Methods for improving the efficacy of herbicides

Abstract

1. A method for improving the efficacy of a herbicide comprising applying an aqueous spray of the herbicide in combination with an anionic copolymer CP, the copolymer CP being made from repeat units of polymerized ethylenically unsaturated monomer M, the polymerized ethylenically unsaturated monomer M being a) 50 to 99.5% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Ma selected from the group consisting of primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms; b) 0 to 50% by weight of one or more monomers Mb, based on the total weight of the ethylenically unsaturated monomers M; at least one monomer Mb.1 selected from the group consisting of monoethylenically unsaturated sulfonic acids and their salts, or at least one monomer Mb.2 selected from the group consisting of monoethylenically unsaturated monomers having at least one quaternary ammonium group; c) one or more monoethylenically unsaturated monomers Mc having at least one poly C2-C6 alkylene oxide moiety having a terminal OH group or a terminal C1-C6 alkoxy group in an amount of 0 to 15% by weight based on the total weight of the ethylenically unsaturated monomers M in addition to a moiety having an ethylenically unsaturated double bond; The total amount of monomers Ma and Mb is at least 85% by weight, based on the total weight of ethylenically unsaturated monomers M, and the total amount of monomers Mb and Mc is 0.5 to 50% by weight, based on the total weight of ethylenically unsaturated monomers M.

Description

[Technical field]

[0001] The present invention relates to a method for improving the efficacy of a herbicide, the method comprising applying an aqueous spray of the herbicide in combination with a copolymer CP. The present invention also relates to the use of the copolymer CP as defined herein for improving the biological activity (hereinafter efficacy) of the herbicide. [Background technology]

[0002] In agriculture, herbicides are widely used to control the growth of undesirable plants, such as weeds, because they compete with crop plants for water, nutrients, and sunlight, resulting in reduced crop yield and crop quality. Herbicides can be applied to eliminate undesirable plants from cultivated land before sowing or planting crop plants. However, depending on the crop and the compatibility of the herbicide with the crop, herbicides can also be applied to the agricultural land where crop plants grow.

[0003] To be effective, herbicides must overcome various (morphological, biological, and environmental) barriers to their penetration into the target plant. For example, trichomes on the leaf surface can reduce herbicide efficacy by blocking spray particles before they come into contact with the epidermal surface. Environmental stress (e.g., hot, dry weather) can cause a thicker than normal wax layer or increase other defense structures, such as slowing down the plant's metabolic and transport processes necessary for proper weed control. As a result, the biological activity of the herbicide may be unsatisfactory, or at least lower than expected. Although higher application rates can provide better herbicidal efficacy, this is often not possible for regulatory reasons and is undesirable for environmental and economic reasons. Instead, there is great interest in improving the biological effectiveness (also called efficacy or biological efficacy) of herbicides to reduce application rates and / or improve weed control in this way.

[0004] It is well known that the efficacy of herbicides can be improved by certain adjuvants. Adjuvants (from the Latin adiuvare, to assist) are commonly used in agriculture to improve the performance of herbicides or other pesticides, including better mixing and handling, improved efficacy and safety, better distribution, and reduced drift. In the broad sense, an adjuvant is an ingredient that assists or modifies the action of the main active ingredient. Adjuvants can be broadly classified into three groups: (1) Surfactant (2) Spray modifiers, and (3) Utility modifier

[0005] Active agents improve the efficacy of herbicides primarily through various mechanisms of action. Active agents are generally surfactants, specifically nonionic surfactants (NIS), including silicone surfactants, oils such as high surfactant oils, crop oil concentrates, vegetable oil concentrates, and modified vegetable oil concentrates, and wetting agents. Spray conditioners modify the properties of the aqueous spray, which may facilitate the aiming of herbicide sprays, reduce airborne drift of herbicides, or allow the spray to adhere more easily to plants through various mechanisms. Utility conditioners help minimize handling and application problems. They can expand the conditions under which the herbicide can be used or maintain the integrity of the spray. For example, utility conditioners reduce foaming, improve solubility, adjust pH, or reduce spray drift. In contrast to active agents, spray conditioners and utility conditioners do not usually improve the biological efficacy of pesticides, but make aqueous pesticide sprays easier to apply.

[0006] A review of adjuvant technology is provided by Z. Pacanosky, Herbicide Adjuvants (2015), DOI: 10.5772 / 60842. A summary of commercially available herbicide adjuvants is provided by BG Young et al. (ed.) “Compendium of Herbicide Adjuvants”, 13th Edition (2016), Purdue Extension and Southern Illinois University (https: / / mdc.itap.purdue.edu / item.asp?Item_Number=PPP-115).

[0007] US Patent No. 6,372,842 describes a copolymer of a hydrophobic monomer selected from N-alkylacrylamide or alkyl acrylate and a hydrophilic monomer selected from acrylamidoalkylsulfonic acid, acrylamidoalkyldisulfonic acid, and styrenesulfonic acid.The copolymer is suitable for suppressing the undesired formation of very small droplets (mist or aerosol) when the aqueous composition is subjected to shear stress, for example when spraying an aqueous pesticide spray.

[0008] US Patent No. 6,288,010 describes aqueous compositions containing a water-soluble inorganic compound, specifically an ammonium fertilizer, and an anti-drift agent selected from 1.9 g / L of a water-soluble anionic polymer, such as a copolymer of acrylamide and acrylic acid. These aqueous compositions are used as additives for aqueous sprays of pesticides, so that the amount of copolymer in the spray is at least 500 ppm.

[0009] US Patent Application Publication No. 2019 / 110467 describes the use of a high molecular weight copolymer of acrylamide, at least one polyether macromonomer, and optionally an acidic monomer selected from 2-acrylamido-2 methylpropanesulfonic acid and acrylic acid to improve the drift performance of aqueous pesticide sprays. The polymer helps to reduce the amount of droplets with a droplet size of less than 100 μm when applying the aqueous spray. The copolymer is not described as improving the activity of the herbicide. Summary of the Invention [Problem to be solved by the invention]

[0010] Although the above-mentioned active agents, i.e. surfactants, oils, and wetting agents, may be suitable for improving the biological activity of herbicidally active compounds, they need to be applied at relatively high rates, which may be undesirable for economic or environmental reasons.There is a continuing need to find substances that improve the biological activity of herbicides at low application rates. [Means for solving the problem]

[0011] Surprisingly, it has been found that the copolymer CP as defined herein enhances the herbicidal activity of the herbicide compound when an aqueous spray of the herbicide compound is applied.

[0012] The copolymer CP is made from repeat units of polymerized ethylenically unsaturated monomers M, where M is a) 50 to 99.5% by weight, in particular 65 to 99% by weight or 70 to 99% by weight, in particular 75 to 98% by weight or 80 to 98% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Ma selected from the group consisting of primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, b) 0 to 50% by weight, for example 0.5 to 50% by weight or 0.5 to 35% by weight or 0.5 to 30% by weight or 0.5 to 25% by weight or 0.5 to 20% by weight or 0.5 to 15% by weight, in particular 1 to 50% by weight or 1 to 35% by weight or 1 to 30% by weight or 1 to 25% by weight or 1 to 20% by weight or 1 to 15% by weight, more in particular 1.5 to 30% by weight or 1.5 to 25% by weight or 1.5 to 20% by weight or 1.5 to 15% by weight, in particular 2.0 to 25% by weight or 2 to 20% by weight or 2.0 to 15% by weight, of one or more monomers Mb, based on the total weight of ethylenically unsaturated monomers M, at least one monomer Mb.1 selected from the group consisting of monoethylenically unsaturated sulfonic acids and their salts, or at least one monomer Mb.2 selected from the group consisting of monoethylenically unsaturated monomers having at least one quaternary ammonium group; c) one or more monoethylenically unsaturated monomers Mc having at least one poly C2-C6 alkylene oxide moiety having a terminal OH group or a terminal C1-C6 alkxoy group in addition to a moiety having an ethylenically unsaturated double bond, in an amount of 0 to 15% by weight or 0.1 to 15% by weight, specifically 0 to 8% by weight or 0.2 to 8% by weight, particularly 0 to 5% by weight or 0.5 to 5% by weight, based on the total weight of the ethylenically unsaturated monomers M, The total amount of monomers Ma and Mb is at least 85% by weight, specifically at least 92% by weight, in particular at least 95% by weight, based on the total weight of ethylenically unsaturated monomers M, and the total amount of monomers Mb and Mc is 0.5 to 50% by weight, specifically 1 to 35% by weight or 1 to 30% by weight or 1 to 25% by weight or 1 to 20% by weight, preferably 1.5 to 25% by weight or 1.5 to 20% by weight or 1.5 to 15% by weight, in particular 2 to 25% by weight or 2 to 20% by weight or 2 to 15% by weight, based on the total weight of ethylenically unsaturated monomers M.

[0013] Thus, the present invention relates to a method for improving the efficacy of a herbicide, the method comprising applying an aqueous spray of the herbicide in combination with a copolymer CP, wherein the copolymer CP is as described herein.

[0014] The present invention also relates to the use of copolymers CP as defined herein for improving the efficacy of herbicides, especially when the herbicides are applied as herbicide-containing aqueous sprays.

[0015] The present invention also relates to an aqueous spray solution containing a herbicide and a copolymer CP as defined herein, wherein the copolymer CP is a) 50 to 99.5% by weight, in particular 65 to 99% by weight or 70 to 99% by weight, in particular 75 to 98% by weight or 80 to 98% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Ma selected from the group consisting of primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, b) one or more monomers Mb, which represent from 0.5 to 50% by weight, or from 0.5 to 35% by weight, or from 0.5 to 30% by weight, or from 0.5 to 25% by weight, or from 0.5 to 20% by weight, or from 0.5 to 15% by weight, in particular from 1 to 50% by weight, or from 1 to 35% by weight, or from 1 to 30% by weight, or from 1 to 25% by weight, or from 1 to 20% by weight, or from 1 to 15% by weight, more particularly from 1.5 to 30% by weight, or from 1.5 to 25% by weight, or from 1.5 to 20% by weight, or from 1.5 to 15% by weight, in particular from 2.0 to 25% by weight, or from 2 to 20% by weight, or from 2.0 to 15% by weight, based on the total weight of the ethylenically unsaturated monomers M, at least one monomer Mb.1 selected from the group consisting of monoethylenically unsaturated sulfonic acids and their salts, or - at least one monomer Mb.2 selected from the group consisting of monoethylenically unsaturated monomers having at least one quaternary ammonium group; and The copolymer CP specifically has the following properties i), ii), iii), iv), v) or vi), namely: i) the monomer Ma being acrylamide; ii) the monomer M comprises 0.5 to 50% by weight of at least one monomer Mb.1; ii) the monomer Mb.1 is 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof; iv) the monomer M is a) 70 to 99% by weight, in particular 75 to 99% by weight, or 75 to 98.5% by weight, or 75 to 98% by weight, preferably 80 to 99% by weight, or 80 to 98.5% by weight, or 80 to 98% by weight, in particular 85 to 99% by weight, or 85 to 98.5% by weight, or 85 to 98% by weight, of acrylamide, based on the total weight of the ethylenically unsaturated monomers M, and b) the property of being composed of 1 to 30% by weight, specifically 1 to 25% by weight, or 1.5 to 25% by weight, or 2 to 25% by weight, preferably 1 to 20% by weight, or 1.5 to 20% by weight, or 2 to 20% by weight, particularly 1 to 15% by weight, or 1.5 to 15% by weight, or 2 to 15% by weight, of 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, based on the total weight of the ethylenically unsaturated monomer M; v) the copolymer CP in its sodium salt form has a weight average molecular weight Mw of at least 100,000 g / mol, particularly at least 250,000 g / mol, more particularly at least 500,000 g / mol, as determined by gel permeation chromatography; vi) the copolymer CP in its sodium salt form has a viscosity of at least 50 cm, determined at 30° C. in a 0.5 M aqueous sodium chloride solution 3 / g, specifically at least 100 cm 3 / g, preferably at least 150 cm 3 / g, especially at least 200 cm 3 The property of having an intrinsic viscosity [η] of / g, vii) the monomer M is a) 95 to 99.5% by weight of acrylamide, based on the total weight of ethylenically unsaturated monomers M; and b) 0.5 to 5% by weight of monomer Mb.2, based on the total weight of ethylenically unsaturated monomers M, specifically N-(3-trimethylammoniumpropyl)acrylamide salt.

[0016] The present invention also relates to an aqueous spray solution containing a herbicide and a copolymer CP as defined herein in an amount of 10 to 100 ppm based on the total weight of the spray solution.

[0017] The present invention also relates to an aqueous spray solution containing a herbicide comprising glufosinate, glyphosate or dicamba or a salt thereof and a copolymer CP as defined herein, wherein the amount of copolymer CP is specifically in the range of 5 to 500 ppm or in the range of 10 to 300 ppm, more preferably in the range of 10 to 200 ppm, in particular in the range of 10 to 100 ppm, based on the total weight of the aqueous spray solution.

[0018] When the herbicide is applied in a normal manner, the presence of the copolymer CP leads to an improvement or enhancement of herbicidal activity, i.e., an improvement in the growth control of the target plant, compared to a control experiment, i.e., when the herbicide is applied in the same manner and at the same application rate, but in the absence of the copolymer CP. The growth control of the target plant is typically indicated on a scale from 0% for no control to 100% for complete control, which is a scale that is commonly used by those skilled in the art of agronomy. A statistically significant improvement in control is achieved when the control achieved in the presence of the copolymer CP is at least 0.5% higher, in particular at least 1.0%, at 14 days after treatment (14 DAT) or 28 days after application (28 DAT) compared to a control experiment. Thus, in the context of the present invention, the term "improving efficacy" is understood as an improvement in the herbicidal activity of the herbicide, i.e., the control of the target plant by the target plant.

[0019] Surprisingly, the improvement in efficacy of the herbicide is achieved at very low concentrations of the copolymer CP in the aqueous spray solution. In particular, a significant improvement in efficacy is observed at a concentration of the copolymer CP of 5 ppm or more. Preferably, the concentration of the copolymer CP in the aqueous spray solution does not exceed 500 ppm, in particular 300 ppm, or in particular 200 ppm. Preferably, the amount of the copolymer CP in the aqueous spray solution is in the range of 5 to 500 ppm, in particular in the range of 10 to 300 ppm, more particularly in the range of 10 to 200 ppm, in particular in the range of 10 to 100 ppm, based on the total weight of the aqueous spray solution. Here and below, ppm means parts per million by weight. In other words, 100 ppm corresponds to 0.01% by weight based on the weight of the spray solution.

[0020] In the context of the present invention, C1-C n The term refers to the number of carbon atoms that the radical may have. For example, C1-C nThe term alkyl relates to a specific alkyl radical within the group of linear or branched alkyl radicals having 1 to n carbon atoms, thus the term C1-C3 alkyl relates to an alkyl radical within the group of linear or branched alkyl radicals having 1 to 3 carbon atoms, i.e. the group consisting of methyl, ethyl, 1-propyl and 2-propyl. The term C1-C6 alkyl thus relates to alkyl groups within the group of linear or branched alkyl radicals having 1 to 6 carbon atoms, i.e. the group comprising methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl (isobutyl), tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 3-methyl-2-butyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-1-pentyl, 3-methyl-2-pentyl, 4-methyl-1-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 3,3-dimethyl-2-butyl, 2,3-dimethyl-1-butyl, 2,3-dimethyl-2-butyl. The term C2-C6 alkylandiyl refers to saturated linear or branched divalent alkyl radicals, including, for example, 1,1-ethanediyl, 1,2-ethanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,2-butanediyl, 2,3-butanediyl, 1,4-butanediyl, 1,2-pentanediyl, 2,3-pentanediyl, 2,2-dimethyl-1,3-propanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,2-hexanediyl, etc. The terms C2-C6 alkylandiyl and C2-C6 alkylene are used synonymously.

[0021] The term poly C2-C6 alkylene oxide refers to a polyether radical made up of C2-C6 alkylene oxide repeating units. In this context, the term C2-C6 alkylene oxide refers to a radical of formula OQ, where Q is a C2-C6 alkylene, in particular the radical -CH2CH2- or the radical -CH2CHR4 -(In the formula, R 4 is C1-C4 alkyl). When the poly C2-C6 alkylene oxide moiety contains different C2-C6 alkylene oxide repeat units, they may be arranged statistically, i.e., alternately or in blocks in any order.

[0022] In the context of the monomer M, the term "monoethylenically unsaturated" means that the monomer has a single ethylenic double bond, specifically in the form of a vinyl group (CH=CH2) or a vinylidene group (C(CH3)=CH2). The vinyl and vinylidene groups can be attached to a saturated carbon atom, or a carbonyl group, or an oxygen atom of the monomer.

[0023] The term "monoethylenically unsaturated monocarboxylic acid having 3 to 6 C atoms" refers to a carboxylic acid having a single carboxyl group (COOH), a single ethylenically unsaturated double bond, and 3 to 6 carbon atoms. Examples of such monoethylenically unsaturated monocarboxylic acids include, but are not limited to, acrylic acid, (propenoic acid), methacrylic acid (2-methylpropenoic acid), crotonic acid (2-butenoic acid), 3-butenoic acid, 2-pentenoic acid, and 2-propenyloxyacetic acid.

[0024] In the context of the present invention, the term "herbicide" relates both to herbicidally active compounds (hereinafter also referred to as active ingredients) and to combinations of herbicidally active ingredients.

[0025] As used herein, the terms "control" and "combat" are synonymous. As used herein, the terms "undesirable vegetation," "undesirable species," "undesirable plants," "harmful plants," "undesirable weeds," or "harmful weeds" are synonymous. As used herein, the term "locus" means the area in which vegetation or plants are growing or will grow, typically a field.

[0026] In the monomers M forming the copolymer CP, the monomers Ma are selected from primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 C atoms, in particular 3 or 4 C atoms. Preferably, the monomers Ma are selected from acrylamide and methacrylamide, and mixtures thereof. In particular, the monomers Ma comprise at least 70% by weight, more particularly at least 90% by weight, of acrylamide, based on the total weight of the monomers Ma. In particular, the monomer Ma is an acrylamide. The relative amount of monomer Ma is in particular in the range of 65 to 99% by weight, or in the range of 70 to 99% by weight, or in the range of 75 to 99% by weight, or in the range of 80 to 99% by weight, in particular in the range of 70 to 98.5% by weight, or in the range of 75 to 98.5% by weight, or in the range of 80 to 98% by weight, or in the range of 85 to 98.5% by weight, based on the total weight of ethylenically unsaturated monomers M forming the copolymer.

[0027] The monomer M may further comprise at least one monomer Mb. The monomer Mb is either a monoethylenically unsaturated monomer Mb.1 or a monomer Mb.2.

[0028] Suitable monomers Mb.1 are primarily any monoethylenically unsaturated sulfonic acid or a salt thereof, in particular an alkali metal salt, such as a sodium or potassium salt, or an ammonium salt. Particularly preferred are monomers Mb.1 which are monomers of formula (I) or a salt thereof, [ka] During the ceremony, R 1 is H or C1-C3 alkyl, specifically H or methyl; X is O or NH; Z is a C2 to C6 alkanediyl, specifically a C2 to C4 alkanediyl, for example, 1,2-ethanylidyl, 1,2-propanediyl, 1,3-propanediyl, or 2-methyl-1,2-propanediyl.

[0029] Examples of monomers Mb.1 of formula (I) are 2-acryloxyethanesulfonic acid, 2-methacryloxyethanesulfonic acid, 2-acrylamidoethanesulfonic acid, 2-methacrylamidoethanesulfonic acid, 2-acryloxypropanesulfonic acid, 2-methacryloxypropanesulfonic acid, 2-acrylamidopropanesulfonic acid, 2-methacrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-acrylamido-2-methylpropanesulfonic acid, as well as their salts, in particular their sodium, potassium, and ammonium salts. Among the monomers Mb.1, particularly preferred is 2-acrylamido-2-methylpropanesulfonic acid, i.e. the monomers of formula (I) (wherein R 1 is H, X is NH, and Z is 2-methyl-1,2-propanediyl) and salts thereof.

[0030] Suitable monomers Mb.2 are primarily any monoethylenic monomers bearing a quaternary ammonium group. The quaternary ammonium group can be, for example, part of a heterocycle in an N-alkyl-N'-vinyl imidzolium salt or an N-alkyl-N-vinylpyrrolidinium salt, or a peralkylammonium group. Particularly preferred are monomers Mb.2 which are monomers of formula (II), or salts thereof, [ka] During the ceremony, R is C1-C3 alkyl, specifically methyl or ethyl; R 2 is H or C1-C3 alkyl, specifically H or methyl; A is O or NH; B is a C2-C6 alkanediyl, specifically a C2-C4 alkanediyl, such as 1,2-ethanoyl, 1,2-propanediyl, 1,3-propanediyl, or 2-methyl-1,2-propanediyl; Y represents a counteranion, such as chloride, sulfate, or methosulfate.

[0031] Examples of monomers Mb.2 of formula (II) are N-(3-trimethylammoniumpropyl)acrylamide salts (dimapa-Q), N-(3-trimethylammoniumpropyl)methacrylamide salts, 2-trimethylammoniumethylacrylate salts, 2-trimethylammoniumethylmethacrylate salts, 3-trimethylammoniumpropylacrylate salts, 3-trimethylammoniumpropylmethacrylate salts, N-(3-triethylammoniumpropyl)acrylamide salts, N-(3-triethylammoniumpropyl)methacrylamide salts, 2-triethylammoniumethylacrylate salts, 2-triethylammoniumethylmethacrylate salts, 3-triethylammoniumpropylacrylate salts, 3-triethylammoniumpropylmethacrylate salts, specifically their chlorides, sulfates or methosulfates. Among the monomers Mb.1, particularly preferred are N-(3-trimethylammoniumpropyl)acrylamide salts, specifically their chlorides, sulfates or methosulfates, i.e. monomers of formula (II) (wherein R 2 is H, A is NH, R is CH3, Z is 1,3-propanediyl, and Y represents a counteranion, such as chloride, sulfate, or methosulfate.

[0032] In the copolymer CP, the monomers Mb may be absent or may be present. The relative amount of the monomers Mb may be zero, but may also be in the range of 0.5 to 50% by weight, or in the range of 0.5 to 35% by weight, or in the range of 0.5 to 30% by weight, in particular in the range of 1 to 50% by weight, or in the range of 1 to 30% by weight, or in the range of 1 to 25% by weight, or in the range of 1 to 20% by weight, more particularly in the range of 1.5 to 30% by weight, or in the range of 1.5 to 25% by weight, or in the range of 1.5 to 20% by weight, or in the range of 1.5 to 15% by weight, in particular in the range of 2 to 25% by weight, or in the range of 2 to 20% by weight, or in the range of 2 to 15% by weight, based on the total weight of the ethylenically unsaturated monomers M.

[0033] The monomer M may further comprise at least one monomer Mc having a moiety with an ethylenically unsaturated double bond and at least one poly C2-C6 alkylene oxide moiety. The poly C2-C6 alkylene oxide moiety may have a terminal hydroxyl group (OH) or a terminal C1-C6 alkoxy group. Suitable moieties with an ethylenically unsaturated double bond may be vinyl, 2-propen-1-yl (allyl) or 2-propen-2-yl. The moiety with an ethylenically unsaturated double may be directly bonded to the terminal oxygen atom of the poly C2-C6 alkylene oxide moiety or may be bonded via a divalent linker. Suitable divalent linkers are C(=O), C1-C6 alkanediyl or O-C1-C6 alkanediyl. In the poly C2-C6 alkylene oxide moiety, different C2-C6 alkylene oxide repeat units may be arranged statistically, i.e., alternately or blockwise in any order. The poly C2-C6 alkylene oxide portion of the monomer Mc preferably contains different C2-C6 alkylene oxide repeating units. Preferably, the different C2-C6 alkylene oxide repeating units are arranged in a block shape. Specifically, the poly C2-C6 alkylene oxide portion of the monomer Mc contains ethylene oxide repeating units, i.e., units of the formula (EO): -CH2CH2-O- (EO) and C3-C6 alkylene oxide repeating units, i.e. repeating units of the formula (AO) and / or (AO') -CH2CHR 4 -O-(AO) -CHR 4 CH2-O-(AO') wherein R 4 is C1-C4 alkyl.

[0034] Preferably, the relative molar amount of EO repeat units to AO / AO' repeat units is in the range of 10:1 to 1:10, particularly in the range of 5:1 to 1:5. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] According to group (a) of embodiments, preference is given to monomers Mc having formula (III) CH2=C(R 1 )-R 5 -O-(EO) k -(AO / AO') l -(EO) m -R 6 (III) During the ceremony, R 1 is H or C1-C3 alkyl, specifically H or methyl; R 5 is a covalent bond, C(═O), C1-C6 alkanediyl, or O—C2-C6 alkanediyl, R 6 is H or C1-C4 alkyl, specifically H or methyl; EO is the radical -CH2CH2-O-, AO / AO' is -CH2CHR 4 -O- or -CHR 4 CH2-O-, where R 4 is C1-C4 alkyl, specifically methyl, ethyl, or n-propyl; k is a number in the range of 2 to 200, specifically in the range of 5 to 150, more specifically in the range of 10 to 75, particularly in the range of 15 to 40, or in the range of 15 to 30; l is a number in the range of 0 to 40, specifically in the range of 5 to 35 or 5 to 30 or 5 to 28 or 5 to 25, in particular in the range of 8.5 to 30 or 10 to 27.5 or 10 to 25 or 15 to 25, m is a number in the range of 0 to 15, specifically in the range of 0 to 10, for example, in the range of 0.5 to 15 or 0.5 to 10, more specifically in the range of 1 to 10, 1 to 7, or 1 to 5.

[0036] In formula (III), the repeating units EO and AO / AO' are arranged in blocks, i.e., in blocks (EO) k , (AO / AO') l , and (EO) mwhere k, l, and m indicate the average number of repeat units EO and AO / AO' in a block. The term AO / AO' means that either AO or AO', or both AO and AO' are not included in the block (AO / AO'). l It is understood that the block (AO / AO') may be present in the l In the formula, the radicals R in AO and AO' are 4 typically have the same meaning. For example, the block (AO / AO') l In the formula (I), in all repeat units AO and AO', the value of R4 is either methyl or ethyl or n-propyl.

[0037] In formula (III), R 5 Specifically, C1-C6 alkanediyl or O-C2-C6 alkanediyl, more specifically, CH2 or O-(C n’ H 2n’ ) where n is 2, 3, 4, or 5, specifically 3, 4, or 5.

[0038] According to group (a.1) of embodiments, particular preference is given to monomers Mc, in which the variables of formula (III) have the following meanings: R 1 is H, R 5 is CH2 or O-(C n’ H 2n’ ), where n is 2, 3, 4, or 5, specifically 3, 4, or 5; R 6 is H or methyl, EO is the radical -CH2CH2-O-, AO / AO' is -CH2CHR 4 -O- or -CHR 4 CH2-O-, where R 4 is methyl, ethyl or n-propyl, in particular ethyl; k is a number in the range of 10 to 75, in particular in the range of 15 to 40 or in the range of 15 to 30, l is a number in the range of 5 to 35 or 5 to 30 or 5 to 28 or 5 to 25, in particular in the range of 8.5 to 30 or 10 to 27.5 or 10 to 25 or 12 to 25, m is a number within the range of 0.5 to 15 or 0.5 to 10, more specifically within the range of 1 to 10 or 1 to 7 or 1 to 5, particularly within the range of 1.5 to 7 or 1.5 to 5.

[0039] According to group (a.2) of embodiments, the monomers Mc are selected from the monomers of formula (III), the variables in formula (III) having the following meanings: R 1 is H, R 5 is O-(C n’ H 2n’ wherein n is 3, 4, or 5; R 6 is H or methyl, EO is the radical -CH2CH2-O-, AO / AO' is -CH2CHR 4 -O- or -CHR 4 CH2-O-, where R 4 is ethyl, k is a number in the range of 15 to 40, particularly in the range of 15 to 35; l is a number in the range of 8.5 to 30, particularly in the range of 10 to 27.5 or 10 to 25, in particular in the range of 12 to 25; m is a number in the range of 0.5 to 10, more specifically in the range of 1 to 7, and particularly in the range of 1.5 to 5.

[0040] According to the invention, the amount of monomer Mc may be in the range of 0 to 15% by weight, in particular 0 to 8% by weight, in particular 0 to 5% by weight, based on the total weight of ethylenically unsaturated monomers M. If present, the amount of monomer Mc is typically in the range of 0.1 to 15% by weight, in particular 0.2 to 8% by weight, in particular 0.5 to 5% by weight, based on the total weight of ethylenically unsaturated monomers M.

[0041] According to a particularly preferred group (1) of embodiments, the monomers M forming the copolymer CP comprise from 0.5 to 50% by weight or from 0.5 to 35% by weight or from 0.5 to 30% by weight of at least one monomer Mb.1, in particular at least one monomer Mb.1 selected from the monomers of formula (I). In this particular group (1) of embodiments, the monomer Mb is in particular 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, in particular the sodium, potassium or ammonium salt thereof. In a group (1) of specific embodiments, the amount of monomers Mb.1 is in particular in the range of 1 to 50% by weight, or in the range of 1 to 35% by weight, or in the range of 1 to 30% by weight, or in the range of 1 to 25% by weight, or in the range of 1 to 20% by weight, more in particular in the range of 1.5 to 30% by weight, or in the range of 1.5 to 25% by weight, or in the range of 1.5 to 20% by weight, or in the range of 1.5 to 15% by weight, in particular in the range of 2 to 25% by weight, or in the range of 2 to 20% by weight, or in the range of 2 to 15% by weight, based on the total weight of the ethylenically unsaturated monomers M.

[0042] In a subgroup (1.a) of group (1) of specific embodiments, the monomers M forming the copolymer CP consist essentially of the monomers Ma and Mb.1. In this subgroup (1.a) of specific embodiments, the monomers M forming the copolymer consist essentially of a) 50 to 99.5% by weight, in particular 65 to 99% by weight, or 70 to 99% by weight, or 75 to 99% by weight, or 80 to 99% by weight, more in particular 70 to 98.5% by weight, or 75 to 98.5% by weight, or 80 to 98.5% by weight, or 85 to 98.5% by weight, in particular 75 to 98% by weight, or 80 to 98% by weight, or 85 to 98% by weight, or 80 to 95% by weight, or 85 to 95% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Ma, preferably selected from acrylamide, methacrylamide and mixtures thereof, and b) 0.5 to 50% by weight, in particular 1 to 35% by weight, or 1 to 30% by weight, or 1 to 25% by weight, or 1 to 20% by weight, more in particular 1.5 to 30% by weight, or 1.5 to 25% by weight, or 1.5 to 20% by weight, or 1.5 to 15% by weight, in particular 2 to 25% by weight, or 2 to 20% by weight, or 2 to 15% by weight, or 5 to 20% by weight, or 5 to 15% by weight, of at least one monomer Mb.1, preferably selected from monomers of formula (I) and salts thereof, based on the total weight of ethylenically unsaturated monomers M.

[0043] In a subgroup (1.a) of group (1) of specific embodiments, the monomers M forming the copolymer CP are preferably essentially a) 50 to 99.5% by weight, in particular 65 to 99% by weight, or 70 to 99% by weight, or 75 to 99% by weight, or 80 to 99% by weight, more particularly 70 to 98.5% by weight, or 75 to 98.5% by weight, or 80 to 98.5% by weight, or 85 to 98.5% by weight, in particular 75 to 98% by weight, or 80 to 98% by weight, 85 to 98% by weight, or 80 to 95% by weight, or 85 to 95% by weight, based on the total weight of the ethylenically unsaturated monomers M, of acrylamide, and b) 0.5 to 50% by weight, in particular 1 to 35% by weight, or 1 to 30% by weight, or 1 to 25% by weight, or 1 to 20% by weight, more in particular 1.5 to 30% by weight, or 1.5 to 25% by weight, or 1.5 to 20% by weight, or 1.5 to 15% by weight, in particular 2 to 25% by weight, or 2 to 20% by weight, or 2 to 15% by weight, or 5 to 20% by weight, or 5 to 15% by weight, of at least one monomer Mb.1, preferably selected from 2-acrylamido-2-methylpropanesulfonic acid and salts thereof, based on the total weight of ethylenically unsaturated monomers M.

[0044] In a subgroup (1.b) of group (1) of another specific embodiment, the monomers M forming the copolymer CP consist essentially of the monomers Ma, Mb.1 and Mc. In this subgroup (1.b) of specific embodiments, the monomers M forming the copolymer consist essentially of: a) 50 to 99.4% by weight, in particular 65 to 98.8% by weight, more in particular 70 to 98.3% by weight, in particular 75 to 97.5% by weight, or 80 to 97.5% by weight, or 80 to 97.5% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Ma, preferably selected from acrylamide, methacrylamide and mixtures thereof, b) 0.5 to 49.9% by weight, in particular 1 to 34.8% by weight, more in particular 1.5 to 29.8% by weight, in particular 2 to 24.5% by weight, or 2 to 19.5% by weight, or 4 to 19.5% by weight, of at least one monomer Mb.1, preferably selected from the monomers of formula (I) and salts thereof, based on the total weight of the ethylenically unsaturated monomers M, c) 0.1 to 15% by weight, in particular 0.2 to 8% by weight and in particular 0.5 to 5% by weight, of at least one monomer Mc, in particular of the monomer Mc of formula (III) and in particular of at least one monomer Mc of group a.1 or a.2 of the embodiments, The total amount of monomers Ma and Mb is at least 85% by weight, particularly at least 92% by weight, in particular at least 95% by weight, based on the total weight of ethylenically unsaturated monomers M, and the total amount of monomers Mb and Mc is 0.6 to 50% by weight, particularly 1.2 to 35% by weight, or 1.2 to 30% by weight, in particular 2.5 to 25% by weight, or 2.5 to 20% by weight, or 4.5 to 20% by weight, based on the total weight of ethylenically unsaturated monomers M.

[0045] In a subgroup (1.b) of group (1) of specific embodiments, the monomers M forming the copolymer CP are preferably essentially a) 50 to 99.4% by weight, specifically 65 to 98.8% by weight, more specifically 70 to 98.3% by weight, in particular 75 to 97.5% by weight, or 80 to 97.5% by weight, or 80 to 97.5% by weight, based on the total weight of the ethylenically unsaturated monomers M, of acrylamide, b) 0.5 to 49.9% by weight, in particular 1 to 34.8% by weight, more in particular 1.5 to 29.8% by weight, in particular 2 to 24.5% by weight, or 2 to 19.5% by weight, or 4 to 19.5% by weight, of at least one monomer Mb.1, preferably selected from 2-acrylamido-2-methylpropanesulfonic acid and salts thereof, based on the total weight of the ethylenically unsaturated monomers M, c) 0.1 to 15% by weight, in particular 0.2 to 8% by weight, in particular 0.5 to 5% by weight, of at least one monomer Mc of group a.1 or a.2 of the embodiments, The total amount of monomers Ma and Mb is at least 85% by weight, particularly at least 92% by weight, in particular at least 95% by weight, based on the total weight of ethylenically unsaturated monomers M, and the total amount of monomers Mb and Mc is 0.6 to 50% by weight, particularly 1.2 to 35% by weight, or 1.2 to 30% by weight, in particular 2.5 to 25% by weight, or 2.5 to 20% by weight, or 4.5 to 20% by weight, based on the total weight of ethylenically unsaturated monomers M.

[0046] According to another embodiment group (2), the monomers M forming the copolymer CP comprise at least one monomer Ma and at least one monomer Mc in the above-mentioned amounts, the monomer Mc being preferably selected from the monomers of formula (III) and in particular at least one monomer Mc of the embodiments group a.1 or a.2.

[0047] In a subgroup (2a) of group (2) of embodiments, the monomers M forming the copolymer CP consist essentially of the monomers Ma and Mc. In this subgroup (2a) of embodiments, the monomers M preferably consist essentially of a) from 95 to 99.5% by weight, in particular from 92 to 99.5% by weight, in particular from 95 to 99.5% by weight or from 95 to 99.3% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Ma, preferably selected from acrylamide, methacrylamide and mixtures thereof, and b) 0.5 to 15% by weight, in particular 0.5 to 8% by weight, in particular 0.5 to 5% by weight or 0.7 to 5% by weight, based on the total weight of ethylenically unsaturated monomers M, of at least one monomer Mc preferably selected from monomers of formula (III) and in particular from at least one monomer Mc of group a.1 or a.2 of the embodiments.

[0048] In subgroup (2.a) of this specific embodiment, the monomers M forming the copolymer CP preferably consist essentially of a) 85 to 99.5% by weight, in particular 92 to 99.5% by weight, in particular 95 to 99.5% by weight or 95 to 99.3% by weight, of acrylamide, based on the total weight of the ethylenically unsaturated monomers M, and b) from 0.5 to 15% by weight, in particular from 0.5 to 8% by weight, in particular from 0.5 to 5% by weight or from 0.7 to 5% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Mc, preferably selected from the monomers of the embodiment groups a.1 or a.2.

[0049] According to a further group (3) of embodiments, the monomers M forming the copolymer CP comprise at least one monomer Ma and at least one monomer Mb.2 in the amounts indicated above, the monomers Mb being preferably selected from the monomers of formula (II) and in particular the salts of N-(3-trimethylammoniumpropyl)acrylamide, in particular the chlorides, sulfates or methosulfates thereof. In a further group (3) of this embodiment, the monomers M may comprise the monomers Mc in the amounts indicated above.

[0050] In subgroup (3a) of group (3) of embodiments, monomer M preferably consists essentially of: a) 65 to 99.5% by weight, in particular 82 to 99% by weight and in particular 90 to 98.5% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Ma, preferably selected from acrylamide, methacrylamide and mixtures thereof, b) 0.2 to 20% by weight, in particular 0.5 to 10% by weight and in particular 1 to 5% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Mb.2, preferably selected from the monomers of the formula (II) and their salts, c) 0.1 to 15% by weight, in particular 0.2 to 8% by weight and in particular 0.5 to 5% by weight, of at least one monomer Mc, in particular of the monomer Mc of formula (III) and in particular of at least one monomer Mc of group a.1 or a.2 of the embodiments, The total amount of monomers Ma and Mb is at least 85% by weight, specifically at least 92% by weight, in particular at least 95% by weight, based on the total weight of ethylenically unsaturated monomers M, and the total amount of monomers Mb and Mc is 0.5 to 35% by weight, specifically 1 to 18% by weight, in particular 1.5 to 10% by weight, based on the total weight of ethylenically unsaturated monomers M.

[0051] In a subgroup (3.a) of group (3) of specific embodiments, the monomers M forming the copolymer CP are preferably essentially a) 65 to 99.5% by weight, in particular 82 to 99% by weight, in particular 90 to 98.5% by weight, of acrylamide, based on the total weight of ethylenically unsaturated monomers M, b) 0.2 to 20% by weight, in particular 0.5 to 10% by weight and in particular 1 to 5% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Mb.2, preferably chosen from N-(3-trimethylammoniumpropyl)acrylamide salts, in particular the chloride, sulfate or methosulfate thereof, c) 0.1 to 15% by weight, in particular 0.2 to 8% by weight, in particular 0.5 to 5% by weight, of at least one monomer Mc of group a.1 or a.2 of the embodiments, The total amount of monomers Ma and Mb is at least 85% by weight, specifically at least 92% by weight, in particular at least 95% by weight, based on the total weight of ethylenically unsaturated monomers M, and the total amount of monomers Mb and Mc is 0.5 to 35% by weight, specifically 1 to 18% by weight, in particular 1.5 to 10% by weight, based on the total weight of ethylenically unsaturated monomers M.

[0052] In subgroup (3b) of group (3) of embodiments, monomer M preferably consists essentially of: d) 95 to 99.5% by weight, in particular 95 to 99% by weight and in particular 95 to 98.5% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Ma, preferably selected from acrylamide, methacrylamide and mixtures thereof, e) 0.5 to 5% by weight, in particular 1 to 5% by weight and in particular 1.5 to 5% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Mb.2, preferably selected from the monomers of the formula (II) and salts thereof.

[0053] With regard to groups of embodiments (1), (2) and (3) and to the specific subgroups (1.a), (1.b), (2a), (3a) and (3b) of groups of embodiments (1), (2) and (3), the term "consisting essentially of" means that the total amount of monomers Ma, and Mb.1 or Mb.2, and Mc, if present, is at least 99% by weight, in particular at least 99.5% by weight or at least 99.9% by weight, in particular 100% by weight, based on the total weight of the ethylenically unsaturated monomers M forming the copolymer CP.

[0054] The copolymer CP preferably has a weight average molecular weight Mw of at least 100,000 g / mol, specifically at least 250,000 g / mol, more preferably at least 500,000, even more preferably at least 750,000 g / mol, especially at least 1,000,000 g / mol, as determined by gel permeation chromatography (GPC), also known as size exclusion chromatography (SEC). The weight average molecular weight may be very high, for example up to 30,000,000 g / mol, specifically up to 20,000,000 g / mol, as determined by GPC / SEC. GPC / SEC is typically carried out using a series of suitable columns and water at pH 7 as eluent, and using polyacrylic acid sodium salt or poly(methy acrylic acid) sodium salt of known molecular weight as standard.

[0055] The molecular weight can also be estimated from the intrinsic viscosity [η] of the copolymer CP by using the following Mark-Howink equation (1): [η]=6.98x10 -4 M w 0.91 (1) In the formula, M w is the weight average molecular weight of the copolymer CP, and [η] is cm 3 The intrinsic viscosity [η] of the copolymer CP in its sodium salt form is generally at least 50 cm, measured at 30° C. in a 0.5 M aqueous solution of sodium chloride. 3 / g, specifically at least 100 cm 3 / g, preferably at least 150, in particular at least 200 cm 3 / g.

[0056] For this purpose, the intrinsic viscosity [η] of the copolymer CP can be calculated, for example, by the specific viscosity η of an aqueous solution of the copolymer CP in a 0.5 molar aqueous solution of the copolymer CP at various concentrations, for example, in the range of 0.05-0.5 mg / ml, according to the method described by H. Zhang and Y. Feng, J. Appl. Polym. Sci. 2021, 138: e50850 (DOI: 10.1002 / app.50850). sp and extrapolating the value to infinite dilution using a capillary viscometer.

[0057] The copolymer CP is known as a flocculant or thickener, for example from WO 2014 / 095608, WO 2014 / 095621 and WO 2015 / 086468, or can be prepared by analogous methods described therein. Similarly, the monomer Mc is known from WO 2014 / 095608, WO 2014 / 095621 and WO 2015 / 086468, or can be prepared by analogous methods described therein.

[0058] Frequently, the copolymers CP described herein are obtainable by free-radical aqueous copolymerization of the monomers M.

[0059] By the term free radical polymerization is understood the polymerization of the ethylenically unsaturated monomers M is carried out in the presence of a polymerization initiator which forms radicals under the polymerization conditions either by thermal decomposition or by redox reactions. By solution polymerization is meant that a solution of the monomers in a solvent capable of also dissolving the copolymer is polymerized by free radical polymerization, i.e. in the presence of a polymerization initiator.

[0060] Suitable solvents for carrying out solution polymerization include water and polar organic solvents, as well as mixtures of polar organic solvents and water. Suitable polar organic solvents are those that are at least partially miscible with water, preferably at least to the extent of 100 g / L at 20° C. and ambient pressure. Suitable organic solvents include, but are not limited to, C1-C4 alkanols, such as methanol, ethanol, propanol, isopropanol (=2-propanol), n-butanol, sec-butanol (=2-butanol), or isobutanol, dimethyl sulfoxide, ethyl acetate. Preferred organic solvents are selected from C1-C4 alkanols, such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, or isobutanol, preferably isopropanol or sec-butanol. Specifically, the solvent for carrying out solution polymerization is selected from water and mixtures of water and one or more C1-C4 alkanols. In particular, the solvent used for the free radical polymerization of the monomers forming the copolymer CP contains at least 50% by volume, in particular at least 70% by volume, of water, based on the total amount of solvent. In particular, water is the only solvent.

[0061] The polymerization of the monomers to form the copolymer or its precursors is preferably a free radical copolymerization and is therefore triggered by free radical polymerization initiators (free radical initiators). These can in principle be peroxides or azo compounds. Of course, redox initiator systems can also be used.

[0062] Suitable peroxides are in principle inorganic peroxides, such as hydrogen peroxide, or peroxodisulfates, for example the mono- or di-alkali metal or ammonium salts of peroxodisulfate, for example the mono- and di-sodium, mono- and di-potassium or mono- and di-ammonium salts, or organic peroxides, such as peroxyacids and esters of peroxyacids, for example diisopropyl peroxydicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-butyl peroxydicarbon ... -Amyl perpivalate, bis(2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl) peroxide, disuccinoyl peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl per-2-ethylhexanoate, t-butyl-2-ethylhexanoate, bis(4-chlorobenzoyl) peroxide, t-butyl perisobutyrate, t- butyl permaleate, 1,1-bis(t-butylperoxy)cyclohexane, t-butylperoxyisopropyl carbonate, t-butylperisononanoate, t-butylperacetate, t-amylperbenzoate, 3-(t-butylperoxy)-3-phenylphthalide, or t-butylperbenzoate; alkyl and cycloalkyl peroxides, such as 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,2-bis(t-butylperoxy)butane (dimethylperoxy)-2,3-dimethylphenylphthalide, 2,4-bis(t-butylperoxy)butane (dimethylperoxy)-1,2-dimethylphenylphthalide, 2,5-bis(t-butylperoxy)butane (dimethylperoxy)-1,2-dimethylphenylphthalide, 2,6-bis(t-butylperoxy)butane (dimethylperoxy)-1,2-dimethylphenylphthalide, 2,7-bis(t-butylperoxy)butane (dimethylperoxy)-1,2-dimethylphenylphthalide, 2,8-bis(t-butylperoxy)butane (dimethylperoxy)-1,2-dimethylphenylphthalide, 2,9 ... -t-butylperoxide), 2,2-bis-10-(t-butylperoxy)propane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di(t-amyl)peroxide, α,α'-bis(t-butylperoxyisopropyl)benzene, 3,5-bis(t-butylperoxy)-3,5-dimethyl-1,2-dioxolane, di(t-butyl)peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne, 3,3,6,6,9,9-hexamethyl-1,2,4,The peroxide may be 5-tetraoxacyclononane, p-menthane hydroperoxide, pinane hydroperoxide, an aromatic peroxide such as dicumyl peroxide, diisopropylbenzene, mono-α-hydroperoxide, or cumene hydroperoxide. A suitable peroxide may also be hydrogen peroxide.

[0063] Typical azo initiators are, for example, 4,4'-azobis-4-cyanovaleric acid (ACVA), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-methylpropionitrile) (AIBN), 2,2'-azobis(2-methylbutanenitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyanocyclohexane), 1,1'-azobis(N,N-dimethylformamide), 2, 2'-Azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(1-cyclohexyl) xancarbonitrile), 2,2'-azobis(isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl 2,2'-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 2,2'-azobis(N,N'-dimethyleneisobutyramidine), 2,2'-azobis(N, N'-dimethyleneisobutylamidine) hydrochloride, 2,2'-azobis(2-amidinopropane), 2,2'-azobis(2-amidinopropane) hydrochloride, 2,2'-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide), azobis(2-amidopropane) dihydrochloride, or 2,2'-azobis(2-methyl-N[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide).

[0064] Typical redox initiators are, for example, oxidizing agents, such as hydrogen peroxide, peroxodisulfates, or mixtures of the abovementioned peroxide compounds with reducing agents. Corresponding reducing agents which can be used are sulfur compounds in the lower oxidation state, such as ammonium sulfite and alkali metal sulfites, such as potassium sulfite and / or sodium sulfite, ammonium bisulfite and alkali metal hydrogen sulfites, such as potassium hydrogen sulfite and / or sodium hydrogen sulfite, ammonium metabisulfite and alkali metal metabisulfites, such as potassium metabisulfite and / or sodium metabisulfite, formaldehyde sulfoxylates, such as potassium formaldehyde sulfoxylate and / or sodium formaldehyde sulfoxylate, and the like. sulfoxylates, ammonium and alkali metal salts, in particular the potassium and / or sodium salts of aliphatic sulfinic acids, and alkali metal hydrogen sulfides, for example potassium hydrogen sulfide and / or sodium hydrogen sulfide, salts of polyvalent metals, in particular Co(II) salts, and Fe(II) salts, for example ferrous sulfate, ammonium ferrous sulfate, or ferrous phosphate, as well as dihydroxymaleic acid, benzoin, and / or ascorbic acid, and reducing sugars, for example sorbose, glucose, fructose, and / or dihydroxyacetone.

[0065] Preferably, the free radical polymerization initiator comprises an inorganic peroxide, specifically a peroxodisulfate, such as a mono- or di-alkali metal or ammonium salt of peroxodisulfate. Specifically, the free radical polymerization initiator is a redox initiator that comprises an inorganic peroxide, specifically a peroxodisulfate, such as a mono- or di-alkali metal or ammonium salt of peroxodisulfate, as an oxidizing agent. In these redox initiators, the reducing agent is preferably selected from the group of sulfur compounds in a low oxidation state, such as alkali metal sulfites, such as potassium sulfite and / or sodium sulfite, alkali metal hydrogen sulfites, such as potassium hydrogen sulfite and / or sodium hydrogen sulfite, alkali metal metabisulfites, such as potassium metabisulfite and / or sodium metabisulfite, formaldehyde sulfoxylates, such as potassium formaldehyde sulfoxylate and / or sodium formaldehyde sulfoxylate, alkali metal salts, particularly potassium and / or sodium salts of aliphatic sulfinic acids, and alkali metal hydrogen sulfides, such as potassium hydrogen sulfide and / or sodium hydrogen sulfide. In these redox initiators, the molar amount of the reducing agent will exceed the molar amount of the oxidizing agent. In particular, the molar ratio of reducing agent to oxidizing agent is in the range of 1.5:1 to 100:1.

[0066] The molecular weight of the copolymer can be adjusted by selecting the appropriate relative amount of free radical polymerization initiator to the monomers to be copolymerized. As a rule of thumb, increasing the relative amount of free radical polymerization initiator decreases the molecular weight, and decreasing the relative amount of free radical polymerization initiator increases the molecular weight. If the free radical polymerization initiator is selected from redox initiators, increasing the molar ratio of reducing agent to oxidizing agent also decreases the molecular weight, and vice versa. Typically, the amount of free radical polymerization initiator is in the range of 0.02 to 20 mmol, specifically 0.5 to 5.0 mmol, per mole of monomer to be copolymerized. In the case of redox initiators, these ranges refer to the oxidizing agent.

[0067] The polymerization of the monomers to form the copolymer CP or its precursors is generally carried out at a temperature ranging from 25 to 150° C. The temperatures employed are generally in the range from 40 to 120° C., in particular in the range from 50 to 110° C. and in particular in the range from 60 to 90° C.

[0068] The polymerization of the monomers to form the copolymer or its precursors can be carried out at less than, equal to or greater than 1 atm (atmospheric pressure), so that the polymerization temperature can be greater than 100° C. and can be up to 150° C. The polymerization of the monomers is usually carried out at ambient pressure, but can also be carried out under elevated pressure. In this case, the pressure can have values ​​of 1.1 to 15 bar (absolute) or even higher values. In general, the free radical polymerization of the present invention is carried out at ambient pressure (about 1 atm) with the exclusion of oxygen, for example under an inert gas atmosphere, for example nitrogen or argon.

[0069] The polymerization of the monomers to form the copolymer or its precursors can be carried out, for example, by a batch or semi-batch procedure, or a continuous procedure. In the batch procedure, the monomers to be polymerized and optionally the solvent used in the polymerization procedure are charged to a reactor, and a major part or the entire amount of the polymerization initiator is added to the reactor during the polymerization reaction. In the semi-batch procedure, at least a part of the total amount of the free radical polymerization initiator and the solvent, and optionally the minor part of the monomers, are charged to the reactor, and a major part of the monomers to be polymerized is added to the reactor during the polymerization reaction. In the continuous process, the monomers, the polymerization initiator, and the solvent are continuously added to the reactor, and the resulting copolymer is continuously discharged from the polymerization reactor. Preferably, the polymerization of the monomers to form the copolymer or its precursors is carried out by a semi-batch procedure. Specifically, at least 90% of the monomers to be polymerized are added to the reactor during the polymerization reaction.

[0070] Specifically, the copolymerization of monomer M is carried out as a gel polymerization in water as a coherent phase. The gel polymerization can be carried out as a free radical polymerization in water or an aqueous solvent as described for the solution polymerization. However, at the start of the gel polymerization, a higher monomer concentration is present, for example a monomer concentration in the range of 20-50 wt. %. Details of gel polymerization and suitable reactions are described in WO 2014 / 095608, WO 2014 / 095621 and WO 2015 / 086468.

[0071] The polymerization of the monomers to form the copolymer or its precursors may also include a step in which any remaining monomers are removed by physical means, for example by distillation, or by chemical means, i.e., forced radical polymerization, for example by using a second free radical polymerization initiator that is added to the polymerization reaction after at least 90% of the monomers to be polymerized have reacted. Preferably, the second free radical polymerization initiator is a hydroperoxide or a persulfate.

[0072] The copolymer CP is useful for improving the efficacy of herbicides, i.e. it improves or enhances the herbicidal activity of herbicidally active compounds. For this purpose, the copolymer CP is applied together with a herbicide, specifically via an aqueous spray solution. As mentioned above, the amount of the copolymer CP in the aqueous spray solution is preferably in the range of 5 to 500 ppm, specifically in the range of 10 to 300 ppm, more specifically in the range of 10 to 200 ppm, especially in the range of 10 to 100 ppm, based on the total weight of the aqueous spray solution. The amount of the herbicide in the aqueous spray solution varies depending on its application rate, which is typically in the range of 10 g / ha to 2 kg / ha, specifically in the range of 20 to 1.2 kg / h, calculated as the active herbicide compound. Generally, the concentration of the herbicide in the aqueous spray solution is in the range of 0.01 to 1.5% by weight, calculated as the active herbicide compound.

[0073] The aqueous spray solution may have any pH value that is acceptable for agricultural purposes. Preferably, the aqueous spray solution has a pH within the range of pH 4 to pH 9, determined at 25°C.

[0074] Herbicidally active compounds suitable for the uses and methods of the present invention are from the herbicide classes of the Compendium of Pesticide Common Names (https: / / pesticidecompendium.bcpc.org / class_herbicides.html), namely: - Amide herbicides, including anilide herbicides, arylalanine herbicides, chloroacetanilide herbicides, sulfoanilide herbicides, sulfonamide herbicides, and thioamide herbicides; - aromatic acid herbicides, including benzoic acid herbicides, pyrimidinyloxybenzoic acid herbicides, pyrimidinylthiobenzoic acid herbicides, phthalic acid herbicides, and picolinic acid herbicides; - arylcyclohexanedione herbicides, - bezofuranly alkylsulfnate herbicides, - benzothiazole herbicides, - Carbamate herbicides, including carbanilate herbicides; - cyclohexene oxime herbicides, - cyclopropylisoxazur herbicides, - dicarboximide herbicides, - Dinitroaniline herbicides, - diphenyl ether herbicides (herbicides), including nitrophenyl ether herbicides; - thiocarbamate herbicides, - Imidazolinone herbicides, - imide herbicides, - nitrile herbicides, - Organophosphate herbicides, - oxadiazolone herbicides, - oxazole herbicides, - phenoxy herbicides, including phenoxyacetate herbicides, phenoxypropionate herbicides and phenoxybutyrate herbicides; - aryloxyphenoxypropionic acid herbicides, - phenylenediamine herbicides, - pyrazole herbicides, including benzoylpyrazole herbicides and phenylpyrazole herbicides; - pyridazine herbicides, - pyridazinone herbicides, - pyridine herbicides, - pyrimidinediamine herbicides, - pyrimidinyloxybenzylamine herbicides, - quaternary ammonium herbicides, - thiocarbamate herbicides, - thiocarbonate herbicides, - Thiourea herbicides, - Triazine herbicides, including chlorotriazine herbicides, fluoroalkyltriazine herbicides, methoxytriazine herbicides, and methylthiotriazine herbicides; - Triazinone herbicides, - Triazole herbicides, - Triazolone herbicides, - Triazolopyrimidine herbicides, - uracil and phenyluracil herbicides, - phenylurea herbicides, sulfonylurea herbicides (including the subclasses pyrimidinylsulfonylurea herbicides and triazinylsuflonylurea herbicides), urea herbicides, including thiadiazolylurea herbicides; - Unclassified herbicides such as azafenidin, bentazone, benzobicylcon, bicyclpyrone, chlorfenac, chlorfenprop, chlorflurazole, chloflurenol, cinmethylin, endothal, fluoromidine, fluridone, fluorochloridone, flurtamone, and fluthiaset.

[0075] Preferably, the herbicide is an organic herbicide compound selected from the following groups (i) to (viii) of herbicide compounds and combinations thereof: (i) herbicides of the group of glutamine synthetase inhibitors (class 10 of the HRAC (Herbicide Resistance Action Committee) classification), (ii) herbicides of the group of 5-enolpyruvylshikimate-3-phosphate synthase inhibitors (EPSP synthase inhibitors) (class 9 of the HRAC classification); (iii) herbicides from the group of auxin agonists (category 4 of the HRAC classification); (iv) herbicides from the group of protoporphyrinogen oxidase inhibitors (PPO inhibitors) (class 14 of the HRAC classification); (v) herbicides of the group of acetolactate synthase inhibitors (ALS inhibitors) (class 2 of the HRAC classification); (vi) herbicides of the group of photosystem II inhibitors (PS II inhibitors) (classes 5 and 6 of the HRAC classification); (vii) Herbicides of the group of hydroxyphenylpyruvate dioxygenase inhibitors (HPPD inhibitors) (class 27 of the HRAC classification); (viii) Herbicides from the group of acetyl-CoA carboxylase inhibitors (ACCase inhibitors) (class 1 of the HRAC classification).

[0076] Suitable herbicides of groups (i)-(viii) are known and may be selected by their mode of action as defined by the Herbicide Resistance Action Committee. Further details can be obtained from https: / / hracglobal.com / tools / classification-lookup / ?s=&mode=9796&letter=&number=#classificationLookup.

[0077] Examples of herbicides of group (i) are glufosinate and bialaphos and their salts.

[0078] An example of a herbicide in group (ii) is glyphosate and its salts.

[0079] Examples of herbicides of group (iii) are Benzoic acids, such as dicamba, TBA, and chloramben, and their salts and esters; - phenoxy herbicides, such as 2,4,5-T, 2,4-D, 2,4-DB, clomeprop, dichlorprop, fenoprop, MCPA, MCPB, and their salts and esters; - Pyridine carboxylic acids (also known as picolinic acid herbicides), such as aminopyralid, clopyralid, florpyrauxifen, halauxifen, picloram, fluroxypyr triclopyr, aminocyclopyrachlor, and their salts and esters; - phenylacetic acids such as chlorfenac and chlorfenprop; - Quinoline carboxylic acids, such as quinclorac and quinomelac, and their salts and esters.

[0080] Preferred herbicides of group (iii) are benzoic acid herbicides, particularly dicamba and its salts, phenoxy herbicides, particularly 2,4-D and its salts, and quinolone carboxylic acids, particularly quinclorac and its salts.

[0081] Examples of herbicides of group (iv) are azafenidin, butafenacil, carfentrazone, carfentrazone-ethyl, cinidon-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluthiacet, fluthiacet-methyl, oxadiargyl, oxadiazon, pentoxazone, profluazolesaflufenacil, sulfentrazone, thidiadimine, thiaphenacyl, trifludimoxazin, and ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31-6; S-3100), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinane-2,4-dione (CAS 451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione (CAS 1300118-96-0), 1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione (CAS 1304113-05-0), 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione (CAS 212754-02-4), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-acetic acid methyl ester (CAS 2158274-96-3), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]acetic acid ethyl ester (CAS 2158274-50-9), 2-[[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetic acid methyl ester (CAS 2271389-22-9), 2-[[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetic acid ethyl ester (CAS 2230679-62-4), 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-acetic acid methyl ester (CAS 2158275-73-9), 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]acetic acid ethyl ester (CAS 2158274-56-5), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-N-(methylsulfonyl)-acetamide (CAS 2158274-53-2), and 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-N-(methylsulfonyl)-acetamide (CAS 2158276-22-1).

[0082] Among the herbicides of the group of PPO inhibitors, the following group of compounds is preferred: flumioxazin, carfentrazone, sulfentrazone, butafenacil, acifluorfen, fomesafen, lactofen, oxyfluorfen, saflufenacil and trifludimoxazine, as well as their agriculturally acceptable salts and esters, such as, in particular, fomesafen-sodium, acifluorfen-sodium, acifluorfen-methyl, carfentrazone-ethyl. Particularly preferred are saflufenacil, fomesafen or its salts, such as fomesafen-sodium, and flumioxazin.

[0083] Examples of herbicides of group (v) are triazolopyrimidine herbicides, such as cloransulam, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam and pyroxsulam, and their salts and esters, such as cloransulam-methyl; sulfonylamino-carbonyl-triazolinone herbicides, also known as sulfonanilides, such as flucarbazone, propoxycarbazone, thiencarbazone, and triafamone, and their salts and esters, such as flucarbazone-sodium, propoxycarbazone-sodium, and thiencarbazone-methyl; - pyrimidinyl(thio)benzoate herbicides, such as bispyribac, pyribenzoxim, pyriftalid, pyrimisulfan, pyrithiobac, pyriminobac, their salts and esters, such as bispyribac-sodium, pyrithiobac-sodium and pyriminobac-methyl, as well as 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid-1-methylethyl ester (CAS 420138-41-6), 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid propyl ester (CAS 420138-40-5) and N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine (CAS 420138-01-8); sulfonylurea herbicides, such as amidosulfuron, azimsulfuron, bensulfuron, chlorimuron, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, iofensulfuron, mesosulfuron, metazosulfuron, metsulfuron, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, propyrisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfuron, Phosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, and tritosulfuron, and their salts and esters, such as bensulfuron-methyl, chlorimuron-ethyl, ethametsulfuron-methyl, flupyrsulfuron-methyl-sodium, halosulfuron-methyl, iodosulfuron-methyl-sodium, iofensulfuron-sodium, metsulfuron-methyl, primisulfuron-methyl, pyrazosulfuron-ethyl, sulfometuron-methyl, thifensulfuron-methyl, tribenuron-methyl, and triflusulfuron-methyl; - Imidazolinone herbicides, such as imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, and imazethapyr, and their salts and esters.

[0084] Preferred herbicides of group (v) are triazolopyrimidine herbicides, in particular cloransulam, and their salts and esters, for example cloransulam-methyl; imidazolinone herbicides, in particular imazamox, imazapic, imazapyr and imazethapyr, and their salts and esters; - sulfonylurea herbicides, in particular chlorimuron and its esters, such as chlorimuron-ethyl.

[0085] Examples of herbicides of group (vi) are anilides, such as propanil, pentanocryl or chloranocryl (dicryl); aryl urea herbicides, such as chlorbromuron, chlorotoluron, chloroxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, methobenzuron, metobromuron, methoxuron, monolinuron, nebulon, siduron, tetrafluron, tebuthiuron, thidiazuron, and their salts and esters (preferred aryl urea herbicides are chlortoluron, diuron, linuron, isoproturon, and tebuthiuron); - triazine(di)one herbicides (i.e. triazinone and triazinedione herbicides), such as ametridione, amivudine, ethiozinone, hexazinone, isomethiozine, metamitron, metribuzin, trifludimoxazine, and their salts and esters (preferred triazine(di)one herbicides include hexazinone, metamitron, and metribuzin, in particular metribuzin); triazine herbicides, such as ametryn, atrazine, adiprothrin, chlorazine, cyanatryn, cyanazine, cyprazine, desmetryn, dimethamethryn, eglinazine, ipazine, mesoprazine, metoprothrin, prometryn, procyazine, proglinadine, prometon, propazine, sebutylazine, simazine, simetryn, terbumeton, terbuthryn, terbutryn, trietazine, and their salts and esters, such as eglinadine-ethyl and proglinadine-ethyl (preferred triazine herbicides include ametryn, atrazine, terbuthryn, and simazine, in particular atrazine); pyridazinone herbicides, such as brompyrazone, chloridazon, dimidazon, methoflurazone, norflurazone, oxapyrazone, pidanone, and their salts and esters (the preferred pyridazinone herbicide is chloridazon); phenylcarbamate herbicides, such as desmedipham, carbutilate, phenisopham, phenmedipham, and their salts and esters, such as phenmedipham-ethyl; nitrile herbicides, such as bromobornyl, bromofenoxime, bromoxynil, chloroxynil, dichlobenil, iodobornyl and ioxynil, and in particular in the case of bromoxynil, chloroxynil and ioxynil, their salts and esters (the preferred nitrile herbicide is bromoxynil); - benzothiadiazinone herbicides, such as bentazone and its salts, in particular its alkali metal salts, such as bentazone-sodium; - uracil herbicides, such as bromacil, flupropacil, isocyl, lenacil, terbacil, and salts of bromacil, particularly the alkali metal salts thereof, such as bromacil-lithium and bromacil-sodium.

[0086] Preferred herbicides of group (vi) are - aryl urea herbicides, in particular chlortoluron, diuron, linuron, isoproturon, and tebuthiuron (especially diuron is preferred); - triazine herbicides, in particular ametryn, atrazine, tertbutylazine, and simazine (atrazine is particularly preferred); - Anilides, specifically propanil, Bentazone and its salts, in particular its alkali metal salts, such as bentazone-sodium.

[0087] Examples of herbicides of group (vii) are - cyclopropylisoxazole herbicides, for example isoxachlorthor and isoxaflutole, - benzoylcyclohexanedione herbicides, such as fenquinotrione, ketospiradox, mesotrione, sulcotrione, tefuryltrione and tembotrione; - benzoylpyrazole herbicides, such as benzofenap, pyrasulfotole, pyrazolinate, pyrazoxyfen, tolpyralate, and topramezone; - and unclassified herbicides, such as benzobicyclon and bicyclopyrone.

[0088] Preferred herbicides of group (vii) are - benzoylcyclohexanedione herbicides, specifically mesotrione and tembotrione, - Benzoylpyrazole herbicides, specifically topramezone.

[0089] Examples of herbicides of group (viii) are Aryloxyphenoxy-propionate herbicides, such as chlorazifop, clodinafop, clofop, cyhalofop, diclofop, fenoxaprop, fentiaprop, fluazifop, haloxyfop, isoxapyrifop, kuicaoxi, metamifop, propaquizafop, quizalofop, trifop, and their enantiomers, salts and esters, such as fenoxaprop-P, fluazifop-P, haloxyfop-P, quizalofop-P, haloxyfop-sodium; um, cloradifop-propargyl, clodinafop-propargyl, clofop-isobutyl, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentiaprop-ethyl, fluazifop-methyl, fluazifop-butyl, fluazifop-P-butyl, haloxyfop-ethotyl, haloxyfop-methyl, haloxyfop-P-ethotyl, haloxyfop-P-methyl, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P-ethyl, and quizalofop-P-tefuryl, Cyclohexanedione herbicides, such as alloxydim, butroxydim, clethodim, cloproxydim, cycloxydim, propoxydim, sethoxydim, tepraloxydim, tralkoxydim and their salts, such as alloxydim-sodium, - Phenylpyrazoline herbicides, for example pinoxaden.

[0090] Preferred herbicides of group (viii) are clethodim, quizalofop, and pinoxaden.

[0091] Suitable salts of the above organic herbicidal compounds, in particular those having a carboxyl group, are salts of cations that have no adverse effect on the action of the herbicidally active compounds ("agriculturally acceptable"). Preferred cations are ions of alkali metals, preferably lithium, sodium and potassium ions, ions of alkaline earth metals, preferably calcium and magnesium ions, and ions of transition metals, preferably manganese, copper, zinc and iron ions, as well as ammonium and substituted ammoniums in which 1 to 4 hydrogen atoms are replaced by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl (hereinafter also referred to as organic ammonium), preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium. , tetraethylammonium, tetrabutylammonium, pentylammonium, hexylammonium, heptylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)eth-1-ylammonium, (diglycolamine salt), di(2-hydroxyeth-1-yl)ammonium (diolamine salt), tris((2-hydroxyeth-1-yl)ammonium (trolamine salt), tris(3-propanol)amonium, benzyltrimethylammonium, benzyltriethylammonium, further phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium such as trimethylsulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.

[0092] In the methods and uses of the present invention, the organic herbicidal compounds having a carboxyl group may be in the form of their derivatives, for example as amides, for example as mono- or di-C1-C6 alkylamides or arylamides, esters, for example as allyl esters, propargyl esters, C1-C6 alkyl ... 10 As alkyl esters, or alkoxyalkyl esters, and also as thioesters, e.g. C1-C 10 They may also be present as alkylthioesters. Preferred mono- and di-C1-C6-alkylamides are methylamides and dimethylamides. Preferred arylamides are, for example, anilidene and 2-chloroanilide. Preferred alkyl esters are, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1-methylhexyl) or isooctyl (2-ethylhexyl) esters. Preferred C1-C4-alkoxy-C1-C4-alkyl esters are linear or branched C1-C4-alkoxyethyl esters, for example the methoxyethyl, ethoxyethyl or butoxyethyl esters. Linear or branched C1-C 10 An example of an alkyl thioester is the ethyl thioester. Preferred derivatives are the esters.

[0093] Specifically, the herbicide compound for the uses, methods, and aqueous compositions of the present invention comprises at least one organic herbicide compound selected from the group consisting of glufosinate, bialaphos, glyphosate, dicamba, chloramben, 2,4-D, endothal, mecoprop, picloram, triclopyr, fluroxypyr, 2,4,5-T, MCPA, MCPB, dichlorprop, dichlorprop-P, imazamox, imazapyr, imazapic, imazethapyr, imazaquin, chloransulam, chlorimuron, acifluorfen, saflufenacil, fomesafen, atrazine, propanil, bentazon, diuron, quizalofop, clethodim, pinoxaden, topramezone, mesotrione, salts thereof, esters thereof, and combinations thereof.

[0094] In particular, the herbicide compound for the uses, methods, and aqueous compositions of the present invention comprises at least one organic herbicide compound selected from the group consisting of glufosinate, glyphosate, and dicamba, salts thereof, esters thereof, and combinations thereof, optionally in combination with at least one of the above herbicide compounds different therefrom.

[0095] In a particular group of embodiments, the herbicide comprises an organic herbicide compound having at least one carboxyl group or its salt. Suitable organic herbicide compounds having at least one carboxyl group include glufosinate, glyphosate, bialaphos, dicamba, acifluorfen, chloramben, 2,4-D, endothal, mecoprop, picloram, 2,4,5-T, benzac, MCPA, MCPB, dichlorprop, dichlorprop-P, dalapon, triclopyr, fluoroxypyr, imazamox, imazapyr, imazapic, imazethapyr, imazaquin, fomesafen, acifluorfen, and combinations thereof. The above compounds can be used in the form of their carboxylic acid or their salt, or in the form of their derivatives, i.e., as their amides or esters. Preferably, the herbicide having a carboxyl group is present in the form of its salt.

[0096] According to group (4) of particular preferred embodiments, the herbicide comprises glufosinate or a salt thereof.

[0097] Glufosinate (CAS Registry Number 51276-47-2; IUPAC name: (2RS)-2-amino-4-[hydroxy(methyl)phosphinoyl]butyric acid, or 4-[hydroxy(methyl)phosphinoyl]-DL-homoalanine, or DL-4-[hydroxyl(methyl)phosphinoyl]-DL-homoalaninate) and its agriculturally acceptable salts, such as glufosinate-sodium, glufosinate-potassium, and in particular glufosinate-ammonium (IUPAC name: ammonium (2RS)-2-amino-4-(methylphosphinate)butyrate, CAS Registry Number 77182-82-2), are known. US Patent 4,168,963 describes phosphorus-containing compounds having herbicidal activity, in particular phosphinothricin (2-amino-4-[hydroxy(methyl)phosphinoyl]butanoic acid; common name: glufosinate) and its salts have become commercially important in the field of agrochemistry (agricultural chemistry). For example, glufosinate and its salts, such as glufosinate ammonium and its herbicidal activity are described, for example, by F. Schwerdtle et al. Z. Pflanzenkr. Pflanzenschutz, 1981, Sonderheft IX, pp. 431-440. Glufosinate and its salts as racemates are commercially available under the trade names Basta™ and Liberty™. Glufosinate is represented by the following structure (IV): [ka]

[0098] The compound of formula (IV) is a racemate. Glufosinate is a racemate of two enantiomers, only one of which shows sufficient herbicidal activity (see, for example, U.S. Pat. No. 4,265,654 and JP92448 / 83). Although various methods are known for preparing L-glufosinate (and corresponding salts), the mixtures known in the art do not mention stereochemistry, which means that racemates exist (e.g., WO2003024221, WO2011104213, WO2016113334, WO2009141367).

[0099] In one embodiment, the herbicide composition comprises a racemic mixture of glufosinate described above, the glufosinate comprising about 50% by weight of the L-enantiomer and about 50% by weight of the D-enantiomer. In another embodiment, the herbicide composition comprises glufosinate, at least 70% by weight of the glufosinate being L-glufosinate or a salt thereof.

[0100] L-Glufosinate, which has the IUPAC name (2S)-2-amino-4-[hydroxy(methyl)phosphinoyl]butyric acid (CAS Registry Number 35597-44-5) and is also called glufosinate-P, can be obtained commercially or prepared as described, for example, in WO 2006 / 104120, U.S. Pat. No. 5,530,142, EP 0248357A2, EP 0249188A2, EP 0344683A2, EP 0367145A2, EP 0477902A2, EP 0127429, and J. Chem. Soc. Perkin Trans. 1, 1992, 1525-1529. Preferably, the salt of glufosinate or the salt of (L)-glufosinate is sodium, potassium or ammonium (NH4 +) salts, in particular for L-glufosinate, glufosinate-P-ammonium (IUPAC name: ammonium (2S)-2-amino-4-(methylphosphinate)butyrate; CAS Registry Number 73777-50-1), glufosinate-P-sodium (IUPAC name: sodium (2S)-2-amino-4-(methylphosphinate)butyrate; CAS Registry Number 70033-13-5) and glufosinate-P-potassium (IUPAC name: potassium (2S)-2-amino-4-(methylphosphinate)butyrate). Thus, the mixture may contain (L)-glufosinate ammonium or (L)-glufosinate sodium or (L)-glufosinate potassium as the (L)-glufosinate salt, and (L)-glufosinate as the free acid, preferably (L)-glufosinate. (L)-Glufosinate ammonium, i.e., ammonium of glufosinate (NH + Herbicidal compositions containing the Glufosinate salt are particularly preferred. The term "glufosinate" as used herein typically comprises, in one embodiment of the invention, about 50% by weight of the L-enantiomer and about 50% by weight of the D-enantiomer, and in another embodiment of the invention, more than 70% by weight of the L-enantiomer, preferably more than 80% by weight of the L-enantiomer, more preferably more than 90% by weight of the L-enantiomer, and most preferably more than 95% by weight of the L-enantiomer, which can be prepared as described above.

[0101] According to another particular embodiment group (5), the herbicide comprises glyphosate or a salt thereof as the herbicidally active compound.

[0102] Suitable salts of glyphosate are, for example, glyphosate-ammonium, glyphosate-diammonium, glyphosate-dimethylammonium, glyphosate-isopropylammonium, glyphosate-potassium, glyphosate-sodium, glyphosate-trimesium, as well as the ethanolamine and diethanolamine salts, preferably glyphosate-diammonium, glyphosate-isopropylammonium, and glyphosate-trimesium (sulfosate).

[0103] According to another particular embodiment of group (6), the herbicide comprises a herbicide of group (iii), which is specifically selected from the group consisting of benzoic acid herbicides, specifically dicamba and its salts, phenoxy herbicides, specifically 2,4-D and its salts, and quinolone carboxylic acids, specifically quinclorac and its salts.

[0104] According to group (6a) of particular preferred embodiments, the herbicide comprises dicamba or a salt thereof. Suitable salts of dicamba are dicamba-sodium, dicamba-potassium, dicamba-methylammonium, dicamba-dimethylammonium, dicamba-isopropylammonium, dicamba-diglycolamine, dicamba-olamine, dicamba-diolamine, dicamba-trolamine, dicamba-N,N-bis-(3-aminopropyl)methylamine, and dicamba-diethylenetriamine. Examples of suitable esters are dicamba-methyl and dicamba-butotyl.

[0105] According to another particular embodiment group (7), the herbicide comprises an herbicide from the group of PPO inhibitors, specifically selected from the group consisting of flumioxazin, carfentrazone, sulfentrazone, butafenacil, acifluorfen, fomesafen, lactofen, oxyfluorfen, saflufenacil and trifludimoxazine, and their agriculturally acceptable salts and esters, such as specifically fomesafen-sodium, acifluorfen-sodium, acifluorfen-methyl, carfentrazone-ethyl. In group (7), particularly preferred is the group of PPO inhibitors selected from saflufenacil, fomesafen or a salt thereof, such as fomesafen sodium, and flumioxazin.

[0106] According to another particular embodiment group (8), the herbicide comprises an herbicide from the group of ALS inhibitors, which in particular are triazolopyrimidine herbicides, in particular cloransulam, and their salts and esters, for example cloransulam-methyl; imidazolinone herbicides, in particular imazamox, imazapic, imazapyr and imazethapyr, and their salts and esters; sulfonylurea herbicides, in particular selected from the group consisting of chlorimuron and its esters, such as chlorimuron-ethyl.

[0107] According to another particularly preferred embodiment group (8a), the herbicide comprises as herbicidally active compound an imidazolinone or a salt thereof, in particular an imidazolinone selected from the group consisting of imazapic, imazamox, imazapyr, imazaquin, imazethapyr, or a combination thereof, or a salt or a combination of salts thereof.

[0108] Suitable salts of imidazolinone herbicides are imazapic salts, imazamox salts, imazapyr salts, imazaquin salts, imazethapyr salts. Suitable salts of imazamox are, for example, imazamox-ammonium. Suitable salts of imazapic are, for example, imazapic-ammonium and imazapic-isopropylammonium. Suitable salts of imazapyr are, for example, imazapyr-ammonium and imazapyr-isopropylammonium. Suitable salts of imazaquin are, for example, imazaquin-ammonium. Suitable salts of imazethapyr are, for example, imazethapyr-ammonium and imazethapyr-isopropylammonium.

[0109] According to another particular embodiment group (9), the herbicide comprises the herbicide of the group of PSII inhibitors, which in particular are - aryl urea herbicides, in particular chlortoluron, diuron, linuron, isoproturon, and tebuthiuron (especially diuron is preferred); - triazine herbicides, in particular ametryn, atrazine, tertbutylazine, and simazine (atrazine is particularly preferred); - Anilides, specifically propanil, bentazone and its salts, in particular its alkali metal salts, for example bentazone-sodium.

[0110] In group (9) of specific embodiments, the herbicide comprises an herbicide compound selected from diuron, atrazine, propanil, and benazone, or salts thereof, such as sodium bentazone.

[0111] According to another particular embodiment group (10), the herbicide comprises the herbicide of the group of HPPD inhibitors, which in particular are - benzoylcyclohexanedione herbicides, specifically mesotrione and tembotrione, - benzoylpyrazole herbicides, in particular selected from the group consisting of topramezone;

[0112] According to another particular embodiment group (11), the herbicide comprises an herbicide from the group of HPPD inhibitors, which is in particular selected from the group consisting of clethodim, quizalofop and pinoxaden.

[0113] Generally, copolymer CP is included in the spray liquid together with a suitable herbicide active ingredient formulation.Generally, the formulation containing the herbicide active ingredient is a formulation that can be easily diluted with water.Suitable herbicide active ingredient formulations include, but are not limited to, water-soluble concentrates (SL or LS formulations), dispersible concentrates (DC formulations), emulsifiable concentrates (EC formulations), emulsions (EW, EO, or ES formulations), suspension concentrates (SC, OD, or FS formulations) that can be water-based or oil-based, microemulsions (ME formulations), microencapsulated formulations (CS formulations), wettable powders or wettable dusts (e.g. WP, SP, WS, DP, DS), wettable granules (e.g. WG, SG, GR, FG, GG, MG), etc. These and further composition types are defined in "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.

[0114] In addition to the herbicidal active ingredient, the formulation may contain one or more of the conventional formulation aids, including solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, antifreeze agents, defoamers, colorants, crystal growth inhibitors, tackifiers, and binders. Of course, these ingredients will be present in the aqueous spray solution. The concentration of the herbicidal active ingredient in the formulation may vary, typically within the range of 50-800 g per kg of formulation.

[0115] Suitable solvents and liquid carriers are water and organic solvents, such as medium to high boiling fractions of mineral oils, e.g., kerosene, diesel; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g., toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g., ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e.g., cyclohexanone; esters, e.g., lactate esters, carbonate esters, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonate esters; amines; amides, e.g., N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof.

[0116] Suitable solid carriers or fillers are mineral earths, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of plant origin, such as grain flour, bark flour, wood flour, nut shell flour, and mixtures thereof.

[0117] Suitable surfactants are surface active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes and mixtures thereof.Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids or adjuvants.Examples of surfactants are listed in McCutcheon's, Vol.1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

[0118] Suitable anionic surfactants are the alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and their mixtures.Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, ligninsulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.Examples of sulfates are sulfates of fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols or fatty acid esters.Examples of phosphates are phosphoric acid esters.Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.

[0119] Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids, or fatty acid esters, alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide, preferably ethylene oxide, may be used for the alkoxylation. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters, or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose, and glucose esters, or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol, or vinyl acetate.

[0120] Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are block polymers of the AB or ABA type, including blocks of polyethylene oxide and polypropylene oxide, or block polymers of the ABC type, including alkanol, polyethylene oxide, and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid, or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

[0121] Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives, such as alkylisothiazolinone and benzisothiazolinone. Suitable antifreeze agents are ethylene glycol, propylene glycol, urea, and glycerin. Suitable defoamers are silicones, long-chain alcohols, and salts of fatty acids. Suitable colorants (e.g. red, blue, or green) are low water-soluble pigments and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titanium oxide, ferricyanide salts) and organic colorants (e.g. alizarin, azo, and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0122] In addition to water, copolymer CP, and herbicide (including herbicidal active ingredient and optional formulation auxiliaries), the aqueous spray solution may contain one or more further agriculturally active ingredients. The further agriculturally active ingredients may be selected from fungicides, insecticides, nematicides, safeners, fertilizers, micronutrients, biopesticides, nitrification inhibitors, urease inhibitors, and / or growth regulators. The combination of a herbicide and a safener may be particularly useful. Suitable safeners include (quinoline-8-oxy)acetic acid, 1-phenyl-5-haloalkyl-1H-1,2,4-triazole-3-carboxylic acid, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acid, 4,5-dihydro-5,5-diaryl-3-isoxazole carboxylic acid, dichloroacetamide, α-oximinophenylacetonitrile, acetophenone oxime, 4,6-diha Examples of suitable aromatic hydrocarbon derivatives include 2-halo-2-phenylpyrimidine, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzoic acid amide, 1,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazole carboxylic acids, phosphorothiolates, and N-alkyl-O-phenylcarbamates, and agriculturally acceptable salts and agriculturally acceptable derivatives thereof, such as amides, esters, and thioesters, provided that they contain an acid group.

[0123] In a group (8) of preferred embodiments, the aqueous spray contains at least one inorganic compound, specifically at least one inorganic salt, or a salt of a carboxylic acid. The salt of the carboxylic acid itself does not have any notable herbicidal activity. Typical carboxylic acids are alkanoic acids having 1-6 carbon atoms. Preferably, the salt is water-soluble, i.e., its solubility in deionized water at 25°C is at least 10 g / L. Specifically, the salt is completely dissolved in the aqueous spray.

[0124] The aqueous compound is particularly a fertilizer-qualified salt, such as a potassium salt, a magnesium salt, or an ammonium salt, such as potassium chloride, potassium sulfate, magnesium sulfate, ammonium sulfate, or a combination thereof. The inorganic compound is particularly an ammonium salt, particularly ammonium sulfate or ammonium acetate.

[0125] In group (8) of preferred embodiments, the herbicide preferably comprises an organic herbicide compound having a carboxyl group or a salt thereof as described above, specifically glufosinate or a salt thereof, dicamba or a salt thereof, or glyphosate or a salt thereof.

[0126] Aqueous spray solutions containing the herbicide and copolymer CP are used to control undesirable vegetation on crop and non-crop areas.

[0127] Aqueous sprays allow for very efficient control of undesirable vegetation on non-crop areas and in crops. Very efficient control on non-crop areas is achieved at high application rates. Depending on the herbicidally active compounds, spray application allows for efficient control of broadleaf weeds and grass weeds in crops such as wheat, rice, corn, soybean and cotton without causing significant damage to crop plants. This effect is mainly observed at low application rates.

[0128] Sprays are generally applied to undesirable plants, mainly by spraying the leaves. Herein, application can be carried out by conventional spraying techniques using a spray volume of about 100-1,000 l / ha. Application of the spray can be carried out before, during and / or after, preferably during and / or after, emergence of the undesirable plants. When used for plant protection, the amount of glufosinate or its salts, not including formulation adjuvants, is 0.001-2 kg / ha, preferably 0.005-2 kg / ha, more preferably 0.05-0.9 kg / ha, specifically 0.1-0.75 kg / ha, depending on the type of effect desired.

[0129] Examples of suitable crops include: onion (Allium cepa), pineapple (Ananas comosus), peanut (Arachis hypogaea), asparagus (Asparagus officinalis), oats (Avena sativa), sugar beet (Beta vulgaris spec. altissima), Korean cabbage (Beta vulgaris spec. rapa), oilseed rape (Brassica napus var. napus), rutabaga (Brassica napus var. napobrassica), Brassica rapa var.silvestris, Brassica oleracea, Brassica nigra, Tea (Camellia sinensis), Safflower (Carthamus tinctorius), Pecan (Carya illinoinensis), Lemon (Citrus limon), Orange (Citrus sinensis), Coffee (Coffea arabica), (Coffee (Coffea canephora), Coffee (Coffea liberica), Cucumis sativus, Corngrass (Cynodon dactylon), Carrot (Daucus carota), Oil palm (Elaeis guineensis), Siberian strawberry (Fragaria vesca), Soybean (Glycine max), Cotton (Gossypium hirsutum), (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), sunflower (Helianthus annuus), rubber tree (Hevea brasiliensis), barley (Hordeum vulgare), hops (Humulus lupulus), sweet potato (Ipomoea batatas), Chinese walnut (Juglans regia), lentil (Lens culinaris), flax (Linum usitatissimum), tomato (Lycopersicon lycopersicum), apple species (Malus spec.), cassava (Manihot esculenta), alfalfa (Medicago sativa), banana species (Musa spec.), tobacco (Nicotiana tabacum) (N. rustica), olive (Olea europaea), rice (Oryza sativa), lima bean (Phaseolus lunatus), common bean (Phaseolus vulgaris), Norway spruce (Picea abies), pine species (Pinus spec.), pistachio (Pistacia vera), pea (Pisum sativum), wild cherry (Prunus avium), peach (Prunus persica), pear (Pyrus communis), apricot (Prunus armeniaca), sweet cherry (Prunus cerasus), almond (Prunus dulcis) and plum (Prunus domestica), redcurrant (Ribes sylvestre), castor bean (Ricinus communis), sugar cane (Saccharum officinarum), rye (Secale cereale), white mustard (Sinapis alba), potato (Solanum tuberosum), sorghum (Sorghum bicolor (s. vulgare)), cocoa (Theobroma cacao), red clover (Trifolium pratense), bread wheat (Triticum aestivum), triticale (Triticale), durum wheat (Triticum durum), broad beans (Vicia faba), grapes (Vitis vinifera), and corn (Zea mays).

[0130] The aqueous spray solution can also be used on crops that have been modified by mutagenesis or genetic engineering to impart new traits to the plant or to modify already existing traits, preferably resistance to glufosinate or a salt thereof.

[0131] As used herein, the term "crop" also includes (crop) plants that have been modified by mutagenesis or genetic engineering to provide the plant with new traits or to modify traits that are already present. Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis to generate mutations at specific loci in the plant genome. Targeted mutagenesis techniques often use oligonucleotides or proteins such as CRISPR / Cas, zinc finger nucleases, TALENs or meganucleases to achieve a targeted effect. Genetic engineering typically uses recombinant DNA techniques to create modifications of the plant genome that are not readily obtainable by breeding, mutagenesis or natural recombination under natural circumstances. Typically, one or more genes are integrated into the genome of the plant to add or improve a trait. These integrated genes are also referred to in the art as transgenes, and plants containing such transgenes are called transgenic plants. During the process of plant transformation, several transformation events usually occur, differing in the genomic loci at which the transgenes are integrated. Plants that contain a particular transgene at a particular genomic locus are usually described as containing a particular "event" and are referred to by the name of the particular event. Traits that have been introduced or modified in plants include herbicide tolerance, insect resistance, high yield, and tolerance to abiotic conditions such as drought, among others.

[0132] Herbicide resistance is produced not only by mutagenesis but also by genetic engineering. Plants that have been made tolerant to acetolactate synthase (ALS) inhibitor herbicides by conventional methods of mutagenesis and breeding include the plant cultivars marketed under the name Clearfield®. However, the majority of herbicide resistance traits are produced through the use of transgenes.

[0133] Herbicide tolerance has been engineered to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides such as bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides, and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors such as isoxaflutole and mesotrione.

[0134] Transgenes that have been used to confer herbicide resistance traits include: glyphosate tolerance: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621, and goxv247; glufosinate tolerance: pat and bar; 2,4-D tolerance: aad-1 and aad-12; dicamba tolerance: dmo; oxynil herbicide tolerance: bxn; sulfonylurea herbicide tolerance: zm-hra, csr1-2, gm-hra, S4-HrA, ALS inhibitor herbicide tolerance: csr1-2; HPPD inhibitor herbicide tolerance: hppdPF, W336, and avhppd-03.

[0135] Transgenic corn events containing herbicide resistance genes include, but are not limited to, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, VCO-φ1981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507, and TC6275.

[0136] Transgenic soybean events containing herbicide resistance genes include, but are not limited to, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHTφH2, W62, W98, FG72, and CV127.

[0137] Transgenic cotton events containing herbicide resistance genes include, but are not limited to, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3, and T304-40.

[0138] Transgenic canola events containing herbicide resistance genes include, but are not limited to, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.

[0139] Insect resistance has been created mainly by introducing bacterial genes for insecticidal proteins into plants. The most used transgenes are the toxin genes of Bacillus spec. such as cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a), vip3Aa20 and their synthetic variants. However, genes from plants have also been introduced into other plants, especially genes encoding protease inhibitors such as CpTI and pinII. In addition, there is also an approach that uses transgenes to produce double-stranded RNA in plants to target and downregulate insect genes. An example of such a transgene is dvsnf7.

[0140] Transgenic corn events containing genes for insecticidal proteins or double-stranded RNA include, but are not limited to, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418, and MZIR098.

[0141] Transgenic soybean events containing genes for insecticidal proteins are, for example, but not exclusive of, MON87701, MON87751, and DAS-81419.

[0142] Transgenic cotton events containing genes for insecticidal proteins include, but are not limited to, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119, and SGK321.

[0143] Increasing panicle biomass using the transgene athb17 present in corn event MON87403 or enhancing photosynthesis using the transgene bbx32 present in soybean event MON87712 results in increased yield.

[0144] The following transgenes have been used to create crops with improved oil content: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events that contain at least one of these genes are: 260-05, MON87705 and MON87769.

[0145] Tolerance to abiotic conditions, particularly drought tolerance, has been conferred by using the transgene cspB contained in the maize event MON87460 and by using the transgene Hahb-4 contained in the soybean event IND-φφ41φ-5.

[0146] The combination of traits is often achieved by combining genes contained in a transformation event or by combining different events during breeding. Preferred trait combinations are herbicide resistance to various groups of herbicides, insect resistance to various types of insects, in particular resistance to lepidopteran and coleopteran insects, herbicide resistance combined with one or more insect resistances, herbicide resistance combined with increased yield, and herbicide resistance combined with resistance to abiotic conditions.

[0147] Plants containing single or stacked traits, as well as the genes and events that confer these traits, are known in the art. For example, detailed information on the genes and respective events that are mutagenized or integrated can be obtained from the website of the organization "International Service for the Acquisition of Agri-biotech Applications (ISAAA)" (http: / / www.isaaa.org / gmapprovaldatabase) and the website of the organization "Center for Environmental Risk Assessment (CERA)" (http: / / cera-gmc.org / GMCropDatabase), as well as patent applications such as EP 3028573 and WO 2017 / 011288.

[0148] By applying the spray of the present invention to crops, effects specific to the crops containing specific genes or events can be obtained. These effects can include changes in growth behavior or changes in resistance to biotic or abiotic stress factors. Such effects can include, inter alia, increased yield, improved resistance or tolerance to insects, nematodes, fungi, bacteria, mycoplasma, viruses or viroid pathogens, and early growth, early or delayed maturation, low or high temperature tolerance, and changes in amino acid or fatty acid spectrum or content.

[0149] Further included are plants in which the content of ingredients has been adjusted or new ingredients have been incorporated using recombinant DNA techniques, particularly to improve the production of raw materials, such as potatoes with increased production of amylopectin (e.g. Amflora® potato, BASF SE, Germany).

[0150] Furthermore, it has been found that the herbicidal compositions according to the invention are also suitable for defoliating and / or drying parts of plants, for which crop plants such as cotton, potato, rapeseed, sunflower, soybean or broad bean, in particular cotton, are suitable. In this connection, herbicidal compositions for drying and / or defoliating plants, processes for preparing these compositions and methods for drying and / or defoliating plants using the herbicidal compositions according to the invention have been found.

[0151] The herbicidal compositions according to the invention as desiccants are particularly suitable for drying the above-ground parts of crop plants such as potato, rapeseed, sunflower and soybean as well as cereals, thereby allowing a complete mechanical harvest of these important crop plants.

[0152] Also of economic interest is the promotion of yield, which can be achieved by concentrating within a certain time the dehiscence or reduction of attachment to the tree of citrus fruits, olives and other pome, stone and nut species and varieties. The same mechanism, i.e. the promotion of the development of abscission tissue between the fruit or leaves and the shoots of the plant, is also essential for the control of defoliation of useful plants, in particular cotton.

[0153] Additionally, shortening the time it takes for individual cotton plants to mature improves the quality of the fiber after harvest.

[0154] The aqueous sprays can be applied in or on permanently cultivated land or on the surface of permanent crops. Permanent crops are those produced from plants that continue for many seasons, rather than being replanted for each harvest. Permanent crops are grown on permanently cultivated land in the form of agricultural land, including grassland and shrubland used for growing, for example, grape vines or coffee trees; orchards used for growing fruit or olives; and plantations used for growing, for example, nuts or rubber. However, this does not include tree farms intended for use in wood or timber.

[0155] Preferred permanent arable lands in the context of the present invention are plantations, grasslands and shrublands. Preferably, the permanent crops in the context of the present invention are plantation crops, preferably selected from the group consisting of fruit crops and orchard crops (preferably fruit trees, citrus trees, mango trees, olive trees, grape vines, coffee trees, cocoa trees, tea plants and berries such as strawberries, raspberries, blueberries and redcurrants), Musaceae sp. crops (e.g. banana or plantain crops), nut trees (preferably almond trees, walnut trees, pistachio trees, pecan trees, hazelnut trees), oil palm trees, rubber trees, sugar cane and cotton.

[0156] More preferably, the perennial crops are fruit trees (preferably pome and stone fruit trees; preferred fruit trees are apple trees, pear trees, apricot trees, plum trees, cherry trees, peach trees), olive trees, grape vines, coffee trees, tea plants, Musaceae sp. crops (preferably banana or plantain crops), nut trees (preferably almond trees, walnut trees, pistachio trees, pecan trees, hazelnut trees), oil palm trees, rubber trees and citrus crops (preferably lemon, orange or grapefruit crops). More preferably, the permanent crop is selected from the group consisting of apple trees, pear trees, apricot trees, plum trees, cherry trees, peach trees, olive trees, grape vines, coffee trees, tea plants, banana crops, nut trees (preferably almond trees, walnut trees, pistachio trees), oil palm trees, rubber trees and citrus crops (preferably lemon, orange or grapefruit crops). Particularly preferably, the permanent crop is selected from the group consisting of apple trees, pear trees, apricot trees, plum trees, cherry trees, peach trees, olive trees, grape vines, coffee trees, tea plants, banana crops, almond trees, walnut trees, oil palm trees, rubber trees, lemon crops, orange crops and grapefruit crops.

[0157] The herbicidal compositions can also be applied to row and specialty crops alike.

[0158] Row crops can be planted in rows wide enough to be tilled or otherwise cultivated by agricultural machinery (machinery designed for seasonal row crop activity). Row crops are characterized by being planted and cultivated seasonally or annually. Thus, they produce profitably in a relatively short and predictable time frame. Row crops are those that continue to produce from a plant for multiple seasons, rather than being replanted for each harvest. Examples of row crops include soybeans, corn, canola, cotton, cereals or rice, as well as sunflowers, potatoes, dry beans, peas, flax, safflower, buckwheat and sugar beets.

[0159] Horticultural crops should be understood to be fruits, vegetables or other garden crops or perennial plantation crops, such as trees, nuts, vines, (dried) fruits, ornamental plants, oil palm, banana, rubber, etc., and horticultural and nursery crops, including floriculture, may also be included within the definition of horticultural crops. Vegetable crops include, for example, aubergine, beans, peppers, cabbage, chilli, cucumber, eggplant, lettuce, melon, onion, potato, sweet potato, spinach and tomato. Plants considered as horticultural crops are generally those that are cultivated intensively. When controlling weeds in vegetable crops, it may be desirable to protect the crop from contact with sprays containing the herbicidal mixture of the present invention.

[0160] In general, the crops that can be treated with the aqueous sprays can be of conventional origin or herbicide-resistant crops, preferably at least one of glufosinate, glyphosate, and / or dicamba-resistant crops. The herbicide composition also exhibits high herbicidal effect on selected crop plants, such as barley and soybean. This effect can be used to control crop plants that were grown in the previous crop cultivation in a crop rotation method. Usually, the crop plant residue after harvesting the previous crop in a crop rotation cycle continues to grow mixed with the crop variety that is cultivated thereafter. This results in a decrease in yield because two types of crop plants from different crop rotation cycles compete in the same growing area. Therefore, the herbicide composition can be applied to control the residue crop plants of the previous crop in the crop rotation cycle so that they are evenly covered by the next crop plant.

[0161] In a preferred embodiment, the herbicide composition is applied once, twice or three times per Gregorian year, i.e., once, twice or three times per year according to the Gregorian calendar. In a preferred embodiment, the herbicide composition is applied twice per Gregorian year, i.e., twice per year according to the Gregorian calendar. In an alternative preferred embodiment, the herbicide composition is applied once per Gregorian year, i.e., once per year according to the Gregorian calendar. In a preferred embodiment, the herbicide composition is applied once about every 12 months, i.e., once about every 12 months. In an alternative preferred embodiment, the herbicide composition is applied once to 10 times per Gregorian year, i.e., not more than 10 times per year according to the Gregorian calendar. This alternative preferred method is particularly useful for perennial crops, especially those grown under tropical conditions. In such cases, the weeds will actively grow all year round and herbicide applications will need to be repeated as soon as the previous treatment has worn off and the weeds begin to grow again.

[0162] In specific embodiments of group 8, the herbicidal compositions are preferably used for post-emergence application.

[0163] The present invention includes the use and method of application of an aqueous spray solution to control undesirable vegetation in a crop in a burndown program, the crop having been produced by genetic engineering or breeding and which is tolerant to one or more herbicides and / or resistant to attack by pathogens such as phytopathogenic fungi and / or insects, preferably tolerant to glufosinate.

[0164] Glufosinate tolerant crops are preferred, and the glufosinate tolerant crop plants are preferably selected from the group consisting of rice, canola, soybean, corn and cotton plants.

[0165] Transgenic corn events containing glufosinate resistance genes include, for example, 5307×MIR604×Bt11×TC1507×GA21×MIR162 (event identifier: SYN-φ53φ7-1×SYN-IR6φ4-5×SYN-BTφ11-1×DAS-φ15φ7-1×MON-φφφ21-9×SYN-IR162-4, gene: pat, commercially available as, for example, Agrisure® Duracade® 5222), 59122 (event identifier: DAS-59122-7, gene: pat, commercially available as, for example, Agrisure® Duracade® 5222), Herculex™ RW), 5307×MIR604×Bt11×TC1507×GA21 (event identifier: SYN-φ53φ7-1×SYN-IR6φ4-5×SYN-BTφ11-1×DAS-φ15φ7-1×MON-φφφ21-9, gene: pat, for example, commercially available as Agrisure® Duracade™ 5122), 59122×NK603 (event identifier: DAS-59122-7×MON-φφ6φ3-6, gene: pat, for example, commercially available as Herculex™ RW Roundup™ Ready™ 2), Bt10 (gene: pat, e.g., commercially available as Bt10), Bt11 (X4334CBR, X4734CBR) (event identifier: SYN-BTφ11-1, gene: pat, e.g., commercially available as Agrisure™ CB / LL), BT11×59122×MIR604×TC1507×GA21 (event identifier: SYN-BTφ11-1×DAS-59122-7×SYN-IR6φ4-5×DAS-φ15φ7-1×MON-φφφ21-9, gene: pat, e.g., Agrisure® 3122 ) Bt11×GA21 (event identifier: SYN-BTφ11-1×MON-φφφ21-9, gene: pat, for example, commercially available as Agrisure® GT / CB / LL), Bt11×MIR162 (event identifier: SYN-BTφ11-1×SYN-IR162-4, gene: pat, for example, commercially available as Agrisure® Viptera® 2100), Bt11×MIR162×GA21 (event identifier: SYN-BTφ11-1×SYN-IR162-4×MON-φφφ21-9, gene: pat, for example,Agrisure® Viptera™ 3110), BT11×MIR162×MIR604 (event identifier: SYN-BTφ11-1×SYN-IR162-4×SYN-IR6φ4-5, gene: pat, e.g., commercially available as Agrisure® Viptera™ 3100), Bt11×MIR162×MIR604×GA21 (event identifier: SYN-BTφ11-1×SYN-IR162-4×SYN-IR6φ4-5, gene: pat, e.g., commercially available as Agrisure® Viptera™ 3100), -IR6φ4-5×MON-φφφ21-9, gene: pat, commercially available as, for example, Agrisure® Viptera® 3111, Agrisure® Viptera® 4), Bt11×MIR162×TC1507×GA21 (event identifier: SYN-BTφ11-1×SYN-IR162-4×DAS-φ15φ7-1×MON-φφφ21-9, gene: pat, commercially available as, for example, Agrisure® Viptera 3220), Bt11×MIR604 (event identifier: SYN-BTφ11-1×SYN-IR6φ4-5, gene: pat, commercially available, for example, as Agrisure™ CB / LL / RW), BT11×MIR604×GA21 (event identifier: SYN-BTφ11-1×SYN-IR6φ4-5×MON-φφφ21-9, gene: pat, commercially available, for example, as Agrisure™ 3000GT), Bt176(176) (event identifier: SYN-EV176-9, gene: bar, commercially available, for example, as NaturGard KnockOut™, Maximizer™), CBH-351 (event identifier: ACS-ZMφφ4-3, gene: bar, commercially available, for example, as Starlink™ Maize), DBT418 (event identifier: DKB-89614-9, gene: bar, commercially available, for example, as Bt Xtra™ Maize), MON89034×TC1507×MON88017×59122 (event identifier: MON-89φ34-3×DAS-φ15φ7-1×MON-88φ17-3×DAS-59122-7, gene: pat, commercially available, for example, as Genuity® SmartStax™),MON89034×TC1507×NK603 (event identifier: MON-89φ34-3×DAS-φ15φ7-1×MON-φφ6φ3-6, gene: pat, commercially available, for example, as Power Core™), NK603×T25 (event identifier: MON-φφ6φ3-6×ACS-ZMφφ3-2, gene: pat, commercially available, for example, as Roundup Ready™ Liberty Link™ Maize), T14 (event identifier: ACS-ZMφφ2-1, gene: pat, commercially available, for example, as Liberty Link™ Maize), T25 (event identifier: ACS-ZMφφ3-2, gene: pat, commercially available, for example, as Liberty Link™ Maize), T25×MON810 (event identifier: ACS-ZMφφ3-2×MON-φφ81φ-6, gene: pat, commercially available, for example, as Liberty Link™ Yieldgard™ Maize), TC1507 (event identifier: DAS-φ15φ7-1, gene: pat, commercially available, for example, as Herculex™ I, Herculex™ CB), TC1507×59122×MON810×MIR604×NK603 (event identifier: DAS-φ15φ7-1×DAS-59122-7×MON-φφ81φ-6×SYN-IR6φ4-5×MON-φφ6φ3, gene: pat, commercially available, for example, as Optimum™ Intrasect Xtreme), TC1507×59122 (event identifier: DAS-φ15φ7-1×DAS-59122-7, gene: pat, commercially available, for example, as Herculex XTRA™), TC1507×59122×MON810×NK603 (event identifier: DAS-φ15φ7-1×DAS-59122-7×MON-φφ81φ-6×MON-φφ6φ3-6, gene: pat, commercially available, for example, as Optimum™ Intrasect XTRA), TC1507×59122×NK603 (event identifier: DAS-φ15φ7-1×DAS-59122-7×MON-φφ6φ3-6, gene: pat, commercially available, for example, as Herculex XTRA™ RR),TC1507×MIR604×NK603 (event identifier: DAS-φ15φ7-1×SYN-IR6φ4-5×MON-φφ6φ3-6, gene: pat, commercially available, for example, as Optimum® TRIsect), TC1507×MON810×NK603 (event identifier: DAS-φ15φ7-1×MON-φφ81φ-6×MON-φφ6φ3-6, gene: pat, commercially available, for example, as Optimum® Intrasect), TC1507×NK603 (event identifier: DAS-φ15φ7-1×MON-φφ6φ3-6, gene: pat, commercially available, for example, as Herculex® I RR), 3272×Bt11 (event identifier: SYN-E3272-5×SYN-BTφ11-1, gene: pat), 3272×Bt11×GA21 (event identifier: SYN-E3272-5×SYN-BTφ11-1×MON-φφφ21-9, gene: pat), 3272×Bt11×MIR604 (event identifier: SYN-E3272-5×SYN-BTφ11 -1×SYN-IR6φ4-5, gene: pat), 3272×BT11×MIR604×GA21 (event identifier: SYN-E3272-5×SYN-BTφ11-1×SYN-IR6φ4-5×MON-φφφ21-9, gene: pat), 33121 (event identifier: DP-φ33121-3, gene: pat), 4114 (event identifier: DP-φφ4114-3, gene: pat), 59122×GA21 (event identifier: DAS-59122-7×MON-φφφ21-9, gene: pat), 59122×MIR604 (event identifier: DAS-59122-7×SYN-IR6φ4-5, gene: pat), 5307×MIR604×Bt11×TC1507×GA21×MIR162 (event identifier: gene: pat), 59122×MIR60 4×GA21 (event identifier: DAS-59122-7×SYN-IR6φ4-5×MON-φφφ21-9, gene: pat), 59122×MIR604×TC1507 (event identifier: DAS-59122-7×SYN-IR6φ4-5×DAS-φ15φ7-1, gene: pat), 59122×MIR604×TC1507×GA21 (event identifier: gene: pat),(Event Identifier: DAS-59122-7×SYN-IR6φ4-5×DAS-φ15φ7-1×MON-φφφ21-9, Gene: pat), 59122×MON810 (Event Identifier: DAS-59122-7×MON-φφ81φ-6, Gene: pat), 59122×MON810×NK603 (Event Identifier: DAS-59122-7×MON-φφ81φ-6×MON-φφ6φ3-6, Gene: pat), 59122×TC1507×GA21 (Event Identifier: DAS-59122-7×DAS-φ1 5φ7-1×MON-φφφ21-9, gene:pat), 676 (event identifier:PH-φφφ676-7, gene:pat), 678 (event identifier:PH-φφφ678-9, gene:pat), 680 (event identifier:PH-φφφ68φ-2, gene:pat), 98140×59122 (event identifier:DP-φ9814φ-6×DAS-59122-7, gene:pat), 98140×TC1507 (event identifier:DP-φ9814φ-6×DAS-φ15φ7-1, gene:pat), 981 40×TC1507×59122 (event identifier: DP-φ9814φ-6×DAS-φ15φ7-1×DAS-59122-7, gene: pat), 59122×MON88017 (event identifier: DAS-59122-7×MON-88φ17-3, gene: pat), Bt11×59122 (event identifier: SYN-BTφ11-1×DAS-59122-7, gene: pat), Bt11×59122×GA21 (event identifier: SYN-BTφ11-1×DAS-59122-7×MON-φφφ21-9 , gene: pat), Bt11×59122×MIR604 (event identifier: SYN-BTφ11-1×DAS-59122-7×SYN-IR6φ4-5, gene: pat), Bt11×59122×MIR604×GA21 (event identifier: SYN-BTφ11-1×DAS-59122-7×SYN-IR6φ4-5×MON-φφφ21-9, gene: pat), Bt11×59122×MIR604×TC1507 (event identifier: Bt11×59122×MIR604×TC1507, gene: pat),Bt11×59122×TC1507 (event identifier: SYN-BTφ11-1×DAS-59122-7×DAS-φ15φ7-1, gene: pat), Bt11×59122×TC1507×GA21 (event identifier: SYN-BTφ11-1×DAS-59122-7×DAS-φ15φ7-1×MON-φφφ21-9, gene: pat), Bt11×MIR162×TC1507 (event identifier: SYN-BTφ11-1×SYN-IR162-4×DAS-φ15φ7-1, gene: pat), Bt11×MIR604×TC1507 (event identifier: SYN-BTφ11-1×SYN-IR6φ4-5×DAS-φ15φ7-1, gene: pat), Bt11×TC1507 (event identifier: SYN-BTφ11-1×DAS-φ15φ7-1, gene: pat), Bt11×TC1507×GA21 (event identifier: SYN-BTφ11-1×DAS-φ15φ7-1×MON-φφφ21-9, gene: pat), GA21×T25 (event identifier: MON-φφφ21-9×ACS-ZMφφ3-2, gene: pat), MIR162×TC1507 (event identifier: SYN-IR162-4×DAS-φ15φ7-1, gene: pat), MIR162×TC 1507×GA21 (event identifier: SYN-IR162-4×DAS-φ15φ7-1×MON-φφφ21-9, gene: pat), MIR604×TC1507 (event identifier: SYN-IR6φ4-5×DAS-φ15φ7-1, gene: pat), MON87427×MON89φ34×TC15φ7×MON88φ17×59122 (event identifier: MON-87427-7×MON-89φ34-3×DAS-φ15φ7-1×MON-88φ17-3×DAS-59122-7, gene: pat), MO N89034×59122 (event identifier: MON-89φ34-3×DAS-59122-7, gene: pat), MON89034×59122×MON88017 (event identifier: gene: pat), MON89034×TC1507 (event identifier: MON-89φ34-3×DAS-59122-7×MON-88φ17-3, gene: pat), (event identifier: MON-89φ34-3×DAS-φ15φ7-1, gene: pat), MIR604×TC1507 (event identifier: SYN-IR6φ4 -5×DAS-φ15φ7-1, gene:pat), MON87427×MON89φ34×TC15φ7×MON88φ17×59122 (event identifier:MON-87427-7×MON-89φ34-3×DAS-φ15φ7-1×MON-88φ17-3×DAS-59122-7, gene:pat), MON89034×59122 (event identifier:MON-89φ34-3×DAS-59122-7, gene:pat), MON89034×59122×MON88017 (event identifier:gene:pat),MON89034×TC1507 (event identifier: MON-89φ34-3×DAS-59122-7×MON-88φ17-3, gene: pat), (event identifier: MON-89φ34-3×DAS-φ15φ7-1, gene: pat), DLL25(B16) (event identifier: DKB-8979φ-5, gene: bar), MIR604×TC1507 (event identifier: SYN-IR6φ4-5×DAS-φ15φ7-1, gene: pat), MON87427×MON89φ34×TC15φ7×MON88φ17×59122(event identifier: MON-89φ34-3×DAS-φ15φ7-1, gene: pat), Vent Identifier: MON-87427-7 x MON-89φ34-3 x DAS-φ15φ7-1 x MON-88φ17-3 x DAS-59122-7, Gene: pat), MON89034 x 59122 (Event Identifier: MON-89φ34-3 x DAS-59122-7, Gene: pat), MON89034 x 59122 x MON88017 (Event Identifier: MON-89φ34-3 x DAS-59122-7 x MON-88φ17-3, Gene: pat), MON89034 x TC1507 (Event Identifier: MON-89φ34-3 x DAS -φ15φ7-1, Gene:pat), MON89034×TC1507×59122 (Event Identifier:MON-89φ34-3×DAS-φ15φ7-1×DAS-59122-7, Gene:pat), MON89034×TC1507×MON88017 (Event Identifier:MON-89φ34-3×DAS-φ15φ7-1×MON-88φ17-3, Gene:pat), MON89034×TC1507×MON88017×59122×DAS40278 (Event Identifier:MON-89φ34-3×DAS-φ15φ7-1×MON- 88φ17-3×DAS-59122-7×DAS-4φ278-9, gene:pat), MON89034×TC1507×MON88017×DAS40278 (event identifier:MON-89φ34-3×DAS-φ15φ7-1×MON-88φ17-3×DAS-59122-7×DAS-4φ278-9, gene:pat), MON89034×TC1507×NK603×DAS40278 (event identifier:MON-89φ34-3×DAS-φ15φ7-1×MON-φφ6φ3-6×DAS-4φ278-9, gene:pat),NK603×MON810×4114×MIR 604 (event identifier: MON-00603-6×MON-00810-6×DP004114-3×SYN-IR604-4, gene: pat), TC1507×MON810×MIR604×NK603 (event identifier: DAS-φ15φ7-1×MON-φφ81φ-6×SYN-IR6φ4-5×MON-φφ6φ3-6, gene: pat), TC1507×59122×MON810 (event identifier: DAS-φ15φ7-1×DAS-59122-7×MON-φφ81φ-6, gene: pat), TC1507×591 22×MON88017 (event identifier: DAS-φ15φ7-1×DAS-59122-7×MON-88φ17-3, gene: pat), TC1507×GA21 (event identifier: DAS-φ15φ7-1×MON-φφφ21-9, gene: pat), TC1507×MON810 (event identifier: DAS-φ15φ7-1×MON-φφ81φ-6, gene: pat), TC1507×MON810×MIR162×NK603 (event identifier: DAS-φ15φ7-1×MON-φφ81φ-6×SYN-IR162-4 ×MON-φφ6φ3-6, gene: pat), 3272×Bt11×MIR604×TC1507×5307×GA21 (event identifier: SYN-E3272-5×SYN-BTφ11-1×SYN-IR6φ4-5×DAS-φ15φ7-1×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), TC1507×MIR162×NK603 (event identifier: DAS-φ15φ7-1×SYN-IR162-4×MON-φφ6φ3-6, gene: pat), TC1507×MON810×MIR162 (event identifier: Identifier: DAS-φ15φ7-1×MON-φφ81φ-6×SYN-IR162-4, gene: pat), MON87419 (event identifier: MON87419-8, gene: pat), TC1507×MON88017 (event identifier: DAS-φ15φ7-1×MON-88φ17-3, gene: pat), TC6275 (event identifier: DAS-φ6275-8, gene: bar), MZHG0JG (event identifier: SYN-φφφJG-2, gene: pat), MZIR098 (event identifier: SYN-φφφ98-3,gene: pat), Bt11×MIR162×MON89034 (event identifier: SYN-BTφ11-1×SYN-IR162-4×MON-89φ34-3, gene: pat) and Bt11×MIR162×MON89φ34×GA21 (event identifier: SYN-BTφ11-1×SYN-IR162-4×MON-89φ34-3×MON-φφφ21-9, gene: pat), 59122×DAS40278 (event identifier: DAS-59122-7×DAS-4φ278-9, gene: p at), 59122×MON810×MIR604 (event identifier: DAS-59122-7×MON-φφ81φ-6×SYN-IR6φ4-5, gene: pat), 59122×MON810×NK603×MIR604 (event identifier: DAS-59122-7×MON-φφ81φ-6×MON-φφ6φ3-6×SYN-IR6φ4-5, gene: pat), 59122×MON88017×DAS40278 (event identifier: DAS-59122-7×MON-88φ17-3×DAS -4φ278-9, gene: pat), 59122×NK603×MIR604 (event identifier: DAS-59122-7×MON-φφ6φ3-6×SYN-IR6φ4-5, gene: pat), Bt11×5307 (event identifier: SYN-BTφ11-1×SYN-φ53φ7-1, gene: pat), Bt11×5307×GA21 (event identifier: SYN-BTφ11-1×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), Bt11×MIR162×5307 (event identifier: SYN-BTφ11-1×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), Vent Identifier: SYN-BTφ11-1×SYN-IR162-4×SYN-φ53φ7-1, Gene: pat), Bt11×MIR162×5307×GA21 (Event Identifier: SYN-BTφ11-1×SYN-IR162-4×SYN-φ53φ7-1×MON-φφφ21-9, Gene: pat), BT11×MIR162×MIR604×5307 (Event Identifier: SYN-BTφ11-1×SYN-IR162-4×SYN-IR6φ4-5×SYN-φ53φ7-1, Gene: pat),Bt11×MIR162×MIR604×5307×GA21 (event identifier: SYN-BTφ11-1×SYN-IR162-4×SYN-IR6φ4-5×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), Bt11×MIR162×MIR604×MON89034×5307×GA21 (event identifier: SYN-BTφ11-1×SYN-IR162-4×SYN-IR6φ4-5×MON-89φ34-3×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), BT11×MIR162×MIR604×TC1507 (event identifier: SYN-BTφ11-1×SYN-IR162-4×SYN-IR6φ4-5×DAS-φ15φ7-1, gene: pat), BT11×MIR162×MIR604×TC1507×5307 (event identifier: SYN-BTφ11-1×SYN-IR162-4×SYN-IR6φ4-5×DAS-φ15φ7-1×SYN-φ53φ7-1, gene: pat), Bt11×MIR162×MIR604×TC1507×GA21 (event Identifier: SYN-BTφ11-1 × SYN-IR162-4 × SYN-IR6φ4-5 × DAS-φ15φ7-1 × MON-φφφ21-9, Gene: pat), Bt11 × MIR162 × TC1507 × 5307 (Event Identifier: SYN-BTφ11-1 × SYN-IR162-4 × DAS-φ15φ7-1 × SYN-φ53φ7-1, Gene: pat), BT11 × MIR162 × MIR604 × TC1507 × 5307 (Event Identifier: SYN-BTφ11-1 × SYN-IR162-4 × SYN-IR6φ 4-5×DAS-φ15φ7-1×SYN-φ53φ7-1, gene: pat), Bt11×MIR162×MIR604×TC1507×GA21 (event identifier: SYN-BTφ11-1×SYN-IR162-4×SYN-IR6φ4-5×DAS-φ15φ7-1×MON-φφφ21-9, gene: pat), Bt11×MIR162×TC1507×5307 (event identifier: SYN-BTφ11-1×SYN-IR162-4×DAS-φ15φ7-1×SYN-φ53φ7-1, gene: pat),Bt11×MIR162×TC1507×5307×GA21 (event identifier: SYN-BTφ11-1×SYN-IR162-4×DAS-φ15φ7-1×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), Bt11×MIR604×5307 (event identifier: SYN-BTφ11-1×SYN-IR6φ4-5×SYN-φ53φ7-1, gene: pat), Bt11×MIR604×5307×GA21 (event identifier: SYN-BTφ11-1×SYN-IR6φ4-5×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), Bt11×MIR604×TC1507×5307 (event identifier: SYN-BTφ11-1×SYN-IR6φ4-5×DAS-φ15φ7-1×SYN-φ53φ7-1, gene: pat), Bt11×MIR604×TC1507×GA21 (event identifier: SYN-BTφ11-1×SYN-IR6φ4-5×DAS-φ15φ7-1×MON-φφφ21-9, gene: pat), Bt11×MON89034 (or Bt11×MON89φ34) (event identifier: SYN-BTφ11-1×MON-89φ34-3, gene: pat), Bt11×MON89034×GA21 (event identifier: SYN-BTφ11-1×MON-89φ34-3×MON-φφφ21-9, gene: pat), Bt11×M ON89φ34×GA21 (event identifier: SYN-BTφ11-1×MON-89φ34-3×MON-φφφ21-9, gene: pat), Bt11×TC1507×5307 (event identifier: SYN-BTφ11-1×DAS-φ15φ7-1×SYN-φ53φ7-1, gene: pat), Bt11×TC1507×5307×GA21 (event identifier: SYN-BTφ11-1×DAS-φ15φ7-1×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), MIR162×MIR604×TC1507×5307( Event identifier: SYN-IR162-4 x SYN-IR6φ4-5 x DAS-φ15φ7-1 x SYN-φ53φ7-1, gene: pat), MIR162 x MIR604 x TC1507 x 5307 x GA21 (Event identifier: SYN-IR162-4 x SYN-IR6φ4-5 x DAS-φ15φ7-1 x SYN-φ53φ7-1 x MON-φφφ21-9, gene: pat), MIR162 x MIR604 x TC1507 x GA21 (Event identifier: SYN-IR162-4 x SYN-IR6φ4-5 x DAS-φ15φ7-1 x MON-φ φφ21-9, gene: pat), MIR162×TC1507×5307 (event identifier: SYN-IR162-4×DAS-φ15φ7-1×SYN-φ53φ7-1, gene: pat), MIR162×TC1507×5307×GA21 (event identifier: SYN-IR162-4×DAS-φ15φ7-1×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), MIR604×TC1507×5307 (event identifier: SYN-IR6φ4-5×DAS-φ15φ7-1×SYN-φ53φ7-1, gene: pat),MIR162×TC1507×5307 (event identifier: SYN-IR162-4×DAS-φ15φ7-1×SYN-φ53φ7-1, gene: pat), MIR162×TC1507×5307×GA21 (event identifier: SYN-IR162-4×DAS-φ15φ7-1×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), MIR604×TC1507×5307 (event identifier: SYN-IR6φ4-5×DAS-φ15φ7-1×SYN-φ53φ7-1, gene: pat) gene:pat), MIR604×TC1507×5307×GA21 (event identifier:SYN-IR6φ4-5×TC1507×SYN-φ53φ7-1×MON-φφφ21-9, gene:pat), MIR604×TC1507×GA21 (event identifier:SYN-IR6φ4-5×TC1507×MON-φφφ21-9, gene:pat), MON87427×59122 (event identifier:MON-87427-7×DAS-59122-7, gene:pat), MON87427×M ON89034×59122 (event identifier: MON-87427-7×MON-89φ34-3×DAS-59122-7, gene: pat), MON87427×MON89034×MON88017×59122 (event identifier: MON-87427-7×MON-89φ34-3×MON-88φ17-3×59122, gene: pat), MON87427×MON89034×TC1507 (event identifier: MON-87427-7×MON-89φ34-3×DAS-φ15φ7 -1, gene: pat), MON87427 × MON89034 × TC1507 × 59122 (event identifier: MON-87427-7 × MON-89φ34-3 × DAS-φ15φ7-1 × DAS-59122-7, gene: pat), MON87427 × MON89034 × TC1507 × MON87411 × 59122 (event identifier: MON-87427-7 × MON-89φ34-3 × DAS-φ15φ7-1 × MON-87411-9 × DAS-59122-7, gene: pat),MON87427×MON89034×TC1507×MON87411×59122×DAS40278 (event identifier: MON-87427-7×MON-89φ34-3×DAS-φ15φ7-1×MON-87411-9×DAS-59122-7×DAS-4φ278-9, gene: pat), MON87427×MON89034×TC1507×MON88017 (event identifier: MON-87427-7×MON-89φ34-3×DAS-φ15φ7-1×MON-88φ17-3, gene: pat), MON87427× TC1507 (event identifier: MON-87427-7 x DAS-φ15φ7-1, gene: pat), MON87427 x TC1507 x 59122 (event identifier: MON-87427-7 x DAS-φ15φ7-1 x DAS-59122-7, gene: pat), MON87427 x TC1507 x MON88017 (event identifier: MON-87427-7 x DAS-φ15φ7-1 x MON-88φ17-3, gene: pat), MON87427 x TC1507 x MON88017 x 59122 (event identifier: MON-87427-7 x DAS-φ15φ7-1 x MON-88φ17-3, gene: pat), 27-7×DAS-φ15φ7-1×MON-88φ17-3×DAS-59122-7, gene:pat), MON89034×59122×DAS40278(event identifier:MON-89φ34-3×DAS-59122-7×DAS-4φ278-9, gene:pat), MON89034×59122×MON88017×DAS40278(event identifier:MON-89φ34-3×DAS-59122-7×MON-88φ17-3×DAS-4φ278-9, gene:pat), MON89034×TC1507×59122 ×DAS40278 (event identifier: MON-89φ34-3×DAS-φ15φ7-1×DAS-59122-7×DAS-4φ278-9, gene: pat), MON89034×TC1507×DAS40278 (event identifier: MON-89φ34-3×DAS-φ15φ7-1×DAS-4φ278-9, gene: pat), MON89034×TC1507×NK603×MIR162 (event identifier: MON-89φ34-3×DAS-φ15φ7-1×MON-φφ6φ3-6×SYN-IR162-4, gene: pat),TC1507×5307 (event identifier: DAS-φ15φ7-1×SYN-φ53φ7-1, gene: pat), TC1507×5307×GA21 (event identifier: DAS-φ15φ7-1×SYN-φ53φ7-1×MON-φφφ21-9, gene: pat), TC1507×59122×DAS40278 (event identifier: DAS-φ15φ7-1×DAS-59122-7×DAS-4φ278-9, gene: pat), TC1507×59122×MON81 0×MIR604 (event identifier: DAS-φ15φ7-1×DAS-59122-7×MON-φφ81φ-6×SYN-IR6φ4-5, gene: pat), TC1507×59122×MON88017×DAS40278 (event identifier: DAS-φ15φ7-1×DAS-59122-7×MON-88φ17-3×DAS-4φ278-9, gene: pat), TC1507×59122×NK603×MIR604 (event identifier: gene: pat), DAS- φ15φ7-1×DAS-59122-7×MON-φφ6φ3-6×SYN-IR6φ4-5, TC1507×DAS40278 (event identifier: DAS-φ15φ7-1×DAS-4φ278-9, gene: pat), TC1507×MON810×MIR604 (event identifier: DAS-φ15φ7-1×MON-φφ81φ-6×SYN-IR6φ4-5, gene: pat), TC1507×MON810×NK603×MIR604 (event identifier: DAS-φ1 5φ7-1×MON-φφ81φ-6×MON-φφ6φ3-6×SYN-IR6φ4-5, gene: pat), TC1507×MON88017×DAS40278 (event identifier: DAS-φ15φ7-1×MON-88φ17-3×DAS-4φ278-9, gene: pat) and TC1507×NK603×DAS40278 (event identifier: DAS-φ15φ7-1×MON-φφ6φ3-6×DAS-4φ278-9, gene: pat), but not excluding others.

[0166] Transgenic soybean events containing a glufosinate tolerance gene include, for example, A2704-12 (event identifier: ACS-GMφφ5-3, gene: pat, commercially available, e.g., as Liberty Link™ soybean), A2704-21 (event identifier: ACS-GMφφ4-2, gene: pat, commercially available, e.g., as Liberty Link™ soybean), A5547-127 (event identifier: ACS-GMφφ6-4, gene: pat, commercially available, e.g., as Liberty Link™ soybean), A5547-35 (event identifier: ACS-GMφφ8-6, gene: pat, commercially available, e.g., as Liberty Link™ soybean), GU262 (event identifier: ACS-GMφφ3-1, gene: pat, commercially available, e.g., as Liberty Link™ soybean), Link™ soybean), W62 (event identifier: ACS-GMφφ2-9, gene: pat, commercially available, e.g., as Liberty Link™ soybean), W98 (event identifier: ACS-GMφφ1-8, gene: pat, commercially available, e.g., as Liberty Link™ soybean), DAS68416-4 (event identifier: DAS-68416-4, gene: pat, commercially available, e.g., as Enlist™ Soybean), DAS44406-6 (event identifier: DAS-444φ6-6, gene: pat), DAS68416-4×MON89788 (event identifier: DAS-68416-4×MON-89788 -1, gene: pat), SYHTφH2 (event identifier: SYN-φφφH2-5, gene: pat), DAS81419×DAS44406-6 (event identifier: DAS-81419-2×DAS-444φ6-6, gene: pat) and FG72×A5547-127 (event identifier: MST-FGφ72-3×ACS-GMφφ6-4, gene: pat), but not to the exclusion of others.

[0167] Transgenic cotton events containing glufosinate resistance genes are, for example, 3006-210-23×281-24-236×MON1445 (event identifier: DAS-21φ23-5×DAS-24236-5×MON-φ1445-2, gene: bar, commercially available as, for example, WideStrike™ Roundup Ready™ Cotton), 3006-210-23×281-24-236×MON88913 (event identifier: DAS-21φ23-5×DAS-24236-5×MON-88913-8, gene: bar, commercially available as, for example, Widestrike™ Roundup Ready™ Cotton), Flex™ Cotton), 3006-210-23×281-24-236×MON88913×COT102 (event identifier: DAS-21φ23-5×DAS-24236-5×MON-88913-8×SYN-IR1φ2-7, gene: pat, e.g., Widestrike™×Roundup Ready Flex™×VIPCOT™ Cotton), GHB614×LLCotton25 (event identifier: BCS-GHφφ2-5×ACS-GHφφ1-3, gene: bar, e.g., GlyTol™ Liberty Link™), GHB614×T304-40×GHB119 (event identifier: BCS-GHφφ2-5×BCS-GHφφ4-7×BCS-GHφφ5-8, gene: bar, commercially available, for example, as Glytol™×Twinlink™), LLCotton25 (event identifier: ACS-GHφφ1-3, gene: bar, commercially available, for example, as ACS-GHφφ1-3), GHB614×T304-40×GHB119 x COT102 (event identifier: BCS-GHφφ2-5 x BCS-GHφφ4-7 x BCS-GHφφ5-8 x SYN-IR1φ2-7, gene: bar, commercially available as, for example, Glytol™ x Twinlink™ x VIPCOT™ Cotton), LLCotton25 x MON15985 (event identifier: ACS-GHφφ1-3 x MON-15985-7, gene: bar, commercially available as, for example, Fibermax™ Liberty Link™ BollgardII™), T304-40×GHB119 (event identifier: BCS-GHφφ4-7×BCS-GHφφ5-8, gene: bar, commercially available, for example, as TwinLink™ Cotton), GHB614×T304-40×GHB119×COT102 (event identifier: BCS-GHφφ2-5×BCS-GHφφ4-7×BCS-GHφφ5-8×SYN-IR1φ2 -7, gene: bar, commercially available, for example, as Glytol™ x Twinlink™ x VIPCOT™ Cotton), GHB119 (event identifier: BCS-GHφφ5-8, gene: bar), GHB614 x LLCotton25 x MON15985 (event identifier: CS-GHφφ2-5 x ACS-GHφφ1-3 x MON-15985-7, gene: bar), MON 887φ1-3 (event identifier: MON88701, gene: bar), T303-3 (event identifier: BCS-GHφφ3-6, gene: bar), T304-40 (event identifier: BCS-GHφφ3-6, gene: bar), (event identifier: BCS-GHφφ4-7, gene: bar), 81910 (event identifier: DAS-81910-7, gene: pat), MON8870 (event identifier: MON 887φ1-3, gene: bar), MON88701×MON88913 (event identifier: MON 887φ1-3×MON-88913-8, gene: bar), MON88701×MON88913×MON15985 (event identifier: MON 887φ1-3×MON-88913-8×MON-15985-7, gene: bar), 281-24-236×3006-210-23×COT102×81910 (event identifier: DAS-24236-5×DAS-21φ23-5×SYN-IR1φ2-7×DAS-81910-7, gene: pat), COT102×MON15985×MON88913×MON88701 (event identifier: SYN-IR1φ2-7×MON-15985-7×MON-88913-8×MON887φ1-3, gene: bar) and 3006-210-23 × 281-24-236 × MON88913 × COT102 × 81910 (event identifier: DAS-21φ23-5 × DAS-24236-5 × MON-88913-8 × SYN-IR1φ2-7 × DAS-81910-7, gene: pat), but not to the exclusion of others.

[0168] Transgenic canola events containing a glufosinate resistance gene include, for example, HCN10 (Topas 19 / 2) (event identifier: gene: bar, commercially available, for example, as Liberty Link™ Independence™), HCN28 (T45) (event identifier: ACS-BNφφ8-2, gene: pat, commercially available, for example, as InVigor™ Canola), HCN92 (Topas 19 / 2 (event identifier: ACS-BNφφ7-1, gene: bar, commercially available, for example, as Liberty Link™ Innovator™), MS1(B91-4) (event identifier: ACS-BNφφ4-7, gene: bar, commercially available, for example, as InVigor™ Canola), MS1×RF1(PGS1) (event identifier: ACS-BNφφ4-7×ACS-BNφφ1-4, gene: bar, commercially available, for example, as InVigor™ Canola), MS1×RF2(PGS2) (event identifier: ACS-BNφφ4-7×ACS-BNφφ2-5, gene: bar, commercially available, for example, as InVigor™ Canola), MS1×RF3 (event identifier: ACS-BNφφ4-7×ACS-BNφφ3-6, gene: bar, commercially available, for example, as InVigor™ Canola), MS8 (event identifier: ACS-BNφφ5-8, gene: bar, commercially available, for example, as InVigor™ Canola), r™ Canola), MS8 x RF3 (event identifier: ACS-BNφφ5-8 x ACS-BNφφ3-6, gene: bar, commercially available, for example, as InVigor™ Canola), RF1 (B93-101) (event identifier: ACS-BNφφ1-4, gene: bar, commercially available, for example, as InVigor™ Canola), RF2 (B94-2) (event identifier: ACS-BNφφ2-5, gene: bar, commercially available, for example, as InVigor™ Canola), RF3 (event identifier: ACS-BNφφ3-6, gene: bar, commercially available, for example, as InVigor™ Canola), MS1 x MON88302 (event identifier: ACS-BNφφ4-7 x MON-883φ2-9, gene: bar, for example, as InVigor™ x TruFlex™ RoundupReady™ Canola), MS8×MON88302 (event identifier: ACS-BNφφ5-8×MON-883φ2-9, gene: bar, for example, commercially available as InVigor™×TruFlex™ Roundup Ready™ Canola), RF1×MON88302 (event identifier: ACS-BNφφ1-4×MON-883φ2-9, gene: bar, for example, commercially available as InVigor™×TruFlex™ Roundup Ready™ Canola), RF2×MON88302 (event identifier: ACS-BNφφ2-5×MON-883φ2-9, gene: bar, for example, commercially available as InVigor™×TruFlex™ Roundup Ready™ Canola), Ready™ Canola), HCN28×MON88302 (event identifier: ACS-BNφφ8-2×MON-883φ2-9, gene: pat, e.g., InVigor™×TruFlex™ Roundup Ready™ Canola), HCN92×MON88302 (event identifier: ACS-BNφφ7-1×MON-883φ2-9, gene: bar, e.g., Liberty Link™ Innovator™×TruFlex™ Roundup Ready™ Canola), HCR-1 (gene: pat), MON88302×MS8×RF3 (event identifier: MON-883φ2-9×ACS-BNφφ5-8×ACS-BNφφ3-6, gene: bar), MON88302×RF3 (event identifier: MON-883φ2-9×ACS-BNφφ3-6, gene: bar), MS8×RF3×GT73(RT73) (event The following genes were identified as monocytes in the 14-kDa subgroup: PHY14 (event identifier: ACS-BNφφ5-8×ACS-BNφφ3-6×MON-φφφ73-7, gene: bar), PHY23 (gene: bar), PHY35 (gene: bar) and PHY36 (gene: bar) and 73496×RF3 (event identifier: DP-φ73496-4×ACS-BNφφ3-6, gene: bar), but not to the exclusion of others.

[0169] Transgenic rice events comprising a glufosinate tolerance gene are, for example, LLRICE06 (event identifier: ACS-OSφφ1-4, commercially available, e.g., as Liberty Link™ rice), LLRICE601 (event identifier: BCS-OSφφ3-7, commercially available, e.g., as Liberty Link™ rice) and LLRICE62 (event identifier: ACS-OSφφ2-5, commercially available, e.g., as Liberty Link™ rice), but are not exclusive of others.

[0170] The application of the combination of herbicides with copolymer CP results in outstanding herbicidal activity against a wide range of economically important harmful monocotyledonous and dicotyledonous plants, in which case post-emergence application is also preferred.

[0171] In particular, some representatives of the monocotyledonous and dicotyledonous weed flora that can be controlled by the combination according to the invention can be exemplified, but this list is not intended to be limited to any particular species.

[0172] In connection with the text, reference is sometimes made to the growth stages from the BBCH monograph "Growth stages of mono- and dicotyledonous plants", 2nd edition, 2001, ed. Uwe Meier, Federal Biological Research Centre for Agriculture and Forestry (Biologische Bundesanstalt für Land und Forstwirtschaft).

[0173] Examples of harmful monocotyledonous plants on which glufosinate combinations can be effective are: Hordeum spp., Echinochloa spp., Poa spp., Bromus spp., Digitaria spp., Eriochloa spp., Setaria spp., Pennisetum spp., Eleusine spp., Eragrostis spp., Panicum spp., Lolium spp., Brachiaria spp., Leptochloa spp., and others. spp.), Avena spp., Cyperus spp., Axonopris spp., Sorghum spp. and Melinus spp.

[0174] Specific examples of harmful monocotyledonous plant species on which the herbicidal composition is effective include Hordeum murinum, Echinochloa crus-galli, Poa annua, Bromus rubens L., Bromus rigidus, Bromus secalinus L., Digitaria sanguinalis, Digitaria insularis, Eriochloa gracilis, Setaria faberi, Setaria viridis, Pearl millet, Eleusine indica, Eragrostis pectinacea, Panicum miliaceum, Lolium multiflorum, Brachiaria platyphylla, Leptochloa fusca, Avena fatua, Cyperus compressus, Cyperus esculentes, Axonopris offinis, Sorghum halapense and Melinus repens.

[0175] In a preferred embodiment, the herbicidal composition is used for controlling harmful monocotyledonous plants, more preferably monocotyledonous plants of the species Echinochloa spp., Digitaria spp., Setaria spp., Eleusine spp. and Brachiarium spp.

[0176] Examples of harmful dicotyledonous plants against which the herbicidal compositions can be effectively acted upon are Amaranthus spp., Erigeron spp., Conyza spp., Polygonum spp., Medicago spp., Mollugo spp., Cyclospermum spp., Stellaria spp., Gnaphalium spp., Taraxacum spp., Oenothera spp., Amsinckia spp., Erodium spp., spp.), Erigeron spp., Senecio spp., Lamium spp., Kochia spp., Chenopodium spp., Lactuca spp., Malva spp., Ipomoea spp., Brassica spp., Sinapis spp., Urtica spp., Sida spp., Portulaca spp., Richardia spp. spp.), Ambrosia spp., Calandrinia spp., Sisymbrium spp., Sesbania spp., Capsella spp., Sonchus spp., Euphorbia spp., Helianthus spp., Coronopus spp., Salsola spp., Abutilon spp., Vicia spp., Epilobium spp., Cardamine spp. spp.), Picris spp.), Trifolium spp., Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp., Metricaria spp., Plantago spp., Tribulus spp., Cenchrus spp., Bidens spp., Veronica spp. and Hypochaeris spp. .

[0177] Specific examples of harmful dicotyledonous plant species against which the herbicidal composition is effective are Amaranthus spinosus, Polygonum convolvulus, Medicago polymorpha, Mollugo verticillata, Cyclospermum leptophyllum, Stellaria media, Gnaphalium purpureum, Taraxacum officinale, Oenothera laciniata, Amsinckia intermedia, Erodium cicutarium, Erodium moschatum, Erigeron bonariensis, and others. Conyza bonariensis, Senecio vulgaris, Lamium amplexicaule, Erigeron canadensis, Polygonum aviculare, Kochia scoparia, Chenopodium album, Lactuca serriola, Malva parviflora, Malva neglecta, Ipomoea hederacea, Ipomoea lacunose, Brassica nigra, Sinapis arvensis, Urtica dioica, Amaranthus blitoides, Amaranthus retroflexus, Amaranthus hybridus, Amaranthus lividus, Sida spinosa, Portulaca oleracea, Richardiascabra, Ambrosia artemisiifolia, Calandrinia caulescens, Sisymbrium irio, Sesbania exaltata, Capsella bursa-pastoris, Sonchus oleraceus, Euphorbia maculate, Helianthus annuus, Coronopus didymus, Salsola tragus, Abutilon theophrasti, Vicia benghalensis L., Epilobium paniculatum, Cardamine spp. spp., Picris echioides, Trifolium spp., Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp., Metricaria matriccarioides, Plantago spp., Tribulus terrestris, Salsola kali, Cenchrus spp., Bidens bipinnata, Veronica spp. and Hypochaeris radicata) species.

[0178] In a preferred embodiment, the herbicidal composition is used for controlling harmful dicotyledonous plant species, more preferably dicotyledonous plants of the species Amaranthus spp., Erigeron spp., Conyza spp., Kochia spp. and Abutilon spp.

[0179] By applying the aqueous spray, the following weeds can be controlled: Cyperus rotundus L., Cyperus esculentus L., Cyperus brevifolius H., Cyperus microiria Steud, Cyperus iria L., Cyperus difformis L., Cyperus difformis L., Cyperus esculentus, Cyperus ferax, Cyperus flavus, Cyperus iria, Cyperus lanceolatus, Cyperus lanceolatus, Cyperus ferax, Cyperus flavus, Cyperus iria, Cyperus lanceolatus, Cyperus ferax ... odoratus, Cyperus rotundus, Cyperus serotinus Rottb. and other Cyperus species, Eleocharis acicularis, Eleocharis kuroguwai, Fimbristylis dichotoma, Fimbristylis miliacea, Scirpus grossus, Scirpus juncoides, Scirpus juncoides Roxb, Scirpus or Bolboschoenus maritimus, Scirpus or Schoenoplectus mucronatus, Scirpus planiculmis Many annual or perennial Cyperaceae weeds such as Cyperaceae (Fr. Schmidt).

[0180] When the spray is applied to the green parts of plants after emergence, growth is drastically stopped within a very short time after treatment, and the weed plants either remain in the growth stage at the time of application or die completely after a certain period of time, thus eliminating competition from weeds harmful to the crop in a very early and sustained manner.

[0181] The application of the combination of herbicide and copolymer CP provides rapid onset and long-lasting herbicidal action.In principle, it is advantageous that the herbicidal active compound in the combination of the present invention is rain-resistant.In particular, the use of this herbicidal composition can reduce application rate, control a wider range of broadleaf weeds and grass weeds, exert herbicidal action more quickly, have a longer period of action, can be used only once or several times to better control harmful plants, and can extend the application period.

[0182] The above-mentioned properties and advantages are advantageous in the practice of weed control to keep agricultural crops free of undesirable competing plants and thus ensure and / or increase yields in qualitative and / or quantitative terms. These herbicidal compositions significantly exceed the prior art with regard to the properties described herein.

[0183] Due to these herbicidal and plant growth regulating properties, the herbicidal composition can be used to control harmful plants in genetically modified crops or crops obtained by mutation / selection. These crops are generally distinguished by certain advantageous properties, such as resistance to herbicidal compositions or resistance to plant diseases or causative agents of plant diseases, for example, specific insects or microorganisms such as fungi, bacteria or viruses. Other specific properties relate, for example, to the quantity, quality, storability, composition and specific components of the harvested material. Thus, for example, transgenic plants are known whose starch content is increased or whose starch quality is altered or whose harvested material has a different fatty acid composition.

[0184] Certain embodiments of the invention also relate to methods for controlling undesirable vegetation (e.g., harmful plants), comprising applying a herbicide composition, preferably by postemergence methods, to the harmful or undesirable plant, to a part of said harmful or undesirable plant, or to an area in which the harmful or undesirable plant grows, e.g., an area under cultivation.

[0185] "Control" in the context of the present invention refers to a significant reduction in the growth of harmful plants compared to untreated harmful plants. Preferably, the growth of harmful plants is essentially reduced (60-79%), more preferably, the growth of harmful plants is significantly or completely inhibited (80-100%), in particular, the growth of harmful plants is almost or completely inhibited (90-100%).

[0186] Therefore, in a further aspect, the present invention relates to a method for suppressing the growth of undesirable plants and / or for controlling harmful plants, which comprises the step of applying an aqueous spray containing a combination of a herbicide and a copolymer CP, preferably in one of the preferred embodiments defined herein, to the undesirable or harmful plants, to parts of the undesirable or harmful plants or to the area in which the undesirable or harmful plants grow.

[0187] Aqueous sprays containing the combination of herbicide and copolymer CP can be used to control undesirable vegetation in burndown programs, in industrial vegetation management and forest management, in vegetable and perennial crops, and in lawns and turf, and the herbicide composition(s) can be applied pre- or post-emergence, i.e., before, during, and / or after, the emergence of undesirable plants.Preferably, they are applied as post-emergence treatments, i.e., during and / or after the emergence of undesirable plants.Herein, the herbicide composition is applied to the location where the crop will be planted, before planting or before emergence of the crop.

[0188] In industrial vegetation management and forest management, it is desirable to control a wide range of weeds for a long period of time. Control of large weeds or tall species such as shrubs or trees may also be desirable. Industrial weed management includes, for example, railroad tracks and right-of-way management, fence lines and non-cultivated areas such as industrial and construction sites, gravel areas, roads or walkways. Forest management includes, for example, clear-cutting existing forests or virgin land, preventing regrowth after mechanical cutting of forest vegetation, or weed management in forest management plantations. In the latter case, it may be desirable to protect desirable trees from contact with sprays containing the herbicidal mixture of the present invention.

[0189] Aqueous sprays containing the combination of herbicide and copolymer CP can also be used to control weeds in turf and lawns, provided that the desired grass species is tolerant to the herbicide composition. In particular, this type of herbicide composition can be used on the desired grass species that have been rendered tolerant to the respective agrochemical active ingredient, for example glufosinate or its salts, by mutagenesis or genetic engineering.

[0190] Glufosinate and its salts are non-selective systemic herbicides that have good post-emergence activity against many weeds and therefore can be used in burndown programs, industrial vegetation management and forestry management, vegetable and perennial crops and transplanted turf and lawns.

[0191] The present invention therefore also relates to a method for burn-down treatment of undesirable vegetation in a crop, comprising applying an aqueous spray containing a combination of a herbicide and a copolymer CP to the locus where the crop is to be planted, before planting (or sowing) the crop or before emergence of the crop, in which case the herbicide composition is applied to the undesirable vegetation or to its locus.

[0192] The present invention also relates to a method for controlling undesirable vegetation, comprising applying an aqueous spray containing a combination of herbicide and copolymer CP to a location where undesirable vegetation is present or expected to be present. Application can be carried out before, during and / or after, preferably during and / or after, the emergence of undesirable vegetation. In one embodiment, application is carried out before emergence of the crop to be grown in the location where undesirable vegetation is present or expected to be present. In another embodiment, application is carried out before planting the crop.

[0193] In a burn-down program, the spray can be applied before sowing (planting) the crop plants, or after sowing (or planting) but before the crop plants germinate, specifically before sowing. The spray is preferably applied before sowing the crop plants. When burn-down is performed, the spray will generally be applied within 9 months, often within 6 months, preferably within 4 months before planting the crop. Burn-down application can be performed up to 1 day before the crop plants germinate, preferably before the sowing / planting date of the crop plants, preferably at least 1 day, preferably at least 2 days, in particular at least 4 days or 6 months to 1 day before germination, in particular 4 months to 2 days before germination, more preferably 4 months to 4 days before germination. Needless to say, burn-down application can be repeated one or more times within the period, for example 1, 2, 3, 4 or 5 times.

[0194] A particular advantage of the sprays containing herbicides and copolymer CP is that the application of the sprays results in very good post-emergence herbicidal activity, i.e. they show good herbicidal activity against undesirable plants after emergence. Thus, in a preferred embodiment of the present invention, the sprays are applied post-emergence, i.e. during and / or after the emergence of undesirable plants. It is particularly advantageous to apply the sprays after emergence, from the onset of leaf development of undesirable plants until flowering. The herbicidal compositions are particularly useful for controlling undesirable vegetation that has already developed to a state where it is difficult to control using conventional burndown mixtures, i.e. where the height of individual weeds exceeds 10 cm (4 inches) or even 15 cm (6 inches) and / or where the weeds are very thick. In the case of post-emergence treatment of plants, the herbicidal compositions are preferably applied foliarly.

[0195] Spray can be applied in a conventional manner by using the techniques that are familiar to those skilled in the art.Suitable techniques include spraying, atomization, dusting or flooding.Application manner varies according to intended purpose and is carried out in a well-known manner, and in any case, they must ensure that the active ingredient according to the present invention is dispersed as finely as possible.

[0196] In one embodiment, the spray solution is applied to the locus primarily by spraying, particularly foliar spraying, of an aqueous dilution of the active ingredients of the mixture. Application can be carried out by conventional spraying techniques, using a spray solution rate of about 10 to 2000 l / ha or 50 to 1000 l / ha (e.g., 100 to 500 l / ha).

[0197] The required application rate of the herbicidally active compound via the spray will vary depending on the density of the undesirable vegetation, the developmental stage of the plants, the climatic conditions where the mixture is used, and the method of application.

[0198] In general, the application rate of L-glufosinate or a salt thereof is usually in the range of 50 g / ha to 3000 g / ha of active substance (ai), preferably 100 g / ha to 2000 g / ha or 200 g / ha to 1500 g / ha.

[0199] The spray solution containing copolymer CP and herbicide maintains herbicidal activity even under severe weather conditions, which allows more flexible application in burndown application and minimizes the risk of weeds escaping.Apart from that, the spray solution containing copolymer CP and herbicide shows good crop compatibility with certain conventional crop plants and herbicide-resistant crop plants, i.e., when the spray solution is used on these crops, the damage of crop plants is reduced and / or the damage of crop plants is not increased.Therefore, the spray solution containing copolymer CP can also be applied after the emergence of crop plants.The spray solution containing copolymer CP can also show accelerated action on harmful plants, i.e., they can have a more rapid effect on the damage of harmful plants.

[0200] Spray solutions containing the copolymer CP are also suitable for controlling weeds resistant to commonly used herbicides, such as glyphosate-resistant weeds, weeds resistant to auxin inhibitor herbicides, such as 2,4-D or dicamba, weeds resistant to photosynthesis inhibitors, such as atrazine, weeds resistant to ALS inhibitors, such as sulfonylureas, imidazolinones or triazolopyrimidines, weeds resistant to ACCase inhibitors, such as clodinafop, clethodim or pinoxaden, or weeds resistant to protoporphyrinogen-IX-oxidase inhibitors, such as sulfentrazone, flumioxazin, fomesafen or acifluorfen, such as those listed in the International Survey of Resistant Weeds (http: / / www.weedscience.org / Summary / SpeciesbySOATable.aspx). Specifically, these include resistant weeds that are resistant to glufosinate or a salt thereof, such as those listed in the International Survey of Resistant Weeds, e.g., ACCase-resistant barnyardgrass (Echinochloa crus-galli), oat (Avena fatua), black foxtail (Alopecurus myosuroides), barnyardgrass (Echinochloa colona), Japanese barnyard grass (Alopecurus japonicus), brook grass (Bromus tectorum), corngrass (Hordeum murinum), Taiwanese foxtail (Ischaemum rugosum), green foxtail (Setaria viridis), corngrass (Sorghum halepense), black foxtail (Alopecurus aequalis), common bean (Apera spica-venti), wild oat (Avena sterilis, Beckmannia szygachne, Bromus diandrus, Digitaria sanguinalis, Echinocloa oryzoidesoryzoides, Echinochloa phyllopogon, Phalaris minor, Phalaris paradoxa, Setaria faberi, Setaria viridis, Brachypodium distachyon, Bromus diandrus, Bromus sterilis, Cynosurus echinatus, Digitaria insularis, Digitaria ischaemum, Leptochloa chinensis, Phalaris brachystachis, Rotboellia cochinchinensis cochinchinensis, crabgrass (Digitaria ciliaris), Ehrharta longiflora, Eriochloa punctata, Leptochloa panicoides, ryegrass (Lolium persicum), barley (Polypogon fugax), Sclerochloa kengiana, Snowdenia polystacha, Sudangrass (Sorghum sudanese), and Brachiaria plantaginea, ALS inhibitor-resistant barnyardgrass (Echinochloa crus-galli), annual bluegrass (Poa annua), oat (Avena fatua), black foxtail (Alopecurus myosuroides, Echinochloa colona, ​​Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Conyzasumatrensis, Amaranthus retroflexus, Ambrosia artemisifolia, Conyza canadensis, Kochia scoparia, Raphanus raphanistrum, Senecio vernalis, Alopecurus japonicus, Bidens pilosa, Bromus tectorum, Chenopodium album, Conyza bonariensis, Hordeum murinum, Ischaemum rugosum, Senecio vulgaris, Setaria viridis, Sisymbrium orientale, Sorghum halepense, Alopecurus aequalis, Amaranthus blitum, Amaranthus powellii, Apera spica-venti, Avena sterilis, Brassica rapa, Bromus diandrus, Descurainia sophia, Digitaria sanguinalis, Echinochloa oryzoides, Echinochloa phyllopogon, Euphorbia heterophylla), Lactuca serriola, Phalaris minor, Phalaris paradoxa, Setaria faberi, Setaria viridis, Sinapis arvensis, Solanum melongenaptycanthum, common sowweed (Sonchus oleraceus), chickweed (Stellaria media), American blackfly (Amaranthus blitoides), Japanese bush clover (Amaranthus spinosus), common ragweed (Amaranthus viridis), giant ragweed (Ambrosia trifida), Bidens subalternans, long-horned brome (Bromus diandrus), ragweed (Bromus sterilis), shepherd's purse (Capsella bursa-pastoris), common cornflower (Centaurea cyanus), common grass (Cynosurus echinatus), common berry (Cyperus difformis), fimbristilis miliacea, and common ragweed (Galeopsis tetrahit, Galium aparine, Galium spurium, Sunflower (Helianthus annuus), False radish (Hirschfeldia incana), Yellow arrowhead (Limnocharis flava), Limnophila erecta, Corn poppy (Papaver rhoeas), American rhinoceros (Parthenium hysterophorus), Phalaris brachystachis, Bindweed (Polygonum convolvulus), Polygonum lapathifolium, Polygonum persicaria, Mountain buttercup (Ranunculus acris), Horned stalk (Rottboellia cochinchinensis, Sagittaria montevidensis, Salsola tragus, Schoenoplectus mucronatus, Setaria pumila, Sonchus asper, Xanthiumstrumarium, Ageratum conyzoides, Alisma canaliculatum, Alisma plantago-aquatica, Ammannia auriculata, Ammannia coccinea, Ammannia arvensis, Anthemis cotula, Bacopa rotundifolia, Bifora radians, Blyxa aubertii, Brassica tournefortii, Bromus japonicus, Bromus secalinus, Lithospermum arvense, Camelina microcarpa, Chamaesyce maculata, Chrysanthemum coronarium, Clidemia hirta, Crepis tectorum, Cuscuta pentagona, Cyperus brevifolis brevifolis, Cyperus compressus, Cyperus esculentus, Cyperus iria, Cyperus odoratus, Damasonium minus, Diplotaxis erucoides, Diplotaxis tenuifolia, Dopatrum junceum, Echium plantagineum, Elatine triandra, Eleocharis acicularis, Erucaria hispanica, Erysimum repandum, Galium tricornutum, Iva xanthifolia, Ixophorus unisetus, Lamium amplexicaule, Limnophilia sessiliflora, Lindernia dubia, Lindernia micrantha, Lindernia procumbens, Ludwigia prostrata, Matricaria recutita, Mesembryanthemum crystallinum, Monochoria korsakowii, Monochoria vaginalis, Myosoton aquaticum, Neslia paniculata, Oryza sativa var. sylvatica var.sylvatica), Pentzia suffruticosa, Picris hieracioides, Radish (Raphanus sativus), Oyster persica (Rapistrum rugosum), Dogwood (Rorippaindica, Rotala indica, Rotala pusilla, Rumex dentatus, Sagittaria guayensis, Sagittaria pygmaea, Sagittaria trifolia, Schoenoplectus fluviatilis, Schoenoplectus juncoides, Schoenoplectus wallichii, Sida spinosa, Silene gallica, Sinapis alba, Sisymbrium thellungii, Sorghum bicolor, Spergula arvensis, Thlaspi arvense, Tripleurospermum perforatum, Vaccaria hispanica and Vicia sativa, photosynthetic inhibitor resistant barnyardgrass (Echinochloa crus-galli), Poa annua, Alopecurus myosuroides, Echinochloa colona, ​​Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Conyza sumatrensis, Amaranthus retroflexus retroflexus, Ambrosia artemisifolia, Conyza canadensis, Kochia scoparia, Raphanus raphanistrum, Senecio vernalis, Alopecurusjaponicus, Bidens pilosa, Bromus tectorum, Chenopodium album, Conyza bonariensis, Ischaemum rugosum, Senecio vulgaris, Setaria viridis, Sisymbrium orientale, Amaranthus blitum, Amaranthus powellii, Apera spica-venti, Beckmannia syzigachne, Brassica rapa, Digitaria sanguinalis, Euphorbia heterophylla), Phalaris minor, Phalaris paradoxa, Setaria faberi, Setaria viridis, Sinapis arvensis, Solanum ptycanthum, Stellaria media, Amaranthus blitoides, Amaranthus viridis, Bidens subalternans, Brachypodium distachyon, Shepherd's purse, Chloris barbata, Cyperus difformis, Echinochloa erecta erecta), Epilobium ciliatum, Polygonum aviculare, Polygonum convolvulus, Polygonum lapathifolium, Polygonum persicaria, Portulacaoleracea, Schoenoplectus mucronatus, Setaria pumila, Solanum nigrum, Sonchus asper, Urochloa panicoides, Vulpia bromoides, Abutilon theophrasti, Amaranthus albus, Amaranthus cruentus, Arabidopsis thaliana, Arenaria serpyllifolia, Bidens tripartita, Chenopodium album, Chenopodium ficifolium, Chenopodium polyspermum polyspermum, Crypsis schoenoides, Datura stramonium, Epilobium tetragonum, Galinsoga ciliata, Matricaria discoidea, Panicum capillare, Panicum dichotomiflorum, Plantago lagopus, Polygonum hydopiper, Polygonum pensylvanicum, Polygonum monspeliensis, Rostraria, Smyrnacea, Rumex acetosella, Setaria verticillata, and Urtica urens, PS-I-electron diversion inhibitor-resistant Poa annua, Conyza sumatrensis, and Conyzacanadensis, Alopecurus japonicus, Bidens pilosa, Conyza bonariensis, Hordeum murinum, Ischaemum rugosum, Amaranthus blitum, Solanum ptycanthum, Arctotheca calendula, Epilobium ciliatum, Hedyotis verticillata, Solanum nigrum, Vulpia bromoides, Convolvulus arvensis, Crassocephalum crepidioides, Cuphea carthagensis, Erigeron philadelphicus, Gamochaeta pensylvanica, Landoltia punctata, Lepidium virginicum, Mazus fauriei, Mazus pumilus, Mitracarpus hirtus, Sclerochloa dura, Solanum americanum, and Youngia japonica, glyphosate-resistant Poa annua, Echinochloa colona), Amaranthus hybridus, Amaranthus palmeri , Amaranthus rudis, Conyza sumatrensis, Ambrosia artemisifolia, Conyza canadensis, Kochia scoparia, Raphanus raphanistrum, Bidens pilosa, Conyza bonariensis, Hordeum murinum, Sorghum halepense, Brassica rapa, Bromus diandrus, Lactuca serriola, Sonchus oleraceus, Amaranthus spinosus, Ambrosia trifida, Digitaria insularis, Hedyotis verticillata, Helianthus annuus, Parthenium hysterophorus, Plantago lanceolata, Salsola tragus, Urochloa panicoides, Brachiaria eruciformis, Bromus rubens, Chloris elata, Chloris truncata, Chloris virgata, Cynodon hirsutus, Lactuca saligna, Leptochloa virgata, Paspalum paniculatum, and Tridax procumbens, microtubule inhibitor-resistant barnyardgrass (Echinochloa crus-galli), annual bluegrass (Poa annua), wild oat (Avenafatua, black foxtail (Alopecurus myosuroides), palmeri (Amaranthus palmeri), green foxtail (Setaria viridis), sorghum (Sorghum halepense), alopecurus aequalis, beckmannia syzigachne, and Fumaria densifloria, auxin herbicide resistant barnyardgrass (Echinochloa crus-galli), horsegrass (Echinochloa colona), amaranthus hybridus, amaranthus rudis, conyza sumatrensis, kochia scoparia, radish (Raphanus sativus), and other herbicides. raphanistrum, Chenopodim album, Sisymbrium orientale, Descurainia sophia, Lactuca serriola, Sinapis arvensis, Sonchus oleraceus, Stellaria media, Arctotheca calendula, Centaurea cyanus, Digitaria ischaemum, Fimbristylis miliacea, Galeopsis tetrahit, Galium aparine, Galium spurium, Hirschfeldia incana, Limnocharis flava, Limnocharis erecta, Papaver rhoeas, Plantago lanceolata, Ranunculus acris, Musk thistle, Carduusnutans, Carduus pycnocephalus, Centaurea soltitialis, Centaurea stoebe ssp.Micranthos, Cirsium arvense, Commelina diffusa, Echinochloa crus-pavonis, Soliva sessilis, and Sphenoclea zeylanica, HPPD inhibitor resistant Amaranthus palmeri and Amaranthus rudis, PPO inhibitor resistant Acalypha australis, Amaranthus hybridus, Amaranthus palmeri, Amaranthus retroflexus, Amaranthus rudis, Ambrosia artemisifolia, Avena fatua, Conyza sumatrensis, Descurainia sophia, Euphorbia heterophylla, Senecio vernalis, carotenoid biosynthesis inhibitor resistant Hydrilla verticillata, Raphanus raphanistrum, Senecio vernalis, and Sisymbrium orientale, VLCFA inhibitor-resistant black grass (Alopecurus myosuroides), oat (Avena fatua), and barnyard grass (Echinochloa crus-galli).

[0201] Spray solutions containing copolymer CP are suitable for the control / elimination of common harmful plants in agricultural land (i.e. in crops) planted with useful plants. The mixtures of the invention are generally suitable for the burndown of undesirable vegetation in agricultural land of the following crops:

[0202] Cereal crops, such as cereals (small grain crops), for example wheat (Triticum aestivum) and wheat-like crops, for example durum wheat (T. durum), einkorn (T. monoccum), emmer wheat (T. dicoccon) and spelt (T. spelta), rye (Secale cereale), Tritiosecale, barley (Hordeum vulgare); maize (Zea mays); sorghum (for example Sorghum bicolour); rice (Oryza spp., for example Oryza sativa and Oryza glaberrima); and sugar cane, etc.; Legumes (Fabaceae), such as, for example, soybean (Glycine max.), groundnut (Arachis hypogaea) and pulse crops, such as peas, such as Pisum sativum, pigeon pea and cowpea, broad beans, such as Vicia faba, Vigna spp. and Phaseolus spp., and lentils, such as lens culinaris var.; Brassicaceae, such as canola (Brassica napus), rapeseed (OSR, (Brassica napus), cabbage (B. oleracea var.), mustard, such as B. juncea, B. campestris, B. narinosa, B. nigra and B. tournefortii; and turnip (Brassica rapa var.); Other broadleaf crops, such as sunflower, cotton, flax, linseed, sugar beet, potato and tomato; TNV crops (TNV: trees, nuts and vines), such as grapes, citrus fruits, pome fruits such as apple and pear, coffee trees, pistachios and oil palm, stone fruits such as peaches, almonds, walnuts, olives, cherries, plums and apricots; Transplanting turf, pasture and rangeland; Onion and garlic; Ornamental bulbous plants, such as tulips and daffodils; Coniferous and deciduous trees, such as pines, firs, oaks, maples, dogwoods, hawthorns, crabapples, and buckthorns (buckthorn); and Ornamental garden plants such as roses, petunias, marigolds and snapdragons.

[0203] In one embodiment, the method for controlling undesirable vegetation is applied to cultivated rice, corn, legume crops, cotton, canola, small grains, soybeans, peanuts, sugarcane, sunflowers, plantation crops, tree crops, nuts, or grapes. In another embodiment, the method is applied to a cultivated crop selected from glufosinate tolerant crops.

[0204] Spray solutions containing copolymer CP are particularly suitable for burning down undesirable vegetation in agricultural fields of the following crop plants: small grains such as wheat, barley, rye, triticale and durum wheat, rice, maize (corn), sugarcane, sorghum, soybean, legume crops such as peas, beans and lentils, groundnuts, sunflowers, sugar beets, potatoes, cotton, Brassica crops such as rape, canola, mustard, cabbage and turnip, transplants. turf, pasture, rangeland, grapes, pome fruits such as apple and pear, stone fruits such as peaches, almonds, walnuts, pecans, olives, cherries, plums and apricots, citrus fruits, coffee, pistachios, ornamental horticultural plants such as roses, petunias, marigolds, snapdragons, ornamental bulbous plants such as tulips and daffodils, coniferous and deciduous trees such as pines, firs, oaks, maples, dogwoods, hawthorns, crabapples and buckthorns.

[0205] The herbicidal composition is most suitable for burning down undesirable vegetation in agricultural fields of the following crop plants: small grains such as wheat, barley, rye, triticale and durum wheat, rice, corn, sugarcane, sorghum, soybeans, legume crops such as peas, beans and lentils, peanuts, sunflowers, cotton, Brassica crops such as rapeseed, canola, transplants, pastures, rangelands, grapes, stone fruits such as peaches, almonds, walnuts, pecans, olives, cherries, plums and apricots, citrus fruits and pistachios. EXAMPLES

[0206] I. Abbreviation: AMS Ammonium Sulfate Days since DAT processing fl oz Fluid ounce fl gal fluid gallon GAP Fluid Gallons Per Acre ha hectare ae acid equivalent

[0207] II. Production of copolymers CP1-CP5: The following monomers were used in the production of the copolymer CP: AMPS-Na: Commercial grade 2-acrylamido-2-methylpropanesulfonic acid sodium salt as a 50 wt% aqueous solution. AM: Commercial grade acrylamide as a 50% by weight solution in water DIMAPA-Q 3-Dimethylaminopropylacrylamide quaternized with methyl chloride Monomer Mc-1: Monomer of formula H2C=CH-O-(CH2)4-O-(EO) prepared according to Example M / 25 of WO 2014 / 095608 A1 24.5 -(BuO) 16 -(EO) 3.5 H monomer Monomer Mc-1: Monomer of formula H2C=CH-O-(CH2)4-O-(EO) prepared according to Example M / 25 of WO 2014 / 095608 A1 24.5 -(BuO) 22 -(EO) 3.5 H monomer

[0208] In the monomers Mc-1 and Mc-2, EO refers to CH2CH2O, and BuO refers to CH2CH(CH2CH3)O and CH(CH2CH3)CH2O.

[0209] The polymers were prepared by a method analogous to the standard protocol of Example C1 on page 43 of WO 2014 / 095608, using the relative amounts of the corresponding monomers shown in Table 1 below, with the relative amounts given as pphm (parts per hundredth of monomer).

[0210] [Table 1]

[0211] All copolymers CP1-CP5 had weight average molecular weights in the range of 1,000,000-30,000,000 g / mol. The intrinsic viscosities of CP1-CP5 were estimated with respect to the Marc-Houwink equation (1) and were determined to be at least 200 cm^2 with reference to the intrinsic viscosity of aqueous solutions of copolymer CP in 0.5 M aqueous NaCl at 30°C. 3 / g.

[0212] For comparison, a commercially available polyacrylamide homopolymer (polymer CP6), namely Magnafloc 351, was used.

[0213] III. Field Testing Protocol, Polymer Adjuvant with Glufosinate or Glyphosate Herbicides: (1) Field trials 1 and 2 using glufosinate Glufosinate was used as a commercially available SL formulation in water (Liberty® 280 SL from BASF SE) containing 24.5 wt. % glufosinate ammonium.

[0214] The fields were seeded with glufosinate resistant soybean (Glycine max) at a rate of 140,000 seeds / acre with 30 inch row spacing. The glufosinate resistant soybean seeds for each test are listed in the test tables below. Weed pests were naturally present at the test locations and are defined in the tables below listing the test results.

[0215] Each treatment plot was 30 feet long and 6.67 feet wide, providing a treatment area of ​​200 square feet. The plots were arranged in a grid pattern. A randomized complete block (RCB) study design was used to create four replicate applications for each treatment. Treatments were administered when weed height averaged 6-8 inches.

[0216] Spray solutions were prepared at 1.4 fl oz per fl gal of Liberty 280 SL. Copolymer CP and optionally AMS were included at concentrations defined in Tables 2-3 below. Treatments were applied using an ATV (all terrain vehicle) equipped with a 6.67 foot boom and XR 11006 nozzles spaced 20 inches apart. The spray tank was operated at 40 psi pressure for a spray volume of 15 gallons / acre (approximately 140 L / ha) and the ATV's ground speed during application was 11.9 mph.

[0217] The application rate of Liberty® 280 SL was 22 fl oz / acre corresponding to 400 g / ha of glufosinate ammonium.

[0218] Observations were made on soybean (negative control) and weed species at 14 and 28 days after treatment (DAT) using a scale commonly used by agronomists ranging from 0% for no control to 100% for complete control. Results were subjected to analysis of variance statistical analysis, a standard technique in interpreting field trial data.

[0219] Field trial 3 with glyphosate: Glyphosate was used as Touchdown HiTech from Syngenta Crop Protection, LLC, a commercially available aqueous SL formulation containing 52.3% by weight monopotassium glyphosate.

[0220] The fields were seeded with glyphosate resistant soybean (Glycine max) at a rate of 142,000 seeds / acre with 30 inch row spacing. The glyphosate resistant soybean seeds for each test are listed in the trail table below. Weed pests were naturally present at the test sites and are defined in the table below listing the test results.

[0221] Each treatment plot was 25 feet long and 6.67 feet wide, providing a treatment area of ​​167 square feet. The plots were arranged in a grid pattern. A randomized complete block (RCB) study design was used to create four replicate applications for each treatment. Treatments were administered when weed height averaged 6-8 inches.

[0222] Spray solutions were prepared at 5 lb ae (acid equivalent) per fl gal of Touchdown HiTech. Copolymer CP was included at the concentrations defined in Table 4 below. Treatments were applied using a backpack sprayer equipped with a 6.67 foot boom and XR 8002 nozzles spaced 20 inches apart. The spray tank was operated at 27 psi pressure for a spray volume of 15 gallons / acre.

[0223] The application rate of Touchdown HiTech was 8 fl oz / acre (0.313 lb ae / acre of glyphosate), corresponding to 350 g / ha of glyphosate.

[0224] Observations were made on soybean (negative control) and weed species at 14 and 28 days after treatment (DAT) using a scale commonly used by agronomists ranging from 0% for no control to 100% for complete control. Results were subjected to analysis of variance statistical analysis, a standard technique in interpreting field trial data.

[0225] Field Trial 1: Trials were conducted in crops of glufosinate resistant soybean subvariety Becks 298L4. The results are summarized in Table 2 below.

[0226] Field trial 2: The trial was conducted in a crop of glufosinate resistant soybean subvariety LL Credenz CZ2915L. The results are summarized in Table 3 below.

[0227] Field Trial 3: Trials were conducted in crops of glyphosate resistant soybean subvariety Stine 32EA12. The results are summarized in Table 4 below.

[0228] [Table 2]

[0229] [Table 3]

[0230] [Table 4]

[0231] IV. Greenhouse Test Protocol, Polymer Adjuvant with Dicamba Herbicide: The dicamba was used as ENGENIA® from BASF SE, a commercially available SL formulation in aqueous solution containing 48% by weight dicamba in the form of its N,N-bis(3-aminopropyl)methylamine salt.

[0232] A greenhouse study was conducted to evaluate the effect of the copolymers of the present invention on the weed control efficacy of dicamba. Chenopodium album (CHEAL), velvetleaf (Abutilon theophrasti (ABUTH)), and waterhemp (Amaranthus tuberculatus (AMATA)) seedlings were grown in 10 × 10 × 10 cm pots filled with Metro-Mix 360 medium (Sun Gro Horticulture, Agawam, MA). Weeds were treated with postemergence applications of 560 g ae / ha dicamba (Engenia herbicide (BASF Agricultural Products, RTP, NC)), alone and in combination with various concentrations of copolymers (20–100 ppm). All treatments were in the form of a nonionic surfactant blend (Induce® (Helena Agri-Enterprises, Collierville, TN): alkyl aryl polyoxyalkane ether (alkyl aryl ether), 1,2-dichlorophenyl ether (1,2-dichlorophenyl ... The mixtures contained 0.25% v / v of an adjuvant based on CP1 (a proprietary blend of polyoxylkane ether, alkanolamide, dimethylsiloxane, and free fatty acid) and were applied at a spray volume of 140 l / ha using a TeeJet AIXR 110015 nozzle (Spraying Systems, Wheaton, IL) when the weeds were approximately 10 cm tall. All mixtures produced stable, clear spray solutions. Some reduction in the width of the spray pattern was observed at the 80 ppm and 100 ppm concentrations of copolymer CP1. A visual assessment of weed control was made on a scale of 0% (no damage) to 100% (complete control).

[0233] [Table 5]

[0234] Weed control responses varied by species, but addition of CP1 provided consistent improvements in control with increasing concentrations. ABUTH was generally less responsive to dicamba, with increases in control plateauing at approximately 20-30 ppm with CP1, while AMATA and CHEAL were more responsive to dicamba, with improvements with DRP continuing up to 40-80 ppm. Amaranthus species such as AMATA are much more troublesome weeds, and an increase in control of over 5% represents a significant benefit to farmers.

Claims

1. 1. A method for improving the efficacy of a herbicide, comprising applying an aqueous spray of said herbicide in combination with a copolymer CP, said copolymer CP being made from repeat units of a polymerized ethylenically unsaturated monomer M, said polymerized ethylenically unsaturated monomer M being a) from 75 to 98% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Ma selected from the group consisting of primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms; b) 2 to 25 wt. % of one or more monomers Mb, based on the total weight of the ethylenically unsaturated monomers M, wherein at least one monomer Mb is selected from the group consisting of monoethylenically unsaturated sulfonic acids and salts thereof; c) 0 to 5% by weight, based on the total weight of ethylenically unsaturated monomers M, of terminal OH groups or terminal C １ ~C ６ At least one polyC having an alkoxy group ２ ~C ６ one or more monoethylenically unsaturated monomers Mc having an alkylene oxide moiety in addition to the moiety having an ethylenically unsaturated double bond, The total amount of monomers Ma and Mb is at least 95% by weight, based on the total weight of ethylenically unsaturated monomers M, and the total amount of monomers Mb and Mc is 2 to 25% by weight, based on the total weight of ethylenically unsaturated monomers M.

2. The method of claim 1 , wherein the monomer Ma is acrylamide.

3. 2. The method of claim 1, wherein the monomer Mb.1 is 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof.

4. The monomer M forming the copolymer is a) 75 to 98% by weight of acrylamide, based on the total weight of the ethylenically unsaturated monomers M; and 2. The method of claim 1, wherein the ethylenically unsaturated monomers M comprise from 2 to 25% by weight of 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, based on the total weight of the ethylenically unsaturated monomers M.

5. 2. The method of claim 1, wherein the monomers M forming the copolymer comprise 0.5 to 5% by weight of at least one monomer Mc, based on the total weight of the monomers M.

6. 2. The method of claim 1, wherein the copolymer CP in its sodium salt form has a weight average molecular weight Mw of at least 100,000 g / mol, specifically at least 250,000 g / mol, more specifically at least 500,000 g / mol, as determined by gel permeation chromatography.

7. The copolymer CP in its sodium salt form has a viscosity of at least 50 cm, determined at 30° C., for a solution of the copolymer CP in 0.5 M aqueous sodium chloride solution. ３ / g, specifically at least 100 cm ３ / g, preferably at least 150 cm ３ / g, in particular at least 200 cm ３ The method of claim 1, wherein the polymer has an intrinsic viscosity [η] of 1 / g.

8. 10. Use of the copolymer CP according to claim 1 for improving the efficacy of herbicides.

9. 9. The method according to claim 1 or the use according to claim 8, wherein the copolymer CP is applied in an amount of 5 to 500 ppm, in particular in an amount of 10 to 300 ppm, more preferably in an amount of 10 to 200 ppm, especially in an amount of 10 to 100 ppm, based on the total weight of the aqueous spray.

10. The spray liquid has the property (1), (2), or (3), i.e., (1) The spray liquid has a pH within the range of pH 4 to pH 9 as determined at 25°C; (2) The spray liquid additionally contains an inorganic salt or a salt of an organic acid; (3) The method according to claim 1 or the use according to claim 8, wherein the spray liquid additionally has at least one of the following properties: it contains an ammonium salt, in particular ammonium sulfate.

11. The herbicide is (i) herbicides of the group of glutamine synthetase inhibitors, (ii) herbicides from the group of 5-enolpyruvylshikimate-3-phosphate synthase inhibitors (EPSP synthase inhibitors); (iii) herbicides from the group of auxin agonists, (iv) herbicides from the group of protoporphyrinogen oxidase inhibitors (PPO inhibitors), (v) herbicides from the group of acetolactate synthase inhibitors (ALS inhibitors), (vi) herbicides from the group of photosystem II inhibitors (PS II inhibitors), (vii) herbicides of the group of the hydroxyphenylpyruvate dioxygenase inhibitors (HPPD inhibitors), (viii) herbicides from the group of the acetyl CoA carboxylase inhibitors (ACCase inhibitors), 9. The method of claim 1 or the use of claim 8, wherein the organic herbicide compound is selected from the group consisting of: and combinations thereof.

12. 12. The method or use of claim 11, wherein the organic herbicide compound comprises at least one herbicide compound selected from the group consisting of glufosinate, bialaphos, glyphosate, dicamba, chloramben, 2,4-D, endothal, mecoprop, picloram, triclopyr, fluroxypyr, 2,4,5-T, benzac, MCPA, MCPB, dichlorprop, dichlorprop-P, imazamox, imazapyr, imazapic, imazethapyr, imazaquin, cloransulam, chlorimuron, acifluorfen, saflufenacil, fomesafen, acifluorfen, atrazine, propanil, bentazone, diuron, quizalofop, clethodim, pinoxaden, topramezone, mesotrione, salts thereof, esters thereof, and combinations thereof.

13. 13. The method or use of claim 12, wherein the organic herbicide compound comprises at least one herbicide compound selected from the group consisting of glufosinate, dicamba, glyphosate, and salts thereof.

14. 1. An aqueous spray solution comprising a herbicide compound and a copolymer CP, wherein the copolymer CP comprises: a) from 75 to 98% by weight, based on the total weight of the ethylenically unsaturated monomers M, of at least one monomer Ma selected from the group consisting of primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms; b) 2 to 25 wt. % of one or more monomers Mb, based on the total weight of the ethylenically unsaturated monomers M, wherein the monomer Mb is at least one monomer Mb selected from the group consisting of monoethylenically unsaturated sulfonic acids and salts thereof.

15. The copolymer CP has one of the following properties i), ii), iii), iv), v), iv) or vii), namely: i) the monomer Ma is acrylamide; ii) the monomer M comprises 2 to 20% by weight of at least one monomer Mb.1; ii) the monomer Mb.1 is 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof; iv) the monomer M is a) 80 to 98% by weight of acrylamide, based on the total weight of the ethylenically unsaturated monomers M; and b) 2 to 20% by weight of a monomer Mb.1, specifically 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, based on the total weight of the ethylenically unsaturated monomer M; v) the copolymer CP in its sodium salt form has a weight average molecular weight Mw of at least 100,000 g / mol, specifically at least 250,000 g / mol, more specifically at least 500,000 g / mol, as determined by gel permeation chromatography; vi) the copolymer CP in its sodium salt form has a viscosity of at least 50 cm, determined at 30° C., in the case of a solution of the copolymer CP in 0.5 M aqueous sodium chloride solution. ３ / g, specifically at least 100 cm ３ / g, preferably at least 150 cm ３ / g, in particular at least 200 cm ３ 15. The aqueous spray liquid according to claim 14, having at least one of the following properties: an intrinsic viscosity [η] of 1 / g.

16. The spray liquid has the property (1), (2), or (3), i.e., (1) The spray liquid has a pH within the range of pH 4 to pH 9 as determined at 25°C; (2) The spray liquid additionally contains an inorganic salt or a salt of an organic acid; (3) The aqueous spray liquid according to claim 14 or 15, wherein the spray liquid additionally has at least one of the following properties: it contains an ammonium salt, specifically ammonium sulfate.