Solid preparation of insecticidal mixture with excellent dispersing performance

Abstract

The present invention relates to solid formulations of tetramic acid derivatives in the form of water dispersible granules and mixtures of these tetramic acid derivatives, which disintegrate particularly well in water and yet have good long-term stability; the invention also relates to a method for preparing the same and to the use thereof for applying the contained active ingredients.

Description

[0001] The present invention relates to solid preparations of tetramic acid derivatives, in particular water-dispersible granules, and mixtures of these tetramic acid derivatives, which are particularly efficient in disintegrating in water and still have good long-term stability, as well as methods for their preparation and their use for administering the active ingredients contained therein.

[0002] The use of formulation adjuvants described in the prior art to prepare WG formulations can result in formulations with undesirable properties. For example, the proportion of insoluble components or the presence of certain active ingredients can have the effect of causing the granules to disintegrate poorly (i.e., incompletely or too slowly) or dissolve poorly after being placed in water. The slow disintegration of the granules can then have the effect of causing sediment to remain, nozzle clogging, or a reduction in the concentration of active ingredients in the spray liquid and the associated efficacy.

[0003] WO2019197631 describes water-dispersible granules of tetramic acid derivatives and mixtures of these tetramic acid derivatives. However, it does not describe additives that are specifically used to improve the solubility properties.

[0004] US2015 / 0164068 describes storage-stable WG formulations with excellent efficacy, which contain active ingredients of different particle sizes and 75% by weight of a poorly hygroscopic water-soluble carrier in the form of an inorganic salt. The preferred carriers mentioned are ammonium sulfate and potassium sulfate, while potassium bicarbonate is only listed as a carrier in a long list in general terms without examples. In addition, the examples do not disclose the explicit use of potassium bicarbonate.

[0005] Compared to US 2015 / 0164068, potassium bicarbonate is present only in much smaller amounts in the compounds according to the invention, and it can react, especially together with another basic salt, and have an adverse effect on the storage stability.

[0006] WO2020 / 240394 describes WG formulations containing a "disintegration system". They also contain inorganic salts, including bicarbonate. However, in this case, no other potentially decomposable salts are present in the formulation, so it is expected that there will be no adverse effect on storage stability. In addition, potassium bicarbonate is not explicitly used in the examples herein, but commonly used potassium sulfate is used.

[0007] Additionally, the widespread use of bicarbonate salts together with acids such as citric acid in dissolving tablets is known.

[0008] We have now surprisingly found that the formulations according to the invention have particularly advantageous properties with regard to storage stability and rapid dissolution.

[0009] We have surprisingly found that the addition of a specific amount of an inorganic carbonate (especially a bicarbonate) ensures that the granules dissolve faster and better even in the presence of alkaline ammonium salts, without adversely affecting the storage stability of the granules (especially also at elevated temperatures).

[0010] A further feature of the preparations according to the invention is that they have good suspendability even under high salt loads, in particular also after storage.

[0011] These formulations then form the subject of the present invention. The invention also relates to a process for the preparation of these water-dispersible granules and to their use for application.

[0012] Therefore, the present invention provides a pesticidal solid composition in the form of a water dispersible granule (solid preparation), which preferably comprises:

[0013] a. Tetramic acid derivatives of formula (I) as component a

[0014]

[0015] in

[0016] W and Y are independently hydrogen, C1-C4 alkyl, chlorine, bromine, iodine or fluorine,

[0017] X is C1-C4 alkyl, C1-C4 alkoxy, chlorine, bromine or iodine,

[0018] A, B and the carbon atoms to which they are bonded are a C3-C6 cycloalkyl group substituted by an alkylenedioxy group, which is optionally substituted by a C1-C4 alkyl group or a C1-C4 alkoxy-C1-C2 alkyl group, and together with the carbon atoms to which they are bonded form a five-membered or six-membered ketal,

[0019] G is hydrogen (a) or one of the following groups,

[0020] E(d)

[0021] in

[0022] E is a metal ion or an ammonium ion,

[0023] M is oxygen or sulfur,

[0024] R 1 is a straight chain or branched C1-C6 alkyl group,

[0025] R 2 is a straight chain or branched C1-C6 alkyl group,

[0026] b. at least one basic salt,

[0027] c. at least one further inorganic salt selected from the group consisting of carbonates and bicarbonates, with the exception of ammonium as cation. Unless explicitly included, ammonium salts of carbonates and bicarbonates are not considered as component c) in the present invention,

[0028] d. at least one dispersant,

[0029] e. at least one wetting agent,

[0030] f. at least one filler,

[0031] g. optional structure forming agent,

[0032] h. Optional other active ingredients, and

[0033] i. Optional other commonly used adjuvants and formulation aids.

[0034] In the present invention, in formulae, for example in formula (I), unless otherwise indicated, optionally substituted groups may be mono- or polysubstituted, wherein in the case of polysubstitution the substituents may be identical or different.

[0035] Furthermore, within the preferred scope of the present invention, it should be understood that different preferred levels can be arranged and combined with each other; but in any case, the same preferred levels, especially the most preferred embodiments / preferred levels in each case, are to be combined with each other and are indeed disclosed in such combinations.

[0036] Compositions as described above consisting only of the essential components (and no optional components) should also be considered disclosed.

[0037] Unless otherwise stated, percentages are to be considered as percentages by weight, wherein the weight % of the composition add up to 100.

[0038] Unless otherwise defined, "alkaline" in the context of the present invention refers to a pH value of an aqueous solution of pH>7.

[0039] The pH of the aqueous dispersion of the preparation according to the invention is >7.

[0040] In a preferred embodiment, the formulation contains at least one defoaming agent (i), preferably solid, preferably based on silicone oil or wax, further preferably PDMS adsorbed on a solid support.

[0041] Preferred defoamers are: Rhodorsil defoamer EP6703 (absorbed polydimethylsiloxane).

[0042] a) Active ingredients

[0043] In a preferred embodiment, component a) in the composition of the present invention is a compound of formula (I)

[0044]

[0045] The compounds of formula (I) have the following definitions:

[0046] W is a methyl group,

[0047] X is chlorine or methyl,

[0048] Y is chlorine, bromine or methyl,

[0049] A, B and the carbon atom to which they are bonded are a saturated C6 cycloalkyl group substituted by an alkylenedioxy group, which together with the carbon atom to which it is bonded forms a five-membered or six-membered ketal,

[0050] G is hydrogen (a) or one of the following groups,

[0051] E(d),

[0052] in

[0053] M is oxygen,

[0054] E is a metal ion equivalent or an ammonium ion,

[0055] R 1 is a straight chain or branched C1-C4 alkyl group,

[0056] R 2 It is a straight chain or branched C1-C4 alkyl group.

[0057] In a further preferred embodiment, component a) in the composition of the present invention is a compound of formula (I)

[0058] It has

[0059]

[0060] In a particularly preferred embodiment, component a) is a compound of the formula

[0061]

[0062] b) Basic salts

[0063] Component b) is preferably selected from inorganic alkaline ammonium salts, excluding carbonates and hydrogencarbonates.In the context of the present invention, unless explicitly mentioned otherwise, alkaline salts b) are not carbonates.

[0064] Further preferably, b) is selected from diammonium hydrogen phosphate (DAHP).

[0065] c) further inorganic salts selected from the group consisting of inorganic carbonates and bicarbonates, excluding the ammonium salts thereof.

[0066] Further preferably, c) is selected from bicarbonates.

[0067] Sodium bicarbonate and potassium bicarbonate are particularly preferred.

[0068] d) Dispersants

[0069] Suitable dispersants within the scope of the present invention are dispersants of the polycarboxylic acid type, for example those such as hydrophobically modified comb polymers, for example polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins (such as isobutylene or diisobutylene), copolymers of acrylic acid with itaconic acid, copolymers of methacrylic acid with itaconic acid, copolymers of maleic acid or maleic anhydride with styrene, copolymers of acrylic acid with methacrylic acid, copolymers of acrylic acid with methacrylates, copolymers of acrylic acid with vinyl acetate, copolymers of styrene with methacrylic acid, modified copolymers of styrene with methacrylic acid, copolymers of maleic acid or maleic anhydride with acrylic acid; N-methyl fatty acids (e.g. C8-C 18 ) sarcosinate; carboxylic acids such as resin acids or fatty acids (e.g. C8-C 18 ) or a salt of such a carboxylic acid, such as an alkali metal or alkaline earth metal salt (preferably Ca, Mg). The above copolymers may also be present in the form of their salts, such as alkali metal salts (preferably Li, Na, K), alkaline earth metal salts (preferably Ca, Mg), ammonium or various amines.

[0070] Further preferred are dispersants selected from the group consisting of sodium salts of copolymers of maleic acid with olefins (eg Geropon T / 36 / Solvay, DURAMAX D-305 / Dow) and sodium salts of copolymers of methacrylic acid with styrene (TERSPERSE 2700 / Indorama, Atlox Metasperse 500S / Croda).

[0071] The dispersant is more preferably a sodium salt of a copolymer of methacrylic acid and styrene.

[0072] The additional addition of stearates, in particular magnesium stearate, is particularly preferred.

[0073] e) Wetting agent

[0074] Useful nonionic surfactants include all such substances which can usually be used in agrochemical compositions. Preferred mention may be made of polyethylene oxide-polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and / or propylene oxide, and polyvinyl alcohol, polyvinyl pyrrolidone, copolymers of polyvinyl alcohol and polyvinyl pyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic esters, furthermore also alkyl ethoxylates and alkylaryl ethoxylates, which may optionally be phosphated and optionally neutralized with a base, sorbitol ethoxylates being mentioned by way of example, and polyoxyalkylene amine derivatives.

[0075] Suitable anionic surfactants include all such substances which can usually be used in agrochemical compositions.

[0076] Useful wetting agents are preferably anionic surfactants selected from the group consisting of salts of polystyrenesulfonic acid, salts of polyvinylsulfonic acid, salts of naphthalenesulfonic acid-formaldehyde condensation products, salts of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde condensation products, and salts of ligninsulfonic acid and sodium salts of alkylated naphthalenesulfonic acids (e.g. EFW), and the sodium salt of dioctyl sulfosuccinate (e.g. OT-B, SDS), and block polymers of propylene oxide and ethylene oxide on ethylenediamine (e.g. T / 905).

[0077] More preferably, suitable wetting agents (e) in the context of the present invention are selected from the sodium salts of alkylated naphthalenesulfonic acids (e.g. EFW) and the sodium salt of dioctyl sulfosuccinate (e.g. OT-B, SDS).

[0078] f) Filling

[0079] Useful inert filler materials are all substances which can usually be used for this purpose in agrochemical compositions. Preference is given to inorganic particles, such as silicates and oxides, and organic substances, such as urea-formaldehyde condensates and cellulose (e.g. Ulmer Weiss 6AL, Celite 209, Argirec B21 and B22, Bentone EW, Luz2 talc, Etiquette Violette). Examples include kaolin, rutile, silicon dioxide, highly dispersed silicon dioxide, silica gel, and natural and synthetic silicates, and also talc.

[0080] The filler is further preferably selected from kaolin, rutile and silica. Kaolin is particularly preferred.

[0081] g) Structure forming agent

[0082] The preparations according to the invention may also contain structure forming agents. Particularly suitable for this purpose are polyacrylic acid and its salts (especially cross-linked polyacrylic acid salts), as well as polyurethanes and derivatized polyurethanes and their salts. Examples of such suitable acrylic resins (acrylates) are: polymethacrylates, polymethyl methacrylates, polyacrylamides, polyethoxyethyl methacrylates, and polymethylurea resins such as M.

[0083] The structure forming agent is more preferably a polymethyl urea resin.

[0084] h) Other active ingredients

[0085] The formulations may in principle comprise one or more further effective agrochemical ingredients, which are preferably selected from the group consisting of insecticides, herbicides, fungicides and host defence inducers.

[0086] Preferred other active ingredients are one or more selected from insecticides, and are further preferably selected from imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, deltamethrin, flubendiamid, tetraniliprole, cyclaniliprole, spirodiclofen, spiromesifen, spirotetramat, avermectin abamectin, acrinathrin, chlorfenapyr, emamectin, ethiprole, fipronil, flonicamid, flupyradifurone, indoxacarb, metaflumizone, methoxyfenozid, milbemycin, pyridaben, pyridalyl, silafluofen, spinosad, spinetoram, sulfoxaflor, triflumuron.

[0087] Particularly preferred are one or more other active ingredients selected from ethiprole, spinetoram, avermectin and flupyradone.

[0088] i) Adjuvants and formulation aids

[0089] Useful antifoams are all substances which can usually be employed for this purpose in agrochemical compositions. Preference is given to silicone oil-based antifoams and magnesium stearate.

[0090] Further preferred are solid defoamers or defoamers adsorbed or absorbed onto a carrier.

[0091] Polydimethylsiloxanes absorbed onto a solid matrix are particularly preferred. An example is Rhodorsil defoamer EP6703.

[0092] Useful preservatives include all such substances which can usually be employed for this purpose in agrochemical compositions. Examples include isothiazolinones (e.g. (from LANXESS AG)) and 1,2-benzisothiazolin-3-one (e.g. ).

[0093] Useful antioxidants are all substances which can usually be employed for this purpose in agrochemical compositions. Butylated hydroxytoluene is preferred.

[0094] Useful dyes are all substances which can usually be employed for this purpose in agrochemical compositions. Examples include titanium dioxide, pigment black, zinc oxide and blue pigments, and also Permanent Red FGR.

[0095] In a preferred embodiment, the present invention provides a pesticidal solid composition in the form of water dispersible granules, comprising:

[0096] a. Compounds of formula (I)

[0097]

[0098] The compounds of formula (I) have the following definitions:

[0099] W is a methyl group,

[0100] X is chlorine or methyl,

[0101] Y is chlorine, bromine or methyl,

[0102] A, B and the carbon atom to which they are bonded are a saturated C6 cycloalkyl group substituted by an alkylenedioxy group, which together with the carbon atom to which it is bonded forms a five-membered or six-membered ketal,

[0103] G is hydrogen (a) or one of the following groups,

[0104] E(d),

[0105] in

[0106] M is oxygen,

[0107] E is a metal ion equivalent or an ammonium ion,

[0108] R 1 is a straight chain or branched C1-C4 alkyl group,

[0109] R 2 A straight chain or branched C1-C4 alkyl

[0110] b. at least one inorganic alkaline ammonium salt,

[0111] c. another inorganic salt selected from carbonates and bicarbonates,

[0112] d. at least one dispersant of the polycarboxylic acid type,

[0113] e. at least one anionic wetting agent,

[0114] f. at least one inert filler,

[0115] g. optional structure forming agent,

[0116] h. other optional effective insecticidal ingredients,

[0117] i. Optional other adjuvants.

[0118] In a further preferred embodiment, the present invention provides a pesticidal solid composition in the form of water dispersible granules, comprising:

[0119] a. a compound of formula (I) selected from the following compounds:

[0120]

[0121] b. at least one inorganic alkaline ammonium salt selected from diammonium hydrogen phosphate (DAHP),

[0122] c. at least one inorganic bicarbonate salt wherein the cation is not ammonium,

[0123] d. at least one dispersant of the polycarboxylic acid type selected from the group consisting of hydrophobically modified comb polymers including polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins, copolymers of acrylic acid with itaconic acid, copolymers of methacrylic acid with itaconic acid, copolymers of maleic acid or maleic anhydride with styrene and modified copolymers of maleic acid or maleic anhydride with styrene, copolymers of acrylic acid with methacrylic acid, copolymers of styrene with methacrylic acid, modified copolymers of styrene with methacrylic acid, copolymers of acrylic acid with methacrylate, copolymers of acrylic acid with vinyl acetate, copolymers of maleic acid or maleic anhydride with acrylic acid), N-methyl fatty acids (e.g. C8-C 18 ) sarcosinate, carboxylic acid such as resin acid or fatty acid (e.g. C8-C 18 ) or salts of such carboxylic acids, and salts of such copolymers,

[0124] e. at least one anionic wetting agent selected from the group consisting of sodium salts of alkylated naphthalenesulfonic acids and sodium salts of dioctylsulfosuccinic acid,

[0125] f. at least one inert filler selected from carbonates, silicates and oxides, and urea-formaldehyde condensates and cellulose,

[0126] g. optionally a structure forming agent selected from polyacrylic acid and its salts, cross-linked polyacrylates and polyureas, polyurethanes and derivatized polyureas and polyurethanes,

[0127] h. other optional effective insecticidal ingredients,

[0128] i. Optional other adjuvants.

[0129] In a particularly preferred embodiment, the present invention provides a pesticidal solid composition in the form of water dispersible granules, comprising:

[0130] a. A compound of formula (I-2) having the following structure:

[0131]

[0132] b. at least one inorganic alkaline ammonium salt selected from diammonium hydrogen phosphate (DAHP),

[0133] c. at least one inorganic bicarbonate selected from sodium bicarbonate and potassium bicarbonate,

[0134] d. at least one dispersant selected from the group consisting of sodium salts of copolymers of methacrylic acid and styrene and sodium salts of modified copolymers of methacrylic acid and styrene,

[0135] e. at least one anionic wetting agent selected from the group consisting of sodium salts of alkylated naphthalenesulfonic acids and sodium salts of dioctylsulfosuccinic acid,

[0136] f. at least one inert filler selected from kaolin, rutile and silica,

[0137] g. optionally a structure forming agent selected from polymethyl urea resins,

[0138] h. other optional effective insecticidal ingredients,

[0139] i. Optional other adjuvants.

[0140] In an alternative embodiment, other effective insecticidal ingredients (g) are essential in the above embodiment, and are preferably selected from imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, deltamethrin, flubendiamide, tetrazobactam, cyclobromofenamide, spirodiclofen, spiromesifen, spirotetramat, abamectin, fluthrin, chlorfenapyr, avermectin, emamectin, ethiprole, fipronil, flonicamid, flupyrazone, indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, trifluoromethylpyralid, flutoxin, spinosad, spinetoram, sulfoxaflor, and triflumuron; more preferably selected from ethiprole, spinetoram, abamectin and flupyrazone.

[0141] In an alternative embodiment, an additional adjuvant i) (preferably a silicone oil-based antifoaming agent, further preferably polydimethylsiloxane absorbed onto a solid matrix) is essential in the above embodiments as well as those described below.

[0142] Single preparation:

[0143] The ratio of the active ingredient (component a / compound of formula I / I-2) in the composition of the present invention containing only one active ingredient is

[0144] Preferably 0.5-25% by weight

[0145] More preferably, 1-18% by weight, and

[0146] More preferably, it is 2-12% by weight.

[0147] The proportion of the salt (component b) in the composition of the present invention containing only one active ingredient is

[0148] Preferably 20-75% by weight

[0149] More preferably, 25-68% by weight, and

[0150] More preferably, it is 30-66% by weight.

[0151] The proportion of the inorganic salt (component c) in the composition of the present invention containing only one active ingredient is

[0152] Preferably 1-10% by weight

[0153] More preferably, 1.5-9% by weight, and

[0154] More preferably, it is 2-7% by weight.

[0155] The proportion of the dispersant (component d) in the composition of the present invention containing only one active ingredient is

[0156] Preferably 1-20% by weight

[0157] More preferably, 5-15% by weight, and

[0158] More preferably, it is 8-12% by weight.

[0159] The proportion of the wetting agent (component e) in the composition of the present invention containing only one active ingredient is

[0160] Preferably 0.5-15% by weight

[0161] More preferably, 1-10% by weight, and

[0162] More preferably, it is 1.5-2.5% by weight.

[0163] The proportion of filler (component f) in the composition of the present invention containing only one active ingredient is preferably 0.5-30% by weight,

[0164] More preferably, 5-25% by weight, and

[0165] More preferably, it is 10-22% by weight.

[0166] The proportion of the structure forming agent (component g) in the composition of the present invention containing only one active ingredient is

[0167] Preferably 0.5-15% by weight

[0168] More preferably, 1-10% by weight, and

[0169] More preferably, it is 3-8% by weight.

[0170] The proportion of the other adjuvants (component i) in the composition according to the invention, if present, is preferably 0-10% by weight,

[0171] More preferably, 0-8% by weight, and

[0172] More preferably, it is 0-5% by weight.

[0173] If component i) is necessary in an alternative embodiment, for example as a defoamer, its proportion in the solid preparations according to the invention is 0.1-5% by weight.

[0174] A preferred embodiment of the present invention is a composition comprising the following components:

[0175] a) 0.5-25 wt %

[0176] b) 20-75% by weight

[0177] c) 1-10% by weight

[0178] d) 1-20% by weight

[0179] e) 0.5-15 wt %

[0180] f) 0.5-30% by weight

[0181] g) 0.5-15% by weight.

[0182] A further preferred embodiment of the present invention is a composition comprising the following components:

[0183] a) 1-18 wt%

[0184] b) 25-68 wt %

[0185] c) 1.5-9% by weight

[0186] d) 5-15% by weight

[0187] e) 1-10% by weight

[0188] f) 5-25% by weight

[0189] g) 1-10% by weight.

[0190] A further preferred embodiment of the present invention is a composition comprising the following components:

[0191] a) 2-12 wt%

[0192] b) 30-66 wt %

[0193] c) 2-7% by weight

[0194] d) 8-12 wt%

[0195] e) 1.5-2.5 wt %

[0196] f) 10-22% by weight

[0197] g) 3-8% by weight.

[0198] In an alternative embodiment where component i) is essential, solid compositions comprising the following components are preferred:

[0199] a) 2-12 wt%

[0200] b) 30-66 wt %

[0201] c) 2-7% by weight

[0202] d) 8-12 wt%

[0203] e) 1.5-2.5 wt %

[0204] f) 10-22% by weight

[0205] g) 3-8% by weight

[0206] i) 0.1-5% by weight.

[0207] Mixed preparations:

[0208] The proportion of other active ingredients (component h) in the composition of the present invention, if present, is

[0209] Preferably 1-30% by weight

[0210] More preferably, 1-25% by weight, and

[0211] More preferably, it is 1.5-20% by weight.

[0212] In an alternative embodiment where components h) and i) are essential, solid compositions comprising the following components are preferred:

[0213] a) 2-12 wt%

[0214] b) 30-66 wt %

[0215] c) 2-7% by weight

[0216] d) 8-12 wt%

[0217] e) 1.5-2.5 wt %

[0218] f) 10-22% by weight

[0219] g) 3-8% by weight

[0220] h) 1.5-20% by weight

[0221] i) 0.1-5% by weight.

[0222] Among the abovementioned compositions, particularly preferably usable are tetramic acid derivatives of the abovementioned formula (I) in which G = hydrogen (a).

[0223] Also most preferably usable are tetramic acid derivatives of the above formula (I) in which G=E(d).

[0224] Compound I-2 is preferably used in the form of its most thermodynamically stable polymorphic structure. The crystal structure and other physical data are determined as follows:

[0225] Sample preparation:

[0226] Compound I-2 (C 19 H 22 ClNO4 / MW=363.84 g / mol), and dried at room temperature to obtain modification A.

[0227] Modification A of I-2 can be determined by X-ray powder diffraction, based on the presence of Cu-Kα1 radiation at 25°C. The corresponding diffraction pattern recorded (Figure 1) is characterized.

[0228] Variant A of the present invention shows at least 3, preferably at least 5, further preferably at least 7, even further preferably at least 10 and most preferably all reflections as shown in Figure 1 and Table 2a). Table 2b) shows all reflections measured for variant A:

[0229] Variant A of the invention is also characterized by the X-ray diffraction diagram shown in FIG. 1 .

[0230] Crystallographic studies of single crystals of modification A show that the crystal structure is monoclinic and the unit cell has a P21 / c space group.

[0231] Table 2: Crystallographic properties of modification A

[0232]

[0233] a, b, c = lengths of the edges of the unit cell

[0234] α, β, γ = angles of the unit cell

[0235] Z = number of molecules in the unit cell

[0236] Table 2a / b: Crystallographic data / reflections [°2θ] of modification A

[0237] 2a 2b [°2θ] Reflection [°2θ] Variant A Variant A 11.3 8.0 14.6 10.8 16.0 11.3 20.1 12.2 21.7 14.6 22.7 16.0 23.1 17.6 24.5 18.4 28.2 19.4 29.0 20.1 21.7 22.7 23.1 23.8 24.5 25.9 26.4 28.2 29.0 29.4 30.1 30.6 32.2 36.2 37.4 38.2 39.1

[0238] The polymorphic form of modification A of I-1 can be determined by infrared spectroscopy using a diamond ATR instrument at 25°C with a wavelength of 4 cm -1 Variant A of the invention exhibits at least 3, preferably at least 5, further preferably at least 7 and particularly preferably all of the bands shown in FIG. 2 and described in Table 2c.

[0239] Table 2c) Infrared bands [cm -1 ]

[0240]

[0241] In addition to the above-mentioned modification A, compound I-2 may also exist in other polymorphic forms as well as pseudo-polymorphic forms (hydrates, solvates, etc.).

[0242] The application rate of the preparations according to the invention can vary within a relatively wide range and is determined by the respective active ingredient and its content in the composition.

[0243] With the aid of the compositions according to the invention, the insecticidal active ingredient mixtures can be applied in a particularly advantageous manner to plants and / or their habitat.

[0244] The composition of the present invention can be used to treat all plants and plant parts. In this article, plants are understood to include all plants and plant populations, such as desired and unwanted wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants that can be obtained by conventional breeding and optimization methods or by biotechnology and genetic engineering methods or a combination of these methods, including transgenic plants and including plant varieties that may be protected by plant breeders' rights or not protected by plant breeders' rights. Plant parts are understood to mean all parts and organs above and below the ground of plants, such as buds, leaves, flowers and roots, examples of which are leaves, needles, stalks, stems, flowers, fruiting bodies, fruits and seeds, as well as tubers, roots and rhizomes. Plant parts also include the material of harvest and vegetative propagation and reproductive propagation materials, such as cuttings, tubers, rhizomes, shoots and seeds.

[0245] Preferably, the compounds of formula (I) are used in the formulations according to the invention by spraying (but can also be applied by pouring, dipping or dripping) against animal pests of the following pest families:

[0246] Preferred are species of the genus Eriosoma and species of the genus Pemphigus in crops such as citrus, pome fruits, stone fruits, leafy vegetables, root and tuber vegetables and ornamental plants from the family of woolly aphids (Pemphigidae).

[0247] From the family of grape lice (Phylloxeridae), preferably: Phylloxera species in grapes, nuts and citrus.

[0248] Preferred among the psyllid family (Psyllidae) are: Psylla species, Paratrioza species, Tenaphalara species, Diaphorina species, Trioza species in crops such as pome fruits, drupes, citrus, vegetables, potatoes, and tropical crops.

[0249] Preferred among the family of soft scale insects (Coccidae) are: Ceroplastes species, Drosicha species, Pulvinaria species, Protopulvinaria species, Saissetia species, and Coccus species in perennial crops such as citrus, pome fruits, drupes, olives, grapes, coffee, tea, tropical crops, ornamental plants, and vegetables.

[0250] Preferred among the family of shield scale insects (Diaspididae) are: Quadraspidiotus species, Aonidiella species, Lepidosaphes species, Aspidiotus species, Aspis species, Diaspis species, Parlatoria species, Pseudaulacaspis species, Unaspis species, Pinnaspis species, and Selenaspidus species in crops such as citrus, pome fruits, drupes, almonds, pistachios, nuts, olives, tea, ornamental plants, grapes, and tropical crops.

[0251] From the family of ensign scale (Ortheziidae), preferably: species of the genus Orthezia in citrus, pome fruit, and drupe.

[0252] Preferred from the family of mealybugs (Pseudococcidae) are: Pericerya species, Pseudococcus species, Planococcus species, Dysmicoccus species in crops such as citrus, stone and pome fruits, tea, grapes, vegetables, ornamentals and tropical crops.

[0253] Also preferred from the family of whiteflies (Aleyrodidae) are: Bemisia tabaci, Bemisia argentifolii, Trialeurodes vaporariorum, Aleurothrixus floccosus, Aleyrodes species, Dialeurodes species, Parabemisia myricae in crops such as vegetables, melons, potatoes, tobacco, soft fruits, citrus, ornamental plants, cotton, soybeans and tropical crops.

[0254] Furthermore, in the aphid family (Aphidae), the following are preferred:

[0255] Myzus species in tobacco, stone fruits, soft fruits, fruiting vegetables, leafy vegetables, tubers and root vegetables, melons, potatoes, ornamentals, spices,

[0256] Donkey bean aphid (Acyrthosiphon onobrychis) in vegetables,

[0257] Tobacco, citrus, pome fruits, stone fruits, melons, strawberries, soft fruits, fruiting vegetables, leafy vegetables, tubers, stems and root vegetables, ornamental plants, potatoes, pumpkins, Aphis species in spices,

[0258] Yellow rose aphid (Rhodobium porosum) in strawberries,

[0259] Nasonovia ribisnigri in leafy vegetables

[0260] Macrosiphum species in ornamental plants, potatoes, leafy and fruiting vegetables, strawberries,

[0261] Phorodon humuli in hops,

[0262] Cabbage aphid (Brevicoryne brassicae) in leafy vegetables,

[0263] Toxoptera species in citrus, stone fruits, almonds, nuts, spices,

[0264] Aulacorthum species in citrus, potatoes, fruiting vegetables and leafy vegetables.

[0265] Anuraphis cardui in vegetables,

[0266] Brachycaudus helicrysi in sunflower,

[0267] Donkey-eating bean aphids in vegetables.

[0268] Similarly, preferred from the family of thrips (Thripidae) are: Anaphothrips species, Baliothrips species, Caliothrips species, Frankliniella species, Heliothrips species, Hercinothrips species, Rhipiphorothrips species, Scirtothrips species, Kakothrips species, Selenothrips species and Thrips species in crops such as fruits, cotton, grapes, tea, nuts, tropical crops, ornamentals, conifers, tobacco, spices, vegetables, soft fruits, melons, citrus and potatoes.

[0269] In addition, from the family of leafminers (Agromyzidae) and the family of root maggot flies (Anthomyiidae), preferably: Agromyza species, Amauromyza species, Atherigona species, Chlorops species, Liriomyza species, Oscinella species, and Pegomya species in crops such as vegetables, melons, potatoes, nuts, and ornamental plants.

[0270] Preferred among the families of leafhoppers (Cicadellidae) and planthoppers (Delphacidae) are: Circulifer species, Dalbulus species, Empoasca species, Erythroneura species, Homalodisca species, Idioscopus species, Laodelphax species, Nephotettix species, Nilaparvata species, Oncometopia species, and Sogatella species in crops such as citrus, fruits, grapes, potatoes, vegetables, ornamental plants, conifers, melons, small fruits, tea, nuts, rice, and tropical crops.

[0271] Preferred among the family of leafminers (Gracillariidae):

[0272] Caloptilia, Gracillaria, Lithocolletis, Leucoptera, Phthorimaea and Phyllocnistis in crops such as pome fruits, drupes, grapes, nuts, citrus, conifers, potatoes and coffee.

[0273] From the family of gall midges (Cecidomyiidae), preferably:

[0274] Contarinia, Dasineura, Diplosis, Prodiplosis, Thecodiplosis, Sitodiplosis and Haplodiplosis in crops such as citrus, pome fruits, drupes, vegetables, potatoes, spices, soft fruit, conifers and hops.

[0275] Similarly, within the fruit fly family (Tephritidae) preference is given to:

[0276] Anastrepha, Ceratitis, Dacus and Rhagoletis species in vegetables, soft fruit, melons, pome and drupe, ornamentals, potatoes, grapes, tropical crops, citrus, olives, etc.

[0277] Furthermore, preference is given to mites from the family of spider mites (Tetranychidae) and the family of gall mites (Eriophyidae):

[0278] Tetranychus, Panonychus and Aculops species in vegetables, potatoes, ornamentals, citrus, grapes, conifers, etc.

[0279] The treatment according to the invention of plants and plant parts with the compositions according to the invention is carried out directly or by allowing the compositions to act on their habitat, environment or storage space by conventional treatment methods, such as pouring, soaking, spraying, evaporating, misting, broadcasting, painting and in the case of propagation materials, in particular seeds, by applying one or more coatings.

[0280] The active ingredient is preferably applied by spraying. Alternatively, the active ingredient is applied by pouring, dripping or dipping.

[0281] Preferably, the plants to be treated are selected from the group consisting of cotton, soybeans, tobacco, vegetables, spices, ornamentals, conifers, citrus, fruits, tropical crops, nuts and grapes.

[0282] Preferably, the composition of the invention is used to combat pests from the following families: woolly aphids, grape root lice, psyllids, soft scale, shield scale, flag scale, mealybugs, whiteflies, aphids, thrips, leafhoppers, planthoppers, leafminers, gall midges, fruit flies, leafminers, spider mites, gall mites.

[0283] We have also found that the composition of the invention can be prepared by wetting a powdery mixture consisting of the active ingredient and the formulation auxiliaries, followed by granulation by low-pressure extrusion, and then drying the wet granules. The relevant equipment for wetting, extrusion and drying is known to those skilled in the art. During the preparation process, it should be ensured in particular that the temperature of the product is maintained below 60°C, and preferably below 50°C in all process steps.

[0284] This method also forms part of the subject matter of the present invention.

[0285] The treatment according to the invention of plants and plant parts with the compositions according to the invention is carried out directly or by allowing the compositions to act on their habitat, environment or storage space by customary treatment methods, for example dipping, spraying, evaporating, misting, broadcasting, painting and in the case of propagation materials, in particular seeds, also by applying one or more coatings.

[0286] The following examples illustrate the subject matter of the invention without limiting the invention. Example

[0287] 1. Sample Preparation and Physical Characterization

[0288] 1 kg of a mixture consisting of compound I-2, an optional second active ingredient, diammonium hydrogen phosphate (DAHP), an (optional) second inorganic salt, Morwet EFW, Pergopak M, kaolin W, a dispersing aid, optional magnesium stearate, and a defoamer was ground in a Hosokawa 100AS 4" air jet mill (nozzle air pressure 5.5 bar, grinding air pressure 4.5 bar, throughput 100 g / min), moistened with water (about 14 wt %), and extruded with a Fuji Paudal dome extruder (die hole size 1 mm) to give WG, which was then further dried in a fluidized bed dryer.

[0289] Composition Examples

[0290]

[0291]

[0292] Example of storing data

[0293]

[0294] Composition Examples

[0295]

[0296]

[0297] Determination of pH (by CIPAC MT 75.3 method):

[0298] The pH was measured at 23°C using a standard pH glass electrode in a 1% dispersion of the granules in deionized water.

[0299] Determination of suspension rate (by CIPAC MT 184.1 method):

[0300] A 1% aqueous suspension is dispersed in a 250 mL measuring cylinder (CIPAC C). The mixture is equilibrated for 30 minutes. Subsequently, the upper 9 / 10 of the suspension is removed. The remaining 1 / 10 is dried and the residue (sediment) is determined gravimetrically. The suspension rate is defined as:

[0301] 10 / 9*100*(sample amount [g]*ai ratio [%] / 100-residue [g]) / (sample amount [g]*ai ratio [%] / 100)

[0302] Therefore, a value of 100% means that all insoluble components are evenly distributed throughout the sample volume.

[0303] Determination of wet sieve residue (by CIPAC MT 185 method):

[0304] 25 g of granules were placed in 250 mL of water in a beaker. After one minute, the mixture was stirred for 5 minutes using a magnetic stirrer. Subsequently, the dispersion and the washing water were transferred to the corresponding sieves to clean the beaker. The sieves were then rinsed thoroughly with cold water until the residue on the sieves was no longer noticeable (maximum 10 min). After the sieves were drip-dried, the residue was quantitatively transferred to an evaporating dish with deionized water and then air-dried, and the residue was then determined gravimetrically.

[0305] 2. Use examples:

[0306] The preparability of the pre-made slurry for spray application was tested with an induction hopper under the following boundary conditions: Tank volume: 400 L

[0307] Water volume: 100L

[0308] · Granule quantity: 2.5kg

[0309] While water was pumped into the circulation, 2.5 kg of product was quickly placed into the inhalation dosing device and then pumped into the circulation for another 10 min. After 5 and 10 min, the residues in the inhalation dosing device, the filter at the inlet and the residues of undispersed product in the tank were checked.

[0310]

[0311] Materials used

[0312] TA / 72 is a sodium salt of polycarboxylate. SDS is dioctyl sodium sulfosuccinate. L-Wet Max is a blend, all from Solvay.

[0313] Kaolin W is from Hydrated aluminum silicate from Lohrheim GmbH & Co. KG, Lohrheim, Germany.

[0314] 2700 is naphthalenesulfonic acid-formaldehyde condensate sodium salt from Indorama Ventures, The Woodlands, Texas, USA.

[0315] The defoamer EP 6703 is an absorbed polydimethylsiloxane from Solvay.

[0316] Morwet EFW is the sodium salt of alkylnaphthalenesulfonic acid from Nouryon, Stenungsund, Sweden.

[0317] M is a polymethylurea resin from Huber Martinswerk, Bergheim, Germany.

[0318] Atlox Metasperse TM 550S is a modified styrene-acrylic polymer from Croda, UK.

[0319] B powder was tetrasodium ethylenediaminetetraacetate from BTC Europe GmbH, Monheim, Germany.

[0320] Flupyralidone is a crop protection active ingredient from Bayer Crop Science.

[0321] Avermectin is a crop protection active ingredient from Syngenta.

[0322] Spinosad is a crop protection active ingredient from Corteva.

Claims

1. A solid composition in the form of water dispersible granules, comprising: a. Tetramic acid derivatives of formula (I) in W and Y are independently hydrogen, C1-C4 alkyl, chlorine, bromine, iodine or fluorine, X is C1-C4 alkyl, C1-C4 alkoxy, chlorine, bromine or iodine, A, B and the carbon atoms to which they are bonded are a C3-C6 cycloalkyl group substituted by an alkylenedioxy group, the alkylenedioxy group being optionally substituted by a C1-C4 alkyl group or a C1-C4 alkoxy-C1-C2 alkyl group, and together with the The bonded carbon atoms together form a five-membered or six-membered ketal. G is hydrogen (a) or one of the following groups, in E is a metal ion or an ammonium ion, M is oxygen or sulfur, R 1 is a straight chain or branched C1-C6 alkyl group, R 2 is a straight chain or branched C1-C6 alkyl group, b. at least one basic salt, c. at least one additional inorganic salt selected from carbonates and bicarbonates, d. at least one dispersant, e. at least one wetting agent, f. at least one filler, g. at least one structure forming agent, h. Optional other active ingredients, i. Optional other commonly used adjuvants and formulation aids.

2. The composition according to claim 1, characterized in that The following components are present: h) at least one other active ingredient.

3. The composition according to claim 1 or 2, characterized in that Component a) in the composition of the present invention is a compound of formula (I) It has 4. The composition according to claim 1 or 2, characterized in that Component a) is a compound of the formula 5. Composition according to one or more of the preceding claims, characterized in that Component b) is diammonium hydrogen phosphate (DAHP).

6. A composition according to any one of the preceding claims, characterised in that Component c) is selected from sodium bicarbonate and potassium bicarbonate.

7. Composition according to one or more of the preceding claims, characterized in that Component d) is a dispersant selected from the group consisting of sodium salts of copolymers of maleic acid and olefins, sodium salts of copolymers of methacrylic acid and styrene, and modified copolymers of methacrylic acid and styrene, more preferably sodium salts of copolymers of methacrylic acid and styrene and modified copolymers of methacrylic acid and styrene.

8. Composition according to one or more of the preceding claims, characterised in that Component e) is selected from the group consisting of sodium salts of alkylated naphthalenesulfonic acids and sodium salts of dioctylsulfosuccinic acid, more preferably sodium salts of alkylated naphthalenesulfonic acids.

9. Composition according to one or more of the preceding claims, characterized in that Component f) is selected from kaolin, rutile and silica, more preferably kaolin.

10. Composition according to one or more of the preceding claims, characterized in that Component g) is selected from polymethylurea resins.

11. Composition according to one or more of the preceding claims, characterized in that Component h) is selected from Imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, cyantraniliprole, chlorantraniliprole, deltamethrin, flubendiamide, tetrazobactam, cyclobromofenamide, spirodiclofen, spiromesifen, spirotetramat, avermectin, fluthrin, chlorfenapyr, avermectin, ethiprole, fipronil, flonicamid, flupyrazone, indoxacarb, metaflumizone, methoxyfenozide, milbemycin, pyridaben, trifluoromethylpyralid, silafluanid, spinosad, spinetoram, sulfoxaflor, and triflumuron; more preferably selected from ethiprole, spinetoram, avermectin and flupyrazone.

12. Composition according to one or more of the preceding claims, comprising: a. Compounds of formula (I) The compounds of formula (I) have the following definitions: W is a methyl group, X is chlorine or methyl, Y is chlorine, bromine or methyl, A, B and the carbon atom to which they are bonded are a saturated C6 cycloalkyl group substituted by an alkylenedioxy group, which together with the carbon atom to which it is bonded forms a five-membered or six-membered ketal, G is hydrogen (a) or one of the following groups, in M is oxygen, E is a metal ion equivalent or an ammonium ion, R 1 is a straight chain or branched C1-C4 alkyl group, R 2 A straight chain or branched C1-C4 alkyl b. at least one inorganic basic salt, c. at least one inorganic salt selected from sodium bicarbonate and potassium bicarbonate, d. at least one dispersant of the polycarboxylic acid type, e. at least one anionic wetting agent, f. at least one inert filler, g. at least one structure forming agent, h. other optional effective insecticidal ingredients, i. Optional other adjuvants.

13. A composition according to one or more of the preceding claims, comprising a compound of formula (I) selected from the group consisting of: b. at least one inorganic alkaline ammonium salt selected from diammonium hydrogen phosphate (DAHP), c. at least one additional inorganic salt selected from carbonates and bicarbonates, d. at least one dispersant of the polycarboxylic acid type selected from the group consisting of hydrophobically modified comb polymers comprising the following polymers: polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymers of maleic acid or maleic anhydride with olefins, copolymers of acrylic acid with itaconic acid, copolymers of methacrylic acid with itaconic acid, copolymers of maleic acid or maleic anhydride with styrene, copolymers of acrylic acid with methacrylic acid, copolymers of acrylic acid with methacrylate, copolymers of acrylic acid with vinyl acetate, copolymers of methacrylic acid with styrene, modified copolymers of methacrylic acid with styrene, copolymers of maleic acid or maleic anhydride with acrylic acid, N-methyl fatty acids (e.g. C8-C 18 )muscle Amino acid salts, carboxylic acids such as resin acids or fatty acids (e.g. C8-C 18 ) or salts of such carboxylic acids, and salts of such copolymers, e. at least one anionic wetting agent selected from the group consisting of sodium salts of alkylated naphthalenesulfonic acids and sodium salts of dioctylsulfosuccinic acid, f. at least one inert filler selected from carbonates, silicates and oxides, and urea-formaldehyde condensates and cellulose, g. at least one structure forming agent selected from polyacrylic acid and its salts, cross-linked polyacrylates and polyureas, polyurethanes and derivatized polyureas and polyurethanes, h. other optional effective insecticidal ingredients, i. Optional other adjuvants.

14. A composition according to one or more of the preceding claims, comprising a compound of formula (I-2) having the following structure: b. at least one inorganic alkaline ammonium salt selected from diammonium hydrogen phosphate (DAHP), c. at least one inorganic salt selected from sodium bicarbonate and potassium bicarbonate, d. at least one dispersant selected from the sodium salt of a copolymer of methacrylic acid and styrene, e. at least one anionic wetting agent selected from the group consisting of sodium salts of alkylated naphthalenesulfonic acids, f. at least one inert filler selected from kaolin, rutile and silica, g. at least one structure-forming agent selected from polymethylurea resins, h. other optional effective insecticidal ingredients, i. Optional other adjuvants.

15. Composition according to one or more of the preceding claims, characterized in that There are components ag as follows: a) 2-12 wt% b) 30-66 wt % c) 2-7% by weight d) 8-12 wt% e) 1.5-2.5 wt % f) 10-22% by weight g) 3-8% by weight.

16. Composition according to one or more of the preceding claims, characterized in that Component h) is also present as follows: h) 1.5-20% by weight.

17. Composition according to one or more of the preceding claims, characterized in that Component i) is present as follows: i) 0.1-5% by weight.

18. Process for the preparation of a composition as claimed in one or more of the preceding claims, characterized in that The composition is prepared by mixing the components and then extruding.

19. Use of a composition as claimed in one or more of claims 1 to 17 for applying the effective agrochemical ingredients contained therein to plants and / or their habitat.

20. The product, characterized in that A composition comprising one or more of claims 1 to 17.

21. Use of a composition as claimed in one or more of claims 1 to 17 for controlling insects.

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