AT517786A1 - Use of aryloxyphenoxypropionic acid herbicides for protection of structural waterproofing and bituminous sheeting containing them - Google Patents

Abstract

The present invention contemplates the use of aryloxyphenoxypropionic acid herbicides (FOP) as an anti-penetration and permeator of rhizomes and roots of monocotyledonous plants, particularly grasses, for protection of structural waterproofing, the aryloxyphenoxypropionic acid herbicides (FOP) in bitumen and a carrier liner Comprehensive bituminous membrane present and the Aryloxyphenoxypropionsäure- herbicides (FOP) a) only in the carrier insert, or b) in the liner insert and the carrier insert directly surrounding bitumen, or c) only in the bitumen immediately surrounding the carrier insert. The invention further relates to the bituminous sheets obtained thereby.

Description

The present invention relates to the use of herbicides to inhibit growth of building materials through rhizomes and roots of monocotyledonous plants, such as grasses.

The growth in building materials leads to undesirable material and structural damage. Particularly plastic materials, such as sealants and roofing membranes, but also asphalt surfaces can be destroyed by plant roots and rhizomes.

The ingress of plant parts in gaskets of sewers, sewers, flat roofs and in bitumen insulation of pipelines, bridges and hydraulic structures as well as the ingrowth and growth of roots and rhizomes in light bitumen roads, there are the well-known problems.

The prevention of ingrowth and growth is a particular challenge, particularly with green roofs. The ingrowth and growth of parts of the plant leads to leaks, corrosion and, in addition, serious damage to buildings and pipelines.

From DE-A 1196115 polyethylene glycol esters of 2- (4-chloro-2-methylphenoxy) propionic acid are known which have a root-inhibiting action. Process for the preparation of the polyethylene glycol esters of 2- (4-chloro-2-methylphenoxy) propionic acid are described in DE-A 4412330.

WO 9506408 describes the use of special esters of 2- (4-chloro-2-methylphenoxy) propionic acid for the protection of structures, building materials and insulating compounds against rooting.

In DE10320551A1 enantiomerically enriched polyethylene glycol esters of R - (+) - 2- (4-chloro-2-methylphenoxy) propionic acid are described.

Raschig and Thonnessen describe in the German Ausle-letter 1109294 also the use of condensation products of monochloroacetic acid with mono- and polychlorophenols and cresols as root protectants. MCPA, the condensation product of monochloroacetic acid and cresol, has been successfully tested as a 2-ethylhexyl ester at the Institute of Horticulture, Weihenstephan-Triesdorf University of Applied Sciences, since 2013 as a root protection agent in a two-year FLL test.

It is also known that various derivatives of pyridoxycarboxylic acids, such as triclopyr and fluroxpyr, and picolinic acid, such as picloram and clopyralid, have anti-rooting activity.

Another group of synthetic auxins that have a root controlling effect are benzoic acid derivatives such as dicamba.

The compounds mentioned are classified in the Herbicide Resistance Action Committee (HRAC) Group 0 or in the WSSA ("Weed Science Society of America") Group 4 and are widely used as herbicides with pronounced activity against dicotyledonous plants in chemical crop protection.

However, the above-mentioned substances have no effect against monocotyledonous plants, such as couch grass and bamboo.

In addition to the dicotyledonous plants and their roots, which can grow through building materials, there are also monocotyledons, which can grow through their roots and rhizomes building materials. According to the state of the art, there is currently no root preservative on the market that can meet the requirement (resistance to rhizomes of grasses) with certainty.

Rhizomes are a metamorphosis of the shoot axils of perennial plants and are used for vegetative propagation. They have a root-like shape and grow underground just below the soil surface. They are distinguishable from true roots but by the presence of nodules and (flaky or threadlike) reduced leaves. The rhizomes also lack the roots typical root. The more or less thickened shoot axis usually has short internodes and carries permanently, but only below shoot-roots, shoots and buds. The latter serve in part for the unlimited growth of the rhizome itself and for the formation of the above-ground deciduous and flowering plants.

Rhizomes are formed by different plants. Typical rhizomes include greylag, wood anemone, lily-of-the-valley, horsetail, cyprus and many other grasses, such as couch grass and bamboo, many species of iris, canna and asparagus. Wheatgrass and bamboo, from the horticultural point of view and with a view to the sealing problem, form particularly aggressive rhizomes.

The ability to control rhizome growth by introducing herbicides into sealants is not considered well by professionals as it is believed that rhizomes interact very little or not at all with their environment and do not absorb matter like roots. However, in the broadest sense, ingestion of a herbicidal substance is the prerequisite for a biological activity.

It is therefore an object to find compounds which have an inhibitory effect on the propagation and intergrowth of building materials by rhizomes of monocotyledons, in particular of the order of the sweet grass, the family of grasses, the subfamily of bamboo plants and the subfamily Pooideae ,

To this end, the effect of various grass herbicides used in chemical crop protection on their action against the growth of roots and rhizomes of grasses was first examined. However, the herbicidal action in crop protection can not necessarily be combined with the desired mode of action, e.g. be equated in films or roofing membranes.

The task of a herbicidal crop protection agent is the selective or non-selective killing of plants, which occur as harmful factors in agriculture and forestry. On the other hand, when using protective agents against the ingrowth or growth of roots or rhizomes, only the growth and growth is to be prevented and there should be no plant-killing effect when used in sealants, films or roofing membranes. This is necessary in particular for sealing material for roofing with green roofs. The roof greening represents a replacement greening of the built-up area and thus, of course, there must be no lasting damage to the plants on the green roof.

Decisive for the long-lasting effect of the preservatives against the ingrowth or growth of roots or rhizomes is that they are not or to the least possible extent washed out of the sealant, the film, or the bituminous sheet. This can be achieved on the one hand by the chemical / physical properties of the substances themselves or by constructive measures, e.g. by covering the surface with a waterproof film, which may optionally also be made non-slip.

Another essential property of the protective agents against the ingrowth or growth of roots or rhizomes is the ease of application, in particular the ease of mixing in polymers and bitumen. Since these either already during mixing or in the course of the further process, e.g. are exposed to the extrusion of polymers to films, higher temperatures up to 220 ° C, the protective agents must be correspondingly temperature stable.

As is known to those skilled in the art, especially the agents from the group of cyclohexenoxime herbicides (DIM) and from the group of aryloxyphenoxypropionic acid herbicides (FOP) have a specific and selective action against different grasses.

In Aigner (Dissertation: "Evaluation of active ingredients in terms of their suitability as a root penetration protection for flat roofs", Johannes Kepler University, Linz, 2002), the herbicides bromoxynil, haloxyfop, ioxnil, isoproturon, mecoprop, propaquizofop and triclopyr were tested for their biological effectiveness. For the lupine test described therein for determining the biological effectiveness of root protectants, various herbicides and herbicidal mixtures were used, including three mixtures of Herbitect (mecoprop-P-2-ethylhexyl) and Haloxyfop-P-methyl in the proportions 1: 5, 1:10 and 1:20 and use concentrations of 0.25 and 0.40 mass%.

These mixing ratios and use concentrations correspond to the following individual concentrations:

Table 1

To produce the test specimens, a bituminous plate having a thickness of 0.8 to 1 cm was produced from a mixture of bitumen and herbicide mixture by pouring out the bitumen at 190 ° C. in each case. Bitumen has an average density of 1.02 g / cm3. This results in an average surface area of about 0,224 m2 +/- 0.025 m2 from the used bitumen mixtures. For the sake of simplicity, in the following Table 2 this value was used to calculate the amount of protective agent per m 2.

Table 2_

Mixtures triclopyr-2-butoxyethyl plus Haloxyfop-P-methyl, Dichlorprop plus Haloxyfop-P-methyl, and Herbitect plus Propaquizafop, in undefined mixing ratios were also mentioned.

The test was modified so that not only the root resistance against dicotyledonous lupins but also against the rhizomes and roots of monocotyledonous leeks should be determined.

As a result it is stated that in all experiments with Herbitect (mecoprop-P-2-ethylhexyl) and Haloxyfop-P-methyl strong to moderate rooting of the lupins templates, which is clearly a negative result.

Results concerning the penetration of rhizomes of couch grass can not be taken from the work, since it is stated that the seeds of couch grass were not germinated in the experiments.

The aim of the present invention is to provide compounds which can serve in bituminous membranes as a means against the penetration and penetration of rhizomes and roots of monocotyledonous plants, in particular grasses, for protection of structural waterproofing.

This object is achieved according to the invention by the use of aryloxyphenoxypropionic acid herbicides (FOP) wherein the aryloxyphenoxypropionic acid herbicides (FOP) are present in a bitumen and a bituminous sheet comprising a bitumen liner and the aryloxyphenoxypropionic acid herbicides (FOP) a) only in the carrier liner, or b ) in the carrier insert and the bitumen directly surrounding the carrier insert, or c) only in the bitumen immediately surrounding the carrier insert.

By "immediately surrounding" in the present specification is meant that the bitumen is in contact with the liner.

As a carrier insert preferably a polyester fleece is used, wherein the polyester fleece is preferably polyester staple fiber fleece, polyester filament spunbond or glass fiber reinforced polyester nonwoven.

As aryloxyphenoxypropionic acid herbicides (FOP) are fluozifop, haloxyfop and quizalofop or their biologically active optical isomers, fluazifop-P, haloxyfop-P and quizalofop-P in the form of their esters with branched or unbranched, a-aliphatic or alicyclic Cl-C8 Alcohols, aliphatic ether alcohols, such as butoxyethyl alcohol, or cyclic ether alcohols, such as tetrahydrofurfuryl alcohol, or propaquizafop, the 2-isopropylideneaminooxyethyl ester of quizalofop-P.

Particularly preferred are the ester of fluazifop-P with butanol, the esters of haloxyfop-P with methanol or ethoxyethanol, the esters of quizalofop-P with ethanol or tetrahydrofurfuryl alcohol, or propaquizafop, the 2-isopropylideneamino-oxyethyl ester of quizalofop-P.

As monocotyledonous plants especially among the grasses, the sweet grasses (family Poaceae), especially bamboo or Wheatgrass into consideration.

The invention further relates to bituminous membranes comprising a carrier liner and bitumen and at least one aryloxyphenoxypropionic acid herbicide (FOP), the at least one aryloxyphenoxypropionic acid herbicide (FOP) a) only in the carrier liner, or b) in the liner liner and the bitumen immediately surrounding the liner, or c) only in the bitumen immediately surrounding the liner.

The carrier insert used is preferably polyester staple fiber fleece, polyester filament spunbonded nonwoven or glass fiber reinforced polyester fleece.

As aryloxyphenoxypropionic acid herbicides, the above-mentioned representatives are preferred, the ester of fluazi-fop-P with butanol, the esters of haloxyfop-P with methanol or ethoxyethanol, the esters of quizalofop or quizalofop-P with ethanol or tetrahydrofurfuryl alcohol, or propaquizafop, the 2-Isopropylidenaminooxyethylester of quizalofop-P, are particularly preferred.

The invention will be explained in more detail with reference to the following, the scope of the invention not limiting examples.

Noninventive Example 1

In Example 1, the substances used in Aigner (2002) were Fluazifop-P (as butyl ester), Haloxyfop-P (as methyl ester) and Propaquizafop (Propaquizafop is a complex ester of Quizalofop-P) in various concentrations with respect to the question whether the penetration of rhizomes is slowed or prevented, tested from the concentrations used by Aigner (2002).

The test was carried out by mixing a given amount of the technical substance in molten polymer bitumen in a proportion of 7% SBS (styrene-butadiene-styrene) at 190 to 210 ° C. The mixture was homogenized by stirring, and using a squeegee, hot the underside of a 1.2 mm thick bituminous membrane GV E 10 SK (polymer bitumen sheet with a glass fleece insert with 60 g / m2 basis weight) applied at 700 g per m2. After application, another 1.2 mm thick bituminous membrane was placed with the underside on the bitumen layer and spread with a fur scooter and pressed. This resulted in a sandwich of bituminous membrane, bituminous layer containing herbicide and bitumen membrane again, weighing approx. 3400 g / m2. The blank test was a corresponding sandwich without preservative.

The amounts used of the substances in the individual experiments are shown in the following Table 3.

Table 3_______

After cooling this sandwich film, strips measuring 15 by 30 cm were cut therefrom. These were installed in transparent plastic containers made of acrylic glass, which were filled to half the height with clay granules along the walls. The plant substrate was then placed on the clay granules (water storage and buffer), so that the test film protruded about 2 cm above the plant substrate.

Bamboo from the family of sweet grasses, subfamily, served as test plants for the testing of biological activity

Bamboo plants, and couch grass (Elymus repens) from the grass family, subfamily Pooidaea.

The rhizomes of the plants grew almost exclusively horizontally in the substrate and reached the side walls of the vessel in vigorous conditions.

After 3 months and 6 months, respectively, the biological tests were evaluated. The planters were visually inspected and the growth of the rhizomes assessed. Subsequently, the films were removed and ingrown growth and growth of the rhizomes determined.

In all experimental members (1 / 1-1 / 12) several, between 3 and 5, rhizomes had grown through the foil after 3 months, but died about 5 mm to 10 mm behind the foil. The volunteering length was not significantly different between the individual experimental subjects.

In none of the test subjects could a growth depression be found compared to the untreated control.

In the untreated control also 5 rhizome tips were grown through the film, but have grown after growing through, between the film and the wall of the test vessel and had at the time of evaluation a length between 9 cm and 14 cm. Surprisingly, it was found that all three tested herbicides, including propaquizafop, showed a strong phytotoxic effect against both the rhizomes of the couch grass and against the rhizomes of the bamboo, and in concentrations of about a factor of 4, based on the percentage and up to a factor of 20, relative to g / m2, below those tested in Aigner (2002).

It was also unexpected that the rhizome tips completely died after penetrating the test film, but that no damage to the plants themselves occurred, which would be expected in this case by the person skilled in the art, since FOPs are systemic in the intake via the leaf and can be found in the Distribute plant.

Nevertheless, the result should be considered negative, because the rhizome tips have grown through the film and it has come to a leak.

Inventive Example 2

In Example 2, Example 1 was repeated as follows: Two types of nonwoven polyester fabrics were used, one known to a person skilled in the art as filament spunbonded nonwoven fabric (nonwoven type 1) and the other as nonwoven staple nonwoven fabric (nonwoven type 2). According to the state of the art, both types of polyester webs are used as reinforcement and insert in the production of polymer bitumen webs. Other nonwovens that can be used are combinations of glasscloth or glass fiber polyester nonwoven fabrics. There are also combinations of polyester fleece and aluminum foil. The person skilled in the various combinations are known. In the case in question, a staple fiber fleece and a filament spunbonded nonwoven with a grammage of 240 g each were used. However, this does not represent a limitation for this type or quality of polyester nonwovens.

The three active ingredients Haloxyfop-P-methyl, Fluazifop-P-butyl and Propaquizafop were dissolved in acetone and this solution applied by means of a lambskin scraper on the fleece and then dried at room temperature over a period of several days. These so impregnated with the active ingredients webs were cut into strips of again 15 x 30 cm and immersed in molten polymer bitumen in a proportion of 7% SBS (styrene-butadiene-styrene), so that the following bitumen foils emerged.

Table 4

These pieces of film were installed analogously to Example 1 in Plexiglas vessels. Bamboo and couch grass were again used as test plants.

After 3 months, the biological experiments were evaluated. The planters were visually inspected and the growth of the rhizomes assessed. Subsequently, the films were removed and ingrown growth and growth of the rhizomes determined.

In none of the treated test subjects, 2/1 to 2/8, after 3 months, the film was interspersed with the rhizomes of couch grass or bamboo. However, it could be observed that the tips of the rhizomes had grown into the untreated bitumen. Once the rhizomes have hit the treated fleeces, the tips have died. Some of the rhizomes have grown along the treated polyester fleeces, but died after a few millimeters, without damaging the plants themselves.

The untreated test elements 2/9 and 2/10 without protective agent, only with fleece insert, were smoothly grown through.

This result suggests that a mechanical resistance given by the polyester webs, in combination with the substances used, prevents rapid penetration, and the rhizomes absorb enough protection during the time they have to overcome the mechanical resistance. so that eventually the rhizome tips die off.

Inventive Example 3

In Example 3 Haloxyfop-P-methyl was dissolved in acetone and this solution by means of a lambskin scraper on polyester web with a grammage of 180, 140 and on a

60 g / m2 glass fleece (non-woven type 3) and then dried at room temperature over a period of several days. These webs so impregnated with the active ingredient were cut into 15 x 30 cm strips and poured into molten polymer bitumen without haloxyfop-P-methyl (Comparative Samples 3/7 and 3/8) and with a content of 1.3 g / kg of haloxypropyl P-methyl respectively 5.0 g / kg of Haloxyfop-P-methyl so that the bitumen films indicated in Table 5 were obtained:

Table 5

These pieces of film were installed analogously to Example 1 in Plexiglas vessels. Wheatgrass were used as test plants.

After 3 months, the biological experiments were evaluated. The planters were visually inspected and the growth of the rhizomes assessed. Subsequently, the films were removed and ingrown growth and growth of the rhizomes determined.

Table 6

As the results of Example 3 show, Ha-loxyfop-P-methyl at low concentration prevents rhizome growth when combined at 1.7 g / m 2 with a polyester nonwoven having the appropriate mechanical resistance. 1.7 g / m2 in the bituminous mass does not prevent the rhizome from growing into the surface. A glass fiber fleece with 60 g / m2 and in each case 1.7 g of Haloxyfop-P-methyl in the fleece and in the bituminous mass can not prevent the rhizomes from growing in and out. The rhizome tips have died after penetrating and ingrowth after about 4 to 15 mm. 6.5 g Haloxyfop-P-methyl per m2 only in the bituminous mass reduce waxing to the usual level, but also prevent it from growing through. By contrast, the samples without protective agent, so only with the 180 g nonwoven insert, smoothly through.

In none of the test subjects could a growth depression be found compared to the untreated control.

Example 4

In Example 4, the effect of Haloxyfop-P, Propaqui-zafop, Fluazifop-P and Quizalofop-P was on the one hand in a polymer bitumen (according to the invention) and on the other hand in a bi-tumen coated EPDM (ethylene-propylene-diene rubber) -Bahn (not according to the invention) tested. The two waterproofing membranes were equipped with dicotyledonous plants with mecoprop-P-2-ethylhexyl / MCPA-2-ethylhexyl in the ratio 60/40, at a rate of 12 g / m2. Against grasses (test plant Wheatgrass), the webs were equipped with four different Aryloxypheno-xypropionsäure-herbicides (FOP).

The polymer bitumen membrane has a 250 g / m2 polyester fiberglass-reinforced polyester fleece backing and was drawn with a thickness of approx. 5 mm. In the bitumen-coated EPDM sheet, the EPDM film serves as an element that causes the corresponding mechanical resistance.

Table 7_

Pieces of size 40 by 60 cm and 17 by 75 cm were cut out of the films produced on an industrial scale and in the laboratory. These pieces of film were installed according to the design plan in cuboid plastic vessels. Figure 1 shows schematically the experimental arrangement. In the KunstStoffgefäß a drainage of about 70mm was arranged from expanded clay, on which a bituminous strip A with weld was placed. In the diagonal vertical two bitumen strip B were arranged, each with at least one vertical weld. In FIG. 1, for reasons of clarity, only one vertical bituminous sheet strip B is shown. An arranged between the bitumen strip B Styrofoam plate (not shown) prevented sticking. The horizontal one

Bitumen strip A and the vertical bitumen strip B were not interconnected. Subsequently, the vessel was filled with substrate and on the one side, leek (monocotyledon) and on the other side, ficus (dicotyledon) were used as test plants.

After 6 months, the biological tests were evaluated. The planters were visually inspected and the growth of rhizomes and roots assessed. Subsequently, the films were removed and ingrowth and growth of rhizomes and roots determined. Although the experimental design was not an FLL ("Research Association for Landscaping Landscaping") test, the evaluation was carried out according to the guidelines of the FLL test.

Table 8_

Fluazifop, haloxyfop, propaquizafop and quizalofop are aryloxyphenoxypropionic herbicides (FOP) and act systemically, i. The uptake is predominantly via the leaf with subsequent transmission (translocation) in the plant and the inhibition of acetyl-CoA carboxylase.

As has been described, the likelihood of controlling rhizome growth by introducing herbicides into sealants was not considered promising, as rhizomes are believed to interact very little or not at all with their environment, rather than taking in substances like roots.

Obviously, the active ingredients are also absorbed by the rhizome tips when the herbicides have been incorporated into structural waterproofing. Obviously, there is no strong systemic effect and translocation. The tip of the rhizome dies, but the plant itself is not damaged further. As can be seen from the results, there is no growth depression of the plants during an observation period of 6 months.

Claims (10)

claims Use of aryloxyphenoxypropionic acid herbicides (FOP) as an anti-penetration and permeator of rhizomes and roots of monocotyledonous plants, especially grasses, for protection of structural waterproofing, comprising the aryloxyphenoxypropionic acid herbicides (FOP) in a bitumen and a liner Are present bitumen membrane and the Aryloxyphenoxypropionsäure herbicides (FOP) a) only in the liner insert, or b) in the liner insert and the carrier insert directly surrounding bitumen, or c) only in the surrounding bitumen immediately surrounding the liner. 2. Use according to claim 1, wherein the carrier insert is a polyester fleece. 3. Use according to claim 2, wherein the polyester fleece is selected from polyester staple fiber fleece, polyester filament spunbonded or glass fiber reinforced polyester fleece. 4. Use according to any one of claims 1 to 3, wherein the aryloxyphenoxypropionic acid herbicides (FOP) under fluazifop, haloxyfop and quizalofop or their biologically active optical isomers, fluazifop-P, Haloxyfop-P and quizalofop-P in the form of their esters with branched or straight chain, α-aliphatic or alicyclic C 1 -C 8 alcohols, aliphatic ether alcohols such as butoxyethyl alcohol, or cyclic ether alcohols such as tetrahydrofurfuryl alcohol, or propaquizafop, the 2-isopropylideneaminooxyethyl ester of quizalofop-P. 5. Use according to claim 4, wherein the aryloxyphenoxypropionic acid herbicides (FOP) under the ester of fluazifop-P with butanol, the esters of haloxyfop-P with methanol or ethoxyethanol, the esters of quizalofop-P with ethanol or tetrahydrofurfuryl alcohol , or propaquizafop, the 2-isopropylideneaminooxyethyl ester of quizalofop-P. 6. Use according to any one of claims 1 to 5, wherein the grasses are sweet grasses (family Poaceae), in particular bamboo or Wheatgrass. 7. A bituminous membrane comprising a base layer and bitumen and at least one aryloxyphenoxypropionic acid (FOP) herbicide, the at least one aryloxyphenoxypropionic acid (FOP) a) only in the base layer, or b) in the base layer and the bitumen immediately surrounding the base layer, or c) is present only in the bitumen immediately surrounding the carrier insert. 8. bitumen sheet according to claim 7, wherein the carrier insert is selected from polyester staple fiber fleece, polyester filament spunbond or fiberglass-reinforced polyester nonwoven. 9. A bituminous membrane according to claim 7 or 8, wherein the aryloxyphenoxypropionic acid herbicides include fluazifop, haloxyfop and quizalofop or their biologically active optical isomers, fluazifop-P, haloxyfop-P and quizalofop-P in the form of their esters with branched or unbranched, aliphatic or alicyclic C 1 -C 8 alcohols, aliphatic ether alcohols, such as butoxyethyl alcohol, or cyclic ether alcohols, such as tetrahydrofurfuryl alcohol, or propaquizafop, the 2-isopropylideneaminooxyethyl ester of quizalofop-P. 10. A bituminous membrane according to claim 9, wherein the aryloxyphenoxypropionic acid herbicides (FOP) under the ester of fluazifop-P with butanol, the esters of haloxyfop-P with methanol or ethoxyethanol, the esters of quizalofop-P with ethanol or tetrahydrofurfuryl alcohol or propaquizafop, the 2-isopropylideneaminooxyethyl ester of quizalofop-P.