ADJUVANT COMBINATIONS AS FOLIAR UPTAKE ACCELERATOR FOR HERBICIDAL COMPOSITIONS

Abstract

The present invention relates to agrochemically active herbicidal compositions and to the use thereof for control of harmful plants. The present invention further relates to adjuvant combinations for improving bioavailability, especially cuticle penetration, of active herbicidal ingredients.

Claims

1. Adjuvant combination comprising a) tris(2-ethylhexyl) phosphate (TEHP), b) at least one alkyl ether phosphate ammonium salt, and c) at least one emulsifier or wetting agent.

2. Adjuvant combination comprising: a) tris(2-ethylhexyl) phosphate, b) at least one alkyl ether phosphate ammonium salt, c) at least one emulsifier, and d) at least one wetting agent.

3. Adjuvant combination according to claim 1, wherein component a) is present at 40% by weight to 60% by weight, optionally at 45% by weight to 55% by weight, and optionally 48% by weight to 52% by weight, based on the total weight of the adjuvant combination.

4. Adjuvant combination according to claim 1, wherein component b) is present at 20% by weight to 35% by weight, optionally at 25% by weight to 35% by weight, and optionally 28% by weight to 32% by weight, based on the total weight of the adjuvant combination.

5. Adjuvant combination according to claim 1, wherein, if either component c) or component d) is present, said c and/or d are present in the adjuvant combination at 10% by weight to 25% by weight, optionally at 12% by weight to 23% by weight, and optionally 12% by weight to 22% by weight, based on the total weight of the adjuvant combination.

6. Adjuvant combination according to claim 1, wherein b) is a 70% blend of C8-C10 mono- and dialkyl ether phosphate ammonium salts with free C8-C10 alcohols <10% and <10% triethylene glycol monobutyl ether.

7. Adjuvant combination according to claim 1, wherein c) is selected from the group consisting of nonionic dispersants comprising ethoxylated nonylphenols, ethylene oxide-propylene oxide block copolymers, endgroup-capped and non-endgroup-capped alkoxylated linear and branched, saturated and unsaturated alcohols (optionally. butoxy polyethylene-propylene glycols), reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols, and also fatty acid esters, fatty acid polyglycol ether esters, alkylsulfonates, alkylsulfates, arylsulfates, ethoxylated arylalkylphenols, and also ethoxylated and propoxylated arylalkylphenols and sulfated or phosphated arylalkylphenol ethoxylates or ethoxy- and propoxylates, and mixtures thereof.

8. Adjuvant combination according to claim 1, wherein d) is selected from the group consisting of alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, optionally alkyl ether sulfates, optionally the sodium salts of alkyl ether sulfates, phosphates, carboxylates and mixtures thereof, optionally the salts of the alkylsulfonic acids or alkylphosphoric acids and alkylarylsulfonic or alkylarylphosphoric acids, diphenylsulfonates, alpha-olefinsulfonates, lignosulfonates, 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, and nonionic wetting agents that are reaction products of linear or branched alcohols with ethylene oxide, which may be endgroup-capped or non-endgroup-capped, and also mixtures thereof.

9. Herbicidal composition comprising: A) at least one active agrochemical ingredient selected from the group consisting of herbicides, plant growth regulators and safeners, and B) an adjuvant combination according to claim 1.

10. Herbicidal composition according to claim 9, wherein the active agrochemical ingredient is selected from the group consisting of bicyclopyrone, mesotrione, fomesafen, tralkoxydim, napropamide, amitraz, propanil, pyrimethanil, dicloran, tecnazene, toclofos-methyl, flamprop-M, 2,4-D, MCPA, mecoprop, clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, haloxyfop, quizalofop-P, indol-3-ylacetic acid, 1-naphthylacetic acid, isoxaben, tebutam, chlorthal-dimethyl, benomyl, benfuresate, dicamba, dichlobenil, benazolin, triazoxide, fluazuron, teflubenzuron, phenmedipham, acetochlor, alachlor, metolachlor, pretilachlor, thenylchlor, alloxydim, butroxydim, clethodim, cyclodim, sethoxydim, tepraloxydim, pendimethalin, dinoterb, bifenox, oxyfluorfen, acifluorfen, fluazifop, S-metolachlor, glyphosate, glufosinate, paraquat, diquat, fluoroglycofen-ethyl, bromoxynil, ioxynil, imazamethabenz-methyl, imazapyr, imazaquin, imazethapyr, imazapic, imazamox, flumiclorac-pentyl, picloram, amidosulfuron, chlorsulfuron, nicosulfuron, rimsulfuron, triasulfuron, triallate, pebulate, prosulfocarb, molinate, atrazine, simazine, cyanazine, ametryn, prometryn, terbuthylazine, terbutryn, sulcotrione, isoproturon, linuron, fenuron, chlorotoluron, metoxuron, diflufenican, flufenacet, fluroxypyr, aminopyralid, pyroxsulam, XDE-848 Rinskor™, halauxifen-methyl, tembotrione, isoxaflutole, metribuzin, topramezone, pyroxasulfone, bixlozone, and also prohexadione and prohexadione-Ca and benoxacor, cloquintocet-mexyl, cyometrinil, dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, mefenpyr-diethyl, MG-191, naphthyl anhydride, and oxabetrinil, isoxadifen-ethyl, furilazole and cyprosulfamide.

11. Herbicidal composition according to claim 9, comprising an emulsion concentrate, oil dispersion, suspension emulsion, capsule suspension, dispersible concentrate, soluble liquid, emulsion in water, suspension concentrate or wettable powder.

12. Herbicidal composition according to claim 9, wherein components A) and B) are present in a spray liquor diluted ready for use at A) 0.1-1.5 g/l, optionally 0.2-1.0 g/l and optionally 0.4-0.8 g/l, and B) 3-8 g/l, optionally 5-7 g/l and optionally 6-7 g/l.

13. A product comprising the adjuvant combination according to claim 1 for improving foliar uptake of herbicides, plant growth regulators and/or safeners.

Description

EXAMPLES

Materials Used

[0097]

TABLE-US-00001 Disflamoll ® Tris(2-ethylhexyl) phosphate TOF = TEHP [TEHP] (Lanxess) Genapol ® LRO paste Aqueous solution of about 70% alkyl ether sulfate, Na salt (Clariant) Genapol ® X-060 Tridecyl polyethylene glycol ether, isotridecyl alcohol polyglycol ether with 6 EO (Clariant) (EO = ethylene oxide) Crovol ® CR/70G Ethoxylated vegetable oil (CRODA) Geronol ® CF/AR-E 70% mixture containing 25% C8-C10 mono- and dialkyl ether phosphate ammonium salts (Solvay) Lucramul ® CO 30 Ethoxylated castor oil, ethoxylated castor oil with 30 EO (Levaco) Lucramul ® HOT 5902 2-Ethylhexanol propylene-ethylene glycol ether (Levaco) Mero ® Emulsion concentrate of 81.4% rapeseed oil methyl ester (Bayer) AMS Ammonium sulfate Genapol ® C 100 Coconut fatty alcohol polyglycol ether with 10 EO (Clariant) Actirob ® B Emulsion concentrate containing 812 g/l rapeseed oil methyl ester Biopower ® Soluble concentrated formulation containing 6.7% w/w (percent by weight) 3,6-dioxaeicosylsulfate sodium salt and 20.1% w/w 3,6-dioxaoctadecylsulfate sodium salt (Bayer) TBEP premix V as TEHP premix V, with TBEP rather than TEHP TEHP premix I 10% Genapol ® LRO paste, 10% Lucramul ® CO 30, 80% Disflamoll ® TOF = TEHP TBEP premix I 10% Genapol ® LRO paste, 10% Lucramul ® CO 30, 80% TBEP (tributoxyethyl phosphate) Mefenpyr-diethyl Diethyl (RS)-1-(2,4-dichlorophenyl)- 4,5-dihydro-5-methyl-1H- pyrazole-3,5-dicarboxylate (Bayer) Pyroxasulfone 3-[5-(Difluoromethoxy)-1-methyl- 3-(trifluoromethyl)pyrazol- 4-ylmethylsulfonyl]-4,5-dihydro-5,5- dimethyl-1,2-oxazole (Kumiai) Cyprosulfamide N-[4-(Cyclopropylcarbamoyl) phenylsulfonyl]-o-anisamide (Bayer) Rinskor ™ Florpyrauxifen-benzyl, benzyl 4-amino-3-chloro-6-(4-chloro-2- fluoro-3-methoxyphenyl)-5- fluoropyridine-2-carboxylate (Dow) Isoxaflutole 5-Cyclopropyl-4-(2-methylsulfonyl- 4-trifluoromethylbenzoyl)isoxazole (Bayer) Tembotrione 2-[2-Chloro-4-(methylsulfonyl)- 3-[(2,2,2-(trifluoroethoxy)methyl] benzoyl]-1,3-cyclohexanedione (Bayer) Synergen ® GA C8-C10 Alkylglucamide (Clariant) Atlas ® G5002L Polyalkylene glycol ether, propoxylated (PO) and ethoxylated (EO) 4-butoxybutyl alcohol, butanol alkoxylates, liquid (CRODA) Agrotin ® SL SL280, adjuvant blend (Bayer) DMA Dimethylacetamide (Aldrich) Bixlozone 2-(2,4-Dichlorobenzyl)-4,4- dimethylisoxazolidin-3-one (FMC) Prohexadione-Ca Calcium 3-oxido-5-oxo-4-propionyl- cyclohex-3-enecarboxylate (BASF) Kuraray Poval ® 26-88 Polymer of polyvinyl alcohol (PVOH) with a hydrolysis level of about 88%; Mowiol ® 26-88 (Kuraray) Laudis ™ SC Commercially available product comprising tembotrione and safener (Bayer) TBEP Tributoxyethyl phosphate (Solvay) Cinmethylin (1S,2R,4R)-4-Isopropyl-1-methyl-2- [(2-methylbenzyl)oxy]-7- oxabicyclo[2.2.1]heptane (BASF) Tolpyralate 1-({1-Ethyl-4-[3-(2-methoxyethoxy)- 2-methyl-4-(methylsulfonyl)benzoyl]- 1H-pyrazol-5-yl}oxy)ethyl methyl carbonate (Ishihara Sangyo Kaisha Ltd) Atplus ® UEP-100 Alkoxylated polyol ester (CRODA) Lab-EC EC formulation as follows: Active ingredient in DMA (dimethylacetamide) with Lucramul ® PS 16 (tristyrylphenol ethoxylate 16 EO) Compound 1 Example I-553 in WO2016/102435 [00001] Compound 2 Example I-1117 in WO2016/102435 [00002] Compound 3 Example Ia in WO2008/131861 [00003] Compound 4 Example 1599 in WO2008/131860 [00004] Compound 5 Example 1.4 in WO2018/184978 [00005] Compound 6 Example I-214 in EP17205161.7 [00006]

[0098] The examples that follow show the effect on biological efficacy of the adjuvant combination according to the invention compared to other adjuvants, for example AMS, Mero®, Genapol® X-060, Genapol® C 100, Biopower®.

Example 1

[0099] The components according to Table 1 are weighed out and mixed by stirring, with addition of Disflamoll® TOF first. The batch sizes vary from 50 ml to 201 without further restrictions.

TABLE-US-00002 TABLE 1 Compositions of TEHP premix V Component Name % (w/w) g/l d Genapol ® LRO paste 6.25 62.5 d Genapol ® X-060 7.5 75 b Geronol ® CF/AR-E 30 300 c Lucramul ® CO 30 6.25 62.5 a Disflamoll ® TOF 50 500

Example 2: Dynamic Wetting Properties of TEHP Premix V—Contact Angle Measurement

[0100] The wetting properties of the adjuvants were measured by measuring the contact angle on barley (HORVS) and on Abutilon theophrasti (ABUTH) (leaf surface of each) in order to represent a plant surface that is difficult to wet and one that is easily wetted. Measurements were made for concentrations of the premix in water at 3 g/l and 6 g/l, with tap water as comparison. The contact angle in ° was measured using a DSA10 goniometer from Krüss GmbH.

TABLE-US-00003 TABLE 2a Sample ABUTH HORVS TEHP premix V, 3 g/l 43 78 TEHP premix V, 6 g/l 44 56 Tap water 95 141

[0101] The results in Table 2a show that the adjuvant combinations according to the invention have excellent wetting properties, even in the case of barley leaves that are difficult to wet, and especially at relatively high concentration.

[0102] Table 2b: Contact angle on Abutilon theophrasti (ABUTH) and Chenopodium album (CHEAL) in ° (easily wetted weeds and those that are difficult to wet) of the adjuvant combination TEHP premix I and TEHP premix I in combination with Lucramol® Hot 5902:

TABLE-US-00004 Sample ABUTH CHEAL TEHP premix I, 6.25 g/l & Geronol ® CF/AR-E, 41 51 3 g/l TEHP premix I, 6.25 g/l & Geronol ® CF/AR-E, 41 58 3 g/l & Lucramul ® HOT 5902, 1 g/l Tap water 105 147

[0103] Table 2b shows that Lucramul® HOT 5902 does not significantly improve the properties of TEHP premix I.

Example 3: Spray Retention Properties of TEHP Premix V

[0104] Spray retention (static wetting) was measured against Kuraray Poval® 26-88 as standard on barley. Application rate according to Table 3, at 300 I/ha water, spray cabin parameters: pressure 3 bar, XR11002VS nozzle.

TABLE-US-00005 TABLE 3 Results in %. Sample Spray retention on barley in % Kuraray Poval ® 26-88, 1 g/l (standard) 82 Tap water 4 Mero ®, 2 l/ha 61 Biopower ®, 1 l/ha 56 TEHP premix V, 6 g/l 68 TEHP premix V, 3 g/l 52

[0105] Spray retention of the adjuvant combination according to the invention is comparable or better as compared with the comparative samples according to Table 3.

Example 4: Dynamic Surface Tension (DST)

[0106] Dynamic surface tension was determined via the bubble pressure method (BP2100 tensiometer, Krüss).

[0107] A value of 50 mN/m (at 20-21° C.) based on water (72.8 mN/m) shows an improvement in adhesion from “zero adhesion” (0%) to about 50% (Baur P., Pontzen R.; 2007; Basic features of plant surface wettability and deposit formation and the impact of adjuvant; in R. E. Gaskin ed. Proceedings of the 8th International Symposium on Adjuvants for Agrochemicals; Publisher: International Society for Agrochemical Adjuvants (ISAA), Columbus, Ohio, USA).

TABLE-US-00006 TABLE 4 TEHP premix V solo and as tankmix; TEHP premix I, 6.25 g/l + Geronol ® CF/AR-E, 3 g/l. Dynamic surface tension was measured for the various adjuvants/combinations and for the individual components. The results are shown in table 4. Sample 20 ms 50 ms 200 ms 500 ms TEHP premix I, 6.25 g/l + 56.8 51.1 45.8 42.4 Geronol ® CF/AR-E, 3 g/l TEHP premix V, 6 g/l 57.5 50.9 42.3 38.4 TEHP premix I, 6 g/l 69.1 63.0 52.5 46.8 Lucramul ® CO 30, 3 g/l 63.3 59.0 52.6 49.5 TEHP, 6 g/l 71.7 71.7 71.6 71.5 Geronol ® CF/AR-E, 3 g/l 61.6 58.1 54.0 52.0 Genapol ® LRO paste, 3 g/l 54.9 43.9 35.4 32.5 Genapol ® X-060 56.2 40.9 28.6 27.2 Tap water 72.0 72.1 72.1 72.0

[0108] The adjuvant combinations according to the invention have a DST close to that of the very good wetting agents Genapol® LRO paste and Genapol® X-060, as can be seen in Table 4. The adjuvant combinations according to the invention, at 200 ms (relevant timeframe between spraying of a droplet and contact with the leaf), have better properties than the two main constituents of the adjuvant combination tested individually.

Example 5: Plant Compatibility—Phytotoxicity

[0109] The tests were conducted on Euphorbia pulcherrima leaves with droplet application. Each test was repeated with 2×10 ml dripped onto the same leaf. After drying, after 24 h, the phytotoxic effects were determined using an in-house checklist. The standard is Genapol® 100. Concentrations measured: 0.1-0.3-1.0-3.0 g/l. For TEHP premix V, phytotoxic effects (brown spots) were observed only at the highest concentration used, whereas the standard showed these effects even at 1 g/l.

Example 6: Penetration Properties of Various Herbicides, Plant Growth Regulators (PGRs) and Safeners

[0110] The properties of the adjuvant combinations according to the invention as penetration enhancers were measured in a membrane penetration test on the cuticula of apple leaves.

[0111] Determination of bioavailability of various herbicides, plant growth regulators (PGRs) and safeners by cuticle penetration test.

[0112] The principle of the determination has already been published (e.g. WO-A-2005/194844; Baur, 1997; Baur, Grayson and Schönherr 1999; Baur, Bodelon and Lowe, 2012), and so only the particular conditions will be given hereinafter.

[0113] The leaf cuticles were isolated enzymatically as described in the literature. The stomata-free cuticles were first dried under air and introduced into stainless steel diffusion cells. After the application of the test liquids to the original top side of the leaf and evaporation of liquid, the diffusion cells were transferred into thermostat blocks and loaded with water. At regular intervals, aliquot samples were taken, and the amount of active ingredient diffused was determined by means of HPLC. During the experiment, relative air humidity was kept constant at 56% at a constant 25° C. The analytical determination by HPLC (1260 II Infinity, Agilent) was conducted on a Kinetex 50×2.1 mm, 2.6μ C18 column (Phenomenex) at a flow rate of 0.8 ml/min in acetonitrile/ultrapure water +0.01 M H.sub.3PO.sub.4 as eluent, using 20 μl aliquots as sample. Detection was effected with a DAD detector. The results given in each case are the geometric penetration averages at the average measurement times. According to the variance, 10 repeat measurements were conducted. The coefficient of variation was below 35%, which corresponds to a typical value of biological variability for the penetration of different plants (Baur 1997).

[0114] Typically, a spray solution of the active ingredient (0.5 g of active ingredient/l) was produced. An aliquot was applied to an apple cuticle and left to dry. The operation was repeated 10 times. The amount absorbed through the cuticles in the uptake solution is determined by HPLC as described above. The measurements were made after 0, 6, 12, 24, 36 or 48 h. The temperature was increased from 25° C. to 35° C. after 24 h in order to test solubility effects of the adjuvant. In some measurements, the temperature was kept at 25° C. or 35° C. from the start.

TABLE-US-00007 TABLE 5 Effect of various adjuvants/adjuvant combinations on cuticle penetration with tembotrione as standard (Laudis ™ SC) Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 6 h in % 12 h in % 24 h in % 1 TEHP premix V, 6 g/l 39 73 86 2 Geronol ® CF/AR-E, 6 26 58 3 g/l 3 Disflamoll ® TOF = 3 10 21 TEHP, 6 g/l 4 Genapol ® LRO 0 3 9 paste, 3 g/l 5 Genapol ® X-060, 3 0 0 0 g/l 6 Lucramul ® CO 30, 3 0 0 0 g/l

[0115] Table 5 shows that none of the individual constituents of the adjuvant combination according to the invention acts as a penetration enhancer for tembotrione, whereas, surprisingly, TEHP premix shows a distinct enhancement.

[0116] Effect of TBEP compared to TEHP in the adjuvant combination according to the invention.

[0117] TBEP is a known solvent which is used in EC formulations. It is structurally similar to TEHP.

TABLE-US-00008 TABLE 6 TBEP vs TEHP with tembotrione (Laudis ™ SC) as standard Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 6 h in % 12 h in % 24 h in % 1 TEHP premix V, 6 g/l 59 94 107 2 TEHP premix I, 6 g/l 8 16 34 3 TBEP premix V, 6 g/l 6 22 28 4 TBEP premix I, 6 g/l 0 8 11 5 AMS, 1 g/l & 59 69 77 Mero ®, 3 g/l 6 — 0 0 0

[0118] Table 6 shows that TBEP does not enhance the uptake of tembotrione.

TABLE-US-00009 TABLE 7 TBEP vs TEHP with bixlozone as standard (standard SC formulation). Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 6 h in % 12 h in % 24 h in % 1 TEHP premix V, 6 g/l 91 89 91 2 TEHP premix I, 6 g/l 78 79 83 3 TBEP premix V, 6 g/l 58 61 66 4 TBEP premix I, 6 g/l 66 70 74 5 Mero ®, 3 g/l 84 82 88 6 none 21 42 62

[0119] Table 7 shows that TBEP shows distinctly lower uptake of bixlozone than TEHP.

TABLE-US-00010 TABLE 8 TBEP vs TEHP with mefenpyr-diethyl (SC formulation as described in WO2017144497). Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 12 h in % 24 h in % 48 h in % 1 TBEP premix V, 6 g/l 69 76 81 2 TBEP-TM1, 6 g/l 76 83 86 3 TEHP premix V, 6 g/l 87 91 94 4 TEHP-TM1, 6 g/l 83 87 87 5 Mero ®, 3 g/l 79 87 87 6 none 4 9 16

[0120] Table 8 shows that, here too, TEHP has better penetration-enhancing properties compared to TBEP in the combination.

TABLE-US-00011 TABLE 9 Biopower ® vs TEHP with mefenpyr-diethyl (SC formulation as described in WO2017144497). Cuticle Cuticle penetration penetration Run Adjuvant 24 h in % 48 h in % 1 — 17 59 2 TEHP premix V, 6 g/l 94 100 3 Biopower ®, 3 g/l 42 94

[0121] Table 9 here too shows faster uptake with the adjuvant combination according to the invention.

TABLE-US-00012 TABLE 10 Mero ® vs TEHP with pyroxasulfone (SC formulation). Cuticle penetration Run Adjuvant 24 h in % 1 — 2 2 TEHP premix V, 6 g/l 34 3 Mero ®, 5 g/l & AMS, 1 g/l 30 4 Mero ®, 5 g/l 27

[0122] Table 10 shows that, even in the case of water-insoluble pyroxasulfone, the adjuvant combinations according to the invention show a slight improvement in uptake.

TABLE-US-00013 TABLE 11 Cyprosulfamide WP20 formulation (wettable powder). Cuticle penetration Run Adjuvant 24 h in % 1 Mero ®, 7 g/l 12 2 TEHP premix V, 6 g/l 62 3 Mero ®, 7 g/l & AMS, 3 g/l 38 4 TEHP premix I, 6 g/l 18

TABLE-US-00014 TABLE 12 Rinskor ™ EC formulation (emulsifiable concentrate). Cuticle Cuticle penetration penetration Run Adjuvant 24 h in % 48 h in % 1 Mero ®, 5 g/l 22 40 2 TEHP premix V, 5 g/l 24 49 3 Mero ®, 5 g/l & AMS, 2 g/l 22 31 4 TEHP premix I, 5 g/l 14 26 5 AMS, 2 g/l 5 15

TABLE-US-00015 TABLE 13 Isoxaflutole OD formulation (oil dispersion) with different loading Cuticle penetration Run Adjuvant 24 h in % OD 50 G — 16 OD 200 G — 8 OD 200 G Mero ®, 5 g/l 76 OD 50 G TEHP premix V, 5 g/l 78 OD 200 G TEHP premix V, 5 g/l 81

TABLE-US-00016 TABLE 14 Tembotrione SC formulation (suspension concentrate). Cuticle from 2016 Cuticle penetration Run Adjuvant 24 h in % 1 — 0 2 TEHP premix V, 6 g/l 57 3 Mero ®, 5 g/l & AMS, 1 g/l 50 4 TEHP premix I, 5.25 g/l 11

TABLE-US-00017 TABLE 15 Tembotrione SC formulation (suspension concentrate). Cuticle from 2015 Cuticle Cuticle penetration penetration Run Adjuvant 24 h in % 48 h in % 1 TEHP premix V, 6 g/l 93 104 2 Mero ®, 5 g/l & AMS, 1 g/l 73 79 3 TEHP premix I, 6.25 g/l 30 45

TABLE-US-00018 TABLE 16 Tembotrione SC formulation (suspension concentrate). Cuticle from 2014 Cuticle penetration Run Adjuvant 24 h in % 1 TEHP premix I, 6.25 g/l 28 2 Mero ®, 5 g/l & AMS, 1 g/l 79 3 TEHP premix V, 6.25 g/l 104

TABLE-US-00019 TABLE 17 Tembotrione OD formulation (oil dispersion). Run Adjuvant Cuticle penetration 24 h in % 1 TEHP premix V, 6 g/l 93 2 TEHP premix I, 6.25 g/l 53 3 none 13

TABLE-US-00020 TABLE 18 Cinmethylin WP20 formulation. Cuticle Cuticle penetration penetration Run Adjuvant 24 h in % 48 h in % 1 Agrotin ® SL, 2 g/l 15 19 2 Lucramul ® CO 30, 2 g/l 38 37 3 Mero ®, 5 g/l & AMS, 2 g/l 52 51 4 TEHP premix V, 5 g/l 52 51

[0123] Other adjuvant classes (ethoxylated castor oils, ethoxylated nonylphenol, ethoxylated NPEs) are ineffective.

TABLE-US-00021 TABLE 19 Bixlozone SC formulation (suspension concentrate) Cuticle Cuticle penetration penetration Run Adjuvant 24 h in % 48 h in % 1 — 24 73 2 TEHP premix V, 6 g/l 93 105 3 Biopower ®, 3 g/l 47 76 4 Synergen ® GA, 3 g/l 37 82 5 TEHP premix I, 6 g/l 85 90

TABLE-US-00022 TABLE 20 Prohexadione-Ca EC formulation Cuticle Cuticle penetration penetration Run Adjuvant 24 h in % 48 h in % 1 — 18 44 2 Agrotin ® SL, 2 g/l 62 85 3 Mero ®, 5 g/l & AMS, 2 g/l 77 92 4 Lucramul ® CO 30, 2 g/l 36 90 5 TEHP premix V, 6 g/l 96 112

TABLE-US-00023 TABLE 21 Compound 1 EC formulation Cuticle Cuticle penetration penetration Run Adjuvant 12 h in % 24 h in % 1 TEHP premix V, 6 g/l 105 104 2 Atplus ® UEP-100, 2 g/l 64 81 3 Biopower ®, 3 g/l 48 62 4 Atlas ® G5002L, 2 g/l 37 58

TABLE-US-00024 TABLE 22 Compound 1 EC formulation compared to WP20 Cuticle Cuticle penetration penetration Run Adjuvant 12 h in % 24 h in % Lab EC TEHP premix V, 5 g/l 70 93 Lab EC Biopower ®, 3 g/l 8 27 Lab EC Mero ®, 3 g/l 25 47 WP20 TEHP premix V, 5 g/l 25 56 WP20 Biopower ®, 3 g/l 0 6 WP20 Mero ®, 3 g/l 21 53

TABLE-US-00025 TABLE 23 Compound 2 WP20 formulation. Cuticle Cuticle penetration penetration Run Adjuvant 12 h in % 24 h in % 1 TEHP premix V, 6 g/l 78 89 2 Mero ®, 5 g/l 72 89 3 Genapol ® X-060, 2 g/l 30 45 4 Crovol ® CR/70G, 2 g/l 15 26 5 Lucramul ® HOT 5209

TABLE-US-00026 TABLE 24 Compound 3 WP20 formulation. Cuticle from 2016 Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 12 h in % 24 h in % 48 h in % 1 TEHP premix V, 5 g/l 76 100 111 2 Agrotin ® SL, 2 g/l 0 3 3 3 Lucramul ® CO 30, 2 2 3 4 g/l 4 Mero ®, 5 g/l & 37 49 86 AMS, 2 g/l 5 none 0 0 0

TABLE-US-00027 TABLE 25 Compound 3 WP20 formulation, cuticle from 2016, but different batch than in Table 24 Cuticle Cuticle Cuticle Cuticle penetration penetration penetration penetration Run Adjuvant 6 h in % 12 h in % 24 h in % 48 h in % 1 TEHP premix V, 5 g/l 42 69 88 110 2 Genapol ® C 100, 2 g/l 0 1 11 15 3 Genapol ® X-060, 2 g/l 0 0 1 14 4 Crovol ® CR/70G, 2 g/l 21 51 76 101 & AMS, 2 g/l 5 Crovol ® CR/70G, 2 g/l 0 0 0 9 6 Mero ®, 5 g/l 9 30 41 52

TABLE-US-00028 TABLE 26 Bixlozone EC formulation. Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 6 h in % 12 h in % 24 h in % 1 Mero ®, 3 g/l 60 62 66 2 TEHP premix V, 5 g/l 60 61 64 3 Genapol ® X-060, 1 34 34 41 g/l 4 Lucramul ® HOT 32 34 37 5902, 1 g/l 5 none 27 29 31 6 Crovol ® CR/70G, 1 20 21 22 g/l

TABLE-US-00029 TABLE 27 Tolpyralate EC formulation. Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 12 h in % 24 h in % 48 h in % 1 TEHP premix V, 5 g/l 28 41 80 2 Actirob ® B, 5 g/l 19 25 41 3 Mero ®, 5 g/l 18 22 32

TABLE-US-00030 TABLE 28 Compound 4 WP20 formulation Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 12 h in % 24 h in % 48 h in % 1 TEHP premix V, 5 g/l 65 84 119 2 Agrotin ® SL, 2 g/l 0 0 0 3 Lucramul ® CO 30, 2 0 0 0 g/l 4 Mero ®, 5 g/l & 16 37 78 AMS, 2 g/l 5 none 0 0 0

TABLE-US-00031 TABLE 29 Compound 4 EC formulation. Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 12 h in % 24 h in % 48 h in % 1 TEHP premix V, 5 g/l 31 44 74 2 Crovol ® CR/70G, 2 0 0 12 g/l 3 Lucramul ® HOT 0 0 1 5902, 2 g/l 4 Mero ®, 5 g/l & 20 30 66 AMS, 2 g/l 5 Mero ®, 5 g/l 36 54 75 6 none 0 0 0

TABLE-US-00032 TABLE 30 Compound 5 WP20 formulation Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 12 h in % 24 h in % 48 h in % 1 TEHP premix V, 5 g/l 107 120 137 2 Agrotin ® SL, 2 g/l 64 79 104 3 Lucramul ® CO 30, 2 79 95 114 g/l 4 Mero ®, 5 g/l & 96 104 119 AMS, 2 g/l 5 none 6 14 52

TABLE-US-00033 TABLE 31 Compound 6 WP20 formulation Cuticle Cuticle Cuticle penetration penetration penetration Run Adjuvant 12 h in % 24 h in % 48 h in % 1 TEHP premix V, 5 g/l 24 36 62 2 Agrotin ® SL, 2 g/l 6 8 12 3 Lucramul ® CO 30, 2 7 8 16 g/l 4 Mero ®, 5 g/l & 36 48 66 AMS, 2 g/l 5 none 0 0 2

[0124] As the preceding examples show, the adjuvant combinations according to the invention show very good properties as penetration enhancers for a number of different active agrochemical ingredients in different formulation types.