m-chlorophenyl) is applied to a PE support film of 150 mx 1.6 m ) carbamate (CIPC) and bonded with a perforated PE cover sheet (250 holes / cm ² ).

This storage aid was tested in a large-scale analogous experiment in a cold storage room with a potato capacity of 700 t at a storage temperature between 6 and 8 ° C and a relative humidity between 85 and 95% over a trial period of about 90 days.

For this purpose, the bearing aid described was mounted in the same manner in tracks on trusses in the movement space of the hall.

Again, the value of 1 mg per kg potato was not exceeded at the end of the trial period.

These potatoes could also have been used as seed potatoes.

Example 6 - Film composite with isopropyl N- (m-chlorophenyl) carbamate as active ingredient

A mixture of 1250 mg of DuroTak 180-156A (acrylate copolymer in acetone / hydrocarbon) and 625 mg of isopropyl N- (m-chlorophenyl) -carbamate (at RT) is applied to a PE support film of 0.5 m × 0.5 m. CIPC) and bonded with a suitably sized perforated PE cover sheet (350 holes per cm ² ). For comparison purposes, a corresponding film was prepared using 2500 mg DuroTak 180-156A without the active ingredient. Two adequate containers with numerous coarser vents were filled with 2.5 kg potatoes each and covered with one of these foils. At a storage temperature of 20 ° C and about 50% relative humidity, the nucleation in the drug-containing sample was effectively suppressed after four weeks analogous to the previous experiments.

Example 7 - Film combination with propyl [3-dimethylamino) propyl carbamate as active ingredient

A mixture of 2250 mg of DuroTak and 125 mg of propyl- [3- (dimethylamino) propyl] carbamate (propamocarb) is applied at RT to a PE support film of 0.5 m × 0.5 m and a perforated PE cover film of correspondingly dimensioned size (250 holes per cm ² ) glued. For comparison, a corresponding film was made using DuroTak 2500 mg without the active ingredient. Two adequate containers with numerous round vents were filled with 2.5 kg potatoes each and covered with one of these foils. Both samples were loaded with 50 g of corn, which was visibly contaminated with Fusarium. At a storage temperature of 20 ° C and about 50% relative humidity nucleation was observed after four weeks in both samples. However, the drug-containing film has completely prevented the transmission of fungal infection on the potatoes and even significantly reduced the formation of sprouts.

Example 8 - Film combination with 2- (4-thiazolyl) -1H-benzimidazole as active ingredient

A mixture of 2250 mg of DuroTak and 125 mg of 2- (4-thiazolyl) -1H-benzimidazole (thiabendazole) is applied at RT to a PE support film of 0.5 m × 0.5 m and coated with an appropriately sized perforated PE Cover foil (150 holes per cm ² ) glued. For comparison, a corresponding film was made using DuroTak 2500 mg without the active ingredient. Two adequate containers with numerous round vents were filled with 2.5 kg potatoes each and covered with one of these foils. Both samples were loaded with 50 g of corn, which was visibly contaminated with Fusarium. At a storage temperature of 20 ° C and about 50% relative humidity nucleation was observed after four weeks in both samples. However, the drug-containing film has completely prevented the transmission of the fungal infection to the potatoes, so that their use as seed potatoes was possible.

Claims

Patent claims

Storage aids comprising at least:

a. a carrier film and/or a carrier paper

b. a permeable top layer,

wherein the carrier film and the cover layer are connected by an adhesive layer, the adhesive layer containing between 0.1 and 70% by weight of a plant protectant.

Storage aid according to claim 1, characterized in that the permeable cover layer is a perforated cover film or a fleece or a perforated paper.

3. Storage aid according to claim 1 or 2, characterized in that the adhesive is a polyolefin, polyurethane adhesive, piastisols, acrylate resins, PSA pressure-sensitive adhesives, natural adhesives or a mixture of these adhesives.

4. Storage aid according to one of claims 1 to 3, characterized in that the plant protectant is a carbamate of formula 1

is, where:

- R ¹ and R ² independently of one another an optionally substituted and/or branched Ci to Ci ₀ alkyl radical or an optionally substituted aryl or hetaryl radical and

- X is oxygen or sulfur, preferably oxygen,

or is a benzimidazole.

5. Storage aid according to one of claims 1 to 4, characterized in that the plant protectant is a growth regulator of formula 2

is, where Ar is an aryl or hetaryl radical or a substituted phenyl or naphtyl radical, R is an alkyl radical and X is oxygen or sulfur.

6. Storage aid according to claims 5, characterized in that the aryl or hetaryl radical of the growth regulator according to formula 2 is phenyl, tolyl, naphthyl, pyridyl, thienyl or isoxazolyl and R is isopropyl.

7. Storage aid according to claims 5 or 6, characterized in that the growth regulator according to formula 1 is isopropyl-N-(m-chlorophenyl) carbamate.

8. Storage aid according to one of claims 1 to 7, characterized in that the carrier film is made of polyethylene, polypropylene, polystyrene, polyethylene terephthalates, polyvinyl chloride, polyamide, polylactide or coated cellophane and blends.

9. Storage aid according to one of claims 2 to 8, characterized in that the perforated cover film made of polyethylene, polypropylene, polystyrene, polyethylene terephthalates, polyvinyl chloride, polylactide or coated cellophane as well as blends and the fleece made of polyethylene, polypropylene, polyester, viscose is polyamide.

10. Storage aid according to one of claims 1 to 9, characterized in that the storage aid has a continuous perforation.

1 1 . Composite material for stored goods, characterized in that the composite material consists entirely or at least partially of a storage aid according to one of claims 1 to 10.

12. Container for stored goods, characterized in that the container consists entirely or at least partially of a storage aid according to one of claims 1 to 10.

13. Use of a storage aid according to one of claims 1 to 10 or a composite material according to claim 1 1 or a container according to claim 12 for loading the storage room or for producing packaging for storage, transport and distribution.