WO2003069996A1

WO2003069996A1 - Molluscicide

Info

Publication number: WO2003069996A1
Application number: PCT/EP2003/001277
Authority: WO
Inventors: Wolfgang Wirth; Udo Reckmann; Gerhard Baron; Torsten Groth; Thomas Sildatke
Original assignee: Bayer Cropscience Aktiengesellschaft
Priority date: 2002-02-21
Filing date: 2003-02-10
Publication date: 2003-08-28
Also published as: AU2003208820A1; DE10207243A1

Abstract

The invention relates to novel molluscicides consisting of: iminodisuccinic acid of formula (I) and/or the ammonium, alkaline metal, earth alkaline metal and/or iron salts thereof, optionally blended with one or more magnesium, calcium and/or iron salt(s); optionally fine-grained meal, and optionally one or more additives. The invention also relates to a method for producing said molluscicides and to their use for combating terrestrial molluscs.

Description

snail bait

The present invention relates to new snail baits based on iminodisuccinic acid, a process for their preparation and their use for controlling snails.

It is already known to control terrestrial snails with the aid of baits which contain feed and moUuscicidal active ingredients, such as methiocarb, metaldehyde or metal chelates (cf. DE 35 03 608A, DE 36 12 161A, WO 96-05 728A, WO

97-26 789A, WO 99-25 194A, WO 99-39 576A and WO 00-11 948A). However, the effectiveness of these preparations is not always satisfactory.

New snail baits have now been found

Iminodisuccinic acid of the formula

and / or their ammonium, alkali metal, alkaline earth metal and / or iron salts,

optionally in a mixture with one or more magnesium, calcium and / or iron salts,

• fine grain cereal flour, • if necessary, binders and

• optionally one or more additives consist.

It was also found that the new snail baits can be produced by

1) a mixture of

Iminodisuccinic acid of the formula

and / or their ammonium, alkali metal, alkaline earth metal and / or

Iron salts,

optionally in a mixture with one or more magnesium, calcium and / or iron salts, • at least one diluent and

• optionally produces additives,

2) _. the premix thus obtained with

• fine grain cereal flour, • if necessary, binders and

• additives if necessary

offset

3) the resulting mixture is stirred with so much water that a homogeneous

Dough arises 4) extrude and chop the dough and

5) the resulting product dries.

Finally, it was found that the new snail baits can be used very well to combat terrestrial snails.

Surprisingly, the baits according to the invention have a significantly better effectiveness in combating snails than the ^" most similar, known preparations for the same application.

The snail baits according to the invention are characterized by the ingredients listed.

The active components contained in the snail baits according to the invention are either

a) one or more ammonium, alkali metal, alkaline earth metal and / or iron salts of iminodisuccinic acid of the formula (I),

or to

b) one or more ammonium, alkali metal, alkaline earth metal and / or iron salts of iminodisuccinic acid of the formula (I) in a mixture with

one or more magnesium, calcium and / or iron salts

or to

- c) Iminodisuccinic acid of the formula (I) in a mixture with one or more magnesium, calcium and / or iron salts. Suitable salts of iminodisuccinic acid are preferably their ammonium, lithium, sodium, potassium, magnesium, calcium, iron (II) and iron (III) salts. These salts can be uniform or mixed salts. Uniform salts are to be understood here as salts which contain only one of the cations mentioned. Mixed salts are understood to mean those salts which contain various of the cations mentioned. In addition, salts are also suitable in which not all carboxyl groups of iminodisuccinic acid are in salt form.

The iminodisuccinic acid of the formula (I) and its salts are known or can be prepared by known methods (cf. "LOS sodium salt", Bayer AG, April 1999).

In addition to the iminodisuccinic acid of the formula (I) or its salts, the snail baits according to the invention may also contain one or more magnesium, calcium and / or iron salts.

Preferred salts of the metals mentioned are sulfates, carbonates and phosphates. Examples include magnesium sulfate, magnesium carbonate, calcium sulfate, calcium carbonate, iron (LT) sulfate, iron (IU) sulfate, iron (II) hydrogen sulfate, iron (III) hydrogen sulfate, iron (II) hydrogen phosphate, iron (III) hydrogen phosphate, iron (II) hydrogen carbonate, iron (II) phosphate, iron (IΙI) phosphate, iron (II) carbonate and iron (JJI) carbonate. The salts can be in the form of hydrates or in anhydrous form.

Commercially available flours, such as wheat flour, rye flour, rice starch and others, can be included as cereal flours in the snail baits according to the invention. Durum wheat flour and soft wheat flour are preferred. The flour is in fine-grained form, preferably in grain sizes below 250 μ. All conventional adhesives which can be used for the production of such preparations can be present as binders in the baits according to the invention. Modified starch, formaldehyde-releasing substances, optionally partially saponified polyvinyl acetate and / or molasses are preferred.

Modified starch in the present case means commercial products of this type. Cold source maize starch is preferred.

Substances which release formaldehyde can contain all customary products which are suitable for releasing formaldehyde. Urea are preferred

Formaldehyde condensation products.

Suitable polyvinyl acetates, which may optionally be in partially saponified form, are preferably the products known under the trade names Mowilith® (Clariant) and Mowiol® (Clariant).

In the present case, molasses are to be understood as the usual syrupy mother liquors produced in the manufacture of sugar.

Suitable additives which may be present in the baits according to the invention are preferably preservatives, dyes, snail attractants, grinding aids, additives, bitter substances, warm-blooded repellents and anticaking agents, and also water and other moUusicidal active ingredients.

All common, suitable for this purpose come as preservatives

Substances into consideration. 2-Hydroxybiphenyl, sorbic acid, p-hydroxybenzaldehyde, p-hydroxybenzoic acid methyl ester, benzaldehyde, benzoic acid, p-hydroxybenzoic acid propyl ester and p-nitrophenol may be mentioned as preferred. All usual substances suitable for this purpose are suitable as dyes. Inorganic pigments, such as iron oxide, titanium dioxide and ferrocyan blue, and organic dyes, such as anthraquinone, azo and metal phthalocyanine dyes, may preferably be mentioned.

All the usual snail attractants come for this purpose. suitable substances into consideration. Plant extracts and their derived products, as well as products of animal origin, may be mentioned as examples.

Suitable additives are substances that are used to adjust the pH in the

Bait preparations are suitable. Citric acid is an example.

All substances suitable for this purpose can be used as grinding aids. Examples include kaolins, clays, talc, chalk, quartz powder and finely divided silica.

As warm-blooded repellants, which have a repellent effect on warm-blooded creatures such as dogs or hedgehogs, all substances customary for this purpose can be considered. An example is nonyl acid vanillylamide.

All substances customary for this purpose are suitable as bitter substances. Denatonium benzoate may be mentioned as an example.

All substances customary for this purpose that prevent clumping and caking are suitable as anticaking agents. May be mentioned as an example

Moisture-adsorbing powders, such as diatomaceous earth, pyrogenic silicas, tricalcium phosphate, calcium silicates, aluminum oxide, magnesium oxide, magnesium carbonate, zinc oxide, stearates and fatty amines.

All suitable for this purpose come as additional moUuscicidal active ingredients

Substances into consideration. Mehtiocarb, metaldehyde and Metal salts, optionally in a mixture with complexing agents, chelates of ethylenediamine tetraacetic acid and iron and / or copper ions being mentioned as examples.

The content of the individual ^' components can in the inventive

Snail baits can be varied within a certain range. So the concentrations are

• Iminodisuccinic acid of the formula (I) and / or its ammonium, alkali metal, alkaline earth metal and / or iron salts, optionally in a mixture with one or more magnesium, calcium and / or iron salts in general between 3.0 and 25% by weight, preferably between 5.0 and 20% by weight. Cereal flour generally between 50 and 95% by weight, preferably between 60 and 90% by weight,

Binder in general between 0 and 20% by weight, preferably between 0 and 15% by weight,

• Additives generally between 0 and 5.0 wt .-%, preferably between 0 and 3.0 wt .-%.

When carrying out the method according to the invention, preference is given to using those components which have already been mentioned as preferred constituents in connection with the description of the snail baits according to the invention.

Inert organic solvents and / or water can be used as diluents during the implementation. Water can preferably be used.

The amounts of the individual components are chosen so that the substances in the snail baits according to the invention in those weight ratios are present, which were mentioned above. However, the amount of water or diluent is measured so that a dough is formed in step (3) of the process. The amount of water used is generally between 25 and 35% by weight, preferably between 27 and 34% by weight, based on the other constituents. In the snail baits according to the invention, however, the water content is significantly lower because the initially moist product is still dried in stage (5) of the production process. There is practically only the residual moisture present in the flour.

The temperatures can be varied within a certain range when carrying out the method according to the invention. One works in the implementation

Stage (1) generally at temperatures between 0 ° C. and 30 ° C., preferably at room temperature,

Stage (2) generally at temperatures between 0 ° C. and 30 ° C., preferably at room temperature,

Stage (3) generally at temperatures between 0 ° C and 40 ° C, preferably between 10 ° C and 30 ° C,

Stage (4) generally at temperatures between 20 ° C and 60 ° C, preferably between 30 ° C and 50 ° C and

• stage (5) generally at temperatures between 20 ° C and 90 ° C, preferably between 30 ° C and 80 ° C.

Steps (1) to (3) and (5) of the process according to the invention are generally carried out under atmospheric pressure. However, it is also possible to borrow the drying process in stage (5) under reduced pressure. to lead. Step (4) is generally carried out under elevated pressure, preferably under a pressure between 30 and 100 bar.

When carrying out the method according to the invention, all devices customary for such processes can be used. For the mixing processes in stages (1) to (3), customary mixers are suitable, into which additional substances, such as flour, binders, diluents or water, can be added during the mixing process. Ploughshare mixers, paddle mixers and twin-screw extruders can preferably be used.

Conventional devices come a dough for extrusion in the step (4) in the food industry in consideration with the aid of through perforated plates strangfb ^'RMIG pressed and can be subsequently comminuted.

Conventional apparatus is used to dry the moist product in stage (5)

Question ^'shaped for removing moisture from particulate solids are suitable. In a preferred embodiment, the procedure is such that the moist product is first predried in a fluidized bed and then dried in a separate device to the desired final moisture.

In detail, the procedure for carrying out the method according to the invention is such that

• in step (1) a solution or suspension (“premix”) of iminodisuccinic acid or its salts, optionally in a mixture with other of the metal salts mentioned, and diluents, preferably water and optionally one or more further molluscicidal active ingredients and optionally additives such as preservatives, dyes, additives, etc., In stage (2) the premix obtained is mixed with fine-grain cereal flour, optionally with binder and optionally with further additives to form a homogeneous product,

In step (3) add so much water with mixing and kneading that a dough is formed,

• in step (4) the dough is extruded and crushed under pressure and

• in stage (5) the particulate material first pre-dries and then dries and then cools to room temperature.

In an alternative embodiment, several can also be carried out in stage (1)

Premixes are provided, which are used in succession in stage 2.

In an alternative embodiment, step (3) can be omitted, in particular if the dough already has the desired consistency.

In an alternative embodiment, the transition from pre-drying and post-drying takes place continuously.

The size of the snail bait can be carried out when carrying out the invention

Process can be varied in the desired manner within a certain range. The dough is generally crushed in such a way that pellets or strand-like particles are formed. The average diameter or length of the particles is generally between 1 and 4 mm, preferably between 1.5 and 3 mm.

The snail baits according to the invention are very suitable for controlling terrestrial snails in agriculture and horticulture. The snails include all land-living nudibranchs and shell snails, most of which occur as polyphage pests from agricultural and horticultural crops.

Important pests of this type are slugs, such as Arion rufüs (great path - left

snail), Arion ater and other Arionidae, Limax species, also field snails, such as Deroceras reticulatum and agreste from the Limacidae family, as well as species from the Milacidae family, and also harmful shell snails, such as those of the genus Cepaea, Discus, Helicigona and Helicella.

When controlling snails, the application rate of the baits according to the invention can be varied within a relatively wide range. In general, between 2 and 15 kg of snail bait are used per hectare, preferably between 3 and 7 kg per hectare.

The snail baits according to the invention can be applied by customary methods, such as, for example, by scattering and drilling in.

The invention is illustrated by the following examples.

Examples

Manufacturing examples

example 1

Production of snail bait according to the invention

878.7 g of durum wheat flour with a grain size of less than 250 μm are mixed in a dough kneader with stirring at room temperature within 2.5 minutes

Solution of 44.8 g of iron U-sulfate heptali hydrate in 140 g of water. A solution of 76.5 g of succinosuccinic acid tetrasodium salt in 140 g of water is then added within 2.5 minutes with stirring. The mixture is stirred and kneaded for 15 minutes. The resulting homogeneous dough is extruded at 40 ° C under a pressure of 60 bar through a perforated disc with holes with a diameter of 2.2 mm in the form of strands, which with the help of rotating knives in cylindrical 2 to 3 mm long Pieces are crushed. The material obtained is dried in a fluidized bed for 30 minutes by an air stream, the temperature of which is continuously increased from 20 ° C. and the exhaust air reaches a temperature of 55 ° C. at the end of the drying process. The product is then allowed to cool to room temperature and is left open to the air for 3 days so that the equilibrium moisture in the pellets is established. In this way, 1,000 g of snail bait are obtained in the form of cylindrical pellets.

To check the pH, some dried pellets are finely ground and stirred as a 10% by weight suspension in water for 15 minutes. The suspension is then left to stand for 1 minute and the pH of the aqueous phase is then measured. It is 6.27. Example 2

Production of snail bait according to the invention

894.2 g of durum wheat flour with a grain size of less are in a dough kneader

250μm within 2.5 minutes with stirring at room temperature with a suspension of 24.3 g iron m-phosphate hydrate and 5.0 g citric acid in 140 g water. A solution of 76.5 g of iminosuccinic acid tetrasodium salt in 140 g of water is then added within 2.5 minutes with stirring. The mixture is stirred for 15 minutes and kneaded. The resulting homogeneous dough is extruded at 40 ° C under a pressure of 60 bar through a perforated disc with holes with a diameter of 2.2 mm in the form of strands, which with the help of rotating knives in cylindrical 2 to 3 mm long Pieces are crushed. The material obtained is dried in a fluidized bed for 30 minutes by an air stream, the temperature of which is continuously increased from 20 ° C. and the exhaust air reaches a temperature of 55 ° C. at the end of the drying process. The product is then allowed to cool to room temperature and is left open to the air for 3 days so that the equilibrium moisture in the pellets is established. In this way, 1,000 g of snail bait are obtained in the form of cylindrical pellets.

To check the pH, some dried pellets are finely ground and stirred as a 10% by weight suspension in water for 15 minutes. The suspension is then left to stand for 1 minute and the pH of the aqueous phase is then measured. It is 7.45. Comparative examples

Example I

According to the method described in Example 1, snail baits are in the form of

Pellets made by using the following components:

891.0 g durum wheat flour

44.8 g of iron U-sulfate heptahydrate

3.0 g sodium hydrogen carbonate

61.2 g of ethylenediamine tetraacetic acid tetrasodium salt

In this way, 1,000 g of snail bait are obtained in the form of cylindrical pellets.

A 10% by weight suspension of finely ground pellets in water has a pH of 7.42 after stirring for 15 minutes and standing for 1 minute in the aqueous phase.

Example II

According to the method described in Example 1, snail baits are produced in the form of pellets by using the following components:

909.5 g durum wheat flour

24.3 g of iron-iπ-phosphate hydrate

5.0 g citric acid

61.2 g of ethylenediamine tetraacetic acid tetrasodium salt

In this way, 1,000 g of snail bait are obtained in the form of cylindrical pellets. A 10% by weight suspension of finely ground pellets in water has a pH of 6.65 after stirring for 15 minutes and standing in the aqueous phase for 1 minute.

Example III

911.0 g durum wheat flour 44.8 g iron U-sulfate heptahydrate 44.2 g nitrilotriacetic acid trisodium salt

Example IV

926.5 g of wheat flour

24.3 g iron ffl phosphate hydrate

5.0 g citric acid

44.2 g of trisodium nitrilotriacetic acid salt In this way, 1,000 g of snail bait are obtained in the form of cylindrical pellets.

A 10% by weight suspension of finely ground pellets in water has a pH of 7.50 after stirring for 15 minutes and leaving to stand for 1 minute in the aqueous phase.

Example of use A

Control of snails / laboratory tests

The bottom of plastic containers with a length of 22 cm and a width of 16 cm is covered with a 2 cm high layer of moist compost. 0.15 g of snail bait pellets are then evenly distributed over the entire width of the test container over a length of 17 cm on the surface of the compost. 20 wheat grains are evenly placed in the spaces between the pellets. On the untreated surface, a 4 x 4 cm large plastic pot, which serves as a protective space and has holes on the sides, is placed with the floor facing upwards. At the start of the experiment, 10 snails (Deroceras reticulatum) are placed on the untreated surface of each test container. Each test container is then covered with gauze so that the screws cannot escape. The test containers are set up at a temperature of 15 ° C and a relative humidity of 95% and illuminated 12 hours a day.

The evaluation is carried out after 7 days. The mortality of the snails is determined and calculated in percent. 0% means that no snails have died, while 100% means that all snails have died.

Preparations used, application rates and test results are shown in the following table. Table A

*) The iron HI-phosphate was used in the form of the snail bait, which is commercially available under the name Ferramol® (Neudorff company).

**) Fe EDTA stands for iron chelate of ethylenediamine tetraacetic acid.

***) Fe SO4 JDS-Na4 stands for iron-sulfate mixed with iminodisuccinic acid tetrasodium salt

Claims

claims

1. Snail bait that made up

Iminodisuccinic acid of the formula

optionally in a mixture with one or more magnesium,

Calcium and / or iron salts, • fine-grain cereal flour,

Optionally binder and optionally one or more additives

consist.

2. A method for producing snail baits according to claim 1, characterized in that

1) a mixture of

• Iminodisuccinic acid of the formula

at least one diluent and optionally additives

manufactures

2) the premix thus obtained with

• fine grain cereal flour, • if necessary, binders and

• additives if necessary

offset

3) if necessary, the resulting mixture is stirred with enough water to form a homogeneous dough,

4) extrude and chop the dough and

5) the resulting product dries. Use of snail baits according to claim 1 for combating tenestrial snails, characterized in that the bait material is applied to the habitat of the snails.