HU193175B - Process for preparing aqueous fungicide suspension containing 2,4'-dichloro-alpha-/pyrimidin-5yl/-diphenyl-methanol as active substance - Google Patents

Abstract

Aq. fungicide suspensions contg. as active agent 4-20 wt% pref. 12 wt% 2,4'dichloro-alpha- (pyrimidin-5-yl)-diphenyl-methanol are obtd. by first preparing an aq. premix contg. pref. 40 wt% active agent together with 2-10 wt% pref. 3-8 wt% surfactant. The surfactant is made up of anionic poly-electrolyte contg. at least two components like a lignin-sulphonate deriv. and a cresol-formaldehyde or naphthalene-formaldehyde condensate, and a non-ionic ethylene-oxide-propylene-oxide condensate. The premix may contain opt. 5-15 wt% ethylene-glycol and 0.1-1.0 wt% anti-foaming agent. - The premix is comminuted in a colloid mill to a particle size of less than 5 micrometer, pref. less than 2 micrometer. The premix is now mixed with an aq. soln. contg. pref. 20-60 wt% ethylene-glycol, 2-5 wt% of a pref. 1:1 wt. ratio mixt. of nonyl-phenol-polyl-glycol-ether ane a sulphonated fatty acid deriv., further 0.1-0.25 wt% poly-saccharide of the xanthan type and opt. 0.5-2.0 wt% anti-foaming agent. The wt. ratio of premix to aq. soln. is between 1:9 and 1:1.

Description

FIELD OF THE INVENTION The present invention relates to a process for the preparation of aqueous suspension concentrates containing from 4 to 20% by weight of an active ingredient of the pyrimidinylmethanol derivative of formula I wherein X and Y are independently halogen. The compositions of the invention are useful for controlling fungicides such as apple and stone fruit orchards, grapes, gooseberries, currants, cucumbers and parsley. Examples of such pests are Venturia inaequalis, Podosphaera lencotricha, Monilia laxa, Uncínula necator, Erysiphe chichoriacearum (cucumber).

Pyrimidinyl methanol derivatives as fungicides are described in British Patent No. 1,218,623. One of the best known of these is 2,4'-dichloro-α- (pyrimidin-5-yl) -diphenylmethanol (FENARIMOL), which is practically in the form of an emulsion-forming concentrate. Given that pyrimidinyl methanol derivatives are highly effective systemic fungicides, the application rate per application per hectare is generally less than 100 g. Due to this low application rate, commercial formulations are also low in active ingredients (12% and 120g / l, respectively).

The low active ingredient content of the formulations is advantageous for the preparation of a spray liquid and for ensuring a precise dosage.

However, another reason for the low concentration of emulsion-forming concentrates is the poor solubility of the active ingredient in non-polar solvents. Emulsifiable concentrates can only be prepared using highly polar solvents. Due to the use of polar solvents, it is extremely difficult to find an excipient composition suitable for the formulation of the active ingredient which, under the conditions of use, can provide the necessary quality characteristics of the spray liquid. So far, it has not been possible to completely solve the stabilization of the spray liquor, preventing the crystallization of the active ingredient from the dispersed phase.

Attempts have been made to suppress application-detrimental drug release, but only very expensive solubilizing additives have been mixed. Therefore, we have chosen a different approach to this problem, and have attempted to formulate aqueous suspension concentrate formulations. While still maintaining the low active ingredient content of the emulsifiable concentrates on the market, the conventional method has failed to produce an aqueous suspension concentrate of suitable quality.

The compositions thus obtained exhibited a high degree of irreversible sedimentation, and the desired particle size of up to 5 micrometers in diameter was not achieved with conventional grinding equipment under normal conditions.

The present invention is based on the discovery that high molecular weight polyelectrolyte can be used as a surfactant in addition to the nonionic component to prevent the formation of a redispersible sediment. It has also been found that formulations of particles up to 5 micrometre in diameter required to produce the desired biological effect can be obtained by finely grinding a premix at a concentration of at least 30% by weight.

According to our studies, the biological effect of the compositions can be increased by the spray-drying retardant component / so-called. humidity /.

All these discoveries have led to a new formulation process which is different from what has been known hitherto, whereby low-concentration, aqueous suspension formulations containing no redispersible sediment can be prepared.

As a first step in the formulation process of the present invention, an aqueous premix comprising 30-60% by weight of a pyrimidinylmethanol derivative of the formula I, an anionic polyelectrolyte and / or a nonionic and / or ionic component as a surfactant is prepared.

In the formula (I) of the pyrimidinylmethanol derivatives, X and Y are each independently halogen. The aqueous premix may optionally further comprise an anti-freeze or spray-drying retardant and / or antifoam agent. The aqueous premix is diluted with an aqueous solution after fine grinding (1:14) to (1: 1). The aqueous diluent solution comprises a thickening agent, antifreeze or spray drop retardant and / or anionic polyelectrolyte and / or nonionic and / or ionic component and / or antifoam as surfactant.

The aqueous suspension concentrate obtained after mixing contains at least 2% by weight of a surfactant, at least 5% by weight of antifreeze or spray-suppressant, 0.1 to 1% by weight of a thickener. The surfactant used is at least one type of anionic polyelectrolyte and at least one nonionic component. The aqueous suspension may optionally comprise more antifoam and / or ionic surfactant is also ^one.

The formulation process utilizes auxiliaries commonly used in the practice of plant protection sc-formulation. The surfactant used is anionic polyelectrolyte, ionic and nonionic excipients.

The anionic polyelectrolytes may be: various lignin sulfonates; formaldehyde with sulfonated cresols or sulfonated naphthalene

Condensation products of -2193175. The ionic surfactants may be: salts of various saturated or unsaturated carboxylic acids; sulfonates of aliphatic, aromatic, aliphatic-aromatic hydrocarbons, sulfates of alkyl, aryl, aralkyl alcohols; sulfonates of alkyl, aryl, aralkyl acids, esters, ethers; sulfonates of phenols, cresols, or naphthalene condensation products; sulphated vegetable or animal oils; alkyl, aryl, aralkyl phosphate esters; sulphates and phosphate esters of polyglycol ethers of ethylene oxide with fatty alcohols or alkyl phenols. Nonionic surfactants may be condensation ethers of ethylene oxide with fatty alcohols; ethylene oxide condensation ethers with alkyl phenols, ethylene oxide condensation esters with various organic acids; ethylene oxide and / or propylene oxide polymerizates and their derivatives.

Suitable tackifiers and thickeners include alkaline earth metal soaps, salts of sulpho-succinic esters, natural and artificial water-soluble or water-swellable macromolecules. Suitable antifoam agents include low molecular weight ethylene oxide / propylene oxide condensates; aliphatic alcohols; special silicone oils; fatty amides. Ethylene glycol, propylene glycol, or glycerol are most commonly used as antifreeze or spray-drying retardant.

In preferred embodiments of the process of the present invention, the aqueous premix contains 35 to 45% by weight of the active ingredient 2,4'-dichloro-a- (pyrimidin-5-yl) diphenylmethanol (FENARIM.OL) or 2-chloro Contains 4'-fluoro-α- (pyrimidin-5-yl) diphenylmethanol (NUARIMOL).

Suitable anionic polyelectrolytes for the preparation of the aqueous premix and diluent are preferably lignin sulfonate (TENSIOFIX LX Special, ULTRAZINE NA) and / or sulfonated cresol / formaldehyde (HOE S 1494) and / or sulfonated naphthalene / formaldehyde (TAMOL). Preferably, the nonionic surfactants are diethylene oxide / propylene oxide condensate and / or alkyl, aryl, polyglycol ether and / or ethoxylated fatty alcohol and / or ethoxylated fatty acid, and the ionic surfactant is preferably aliphatic, aromatic or aliphatic. sulfonates of aromatic hydrocarbons and / or phosphates of polyglycol ethers of ethylene oxide with fatty alcohols or alkylphenols.

Namely ethylene oxide / propylene oxide condensate (PLURIOL PE 10500), ethoxylated castor oil (EMULSOGEN EL), ethoxylated tributyl phenol / SAPOEGENAT T180 /, ethoxylated nonyl phenol / RENEX 650, ARKOPAL N-130 /, ethoxylated 1 a ur i 1 - a 1 alcohol (TENSIOFIX PO-132), alkyl sulfonate (NETZER IS), sodium diisobutyl naphthalene sulfonate (T1NOVETIN B), calcium dodecylbenzene sulfonate and ethoxylated nonyl4

a mixture of phenol (TENSIOFIX LS), a mixture of calcium dodecylbenzenesulfonate and ethoxylated propoxylated nonylphenol (TENSIOFIX B 7425), ethoxylated fatty alcohol, ethoxylated fatty alcohol phosphate ester, ethoxylated nonylphenol and ethoxylated nonylphenol / use it. The antifreeze or spray-drying retardant is preferably ethylene glycol, and the thickener is a "xanthan gum" polysacchar (emulsion containing RHODOPOL 23/33% silicone oil emulsion / SILICON SRE).

The premix is preferably milled, preferably in pearls. Thus, the particles are ground to a size of up to 5 microns, preferably up to 2 to 3 microns. The ground premix is diluted with an aqueous solution (1: 14 / - / 1: 1). The total amount of surfactants in the aqueous suspension concentrate prepared by dilution is preferably 3-8% by weight. The weight ratio of the at least one anionic polyelectrolyte present as the surfactant to the at least one nonionic component is preferably in the range of from 4: 1 to 1: 1.

The aqueous suspension concentrate preferably contains, in addition to the active ingredient, the anionic polyelectrolyte and the nonionic component, 20-60% ethylene glycol and 0.1-0.3% xanthan gum polysaccharide, optionally with an ionic surfactant and / or an antifoam agent.

In preferred embodiments, an aqueous premix comprising 40% FENARIMOL, 3-8% surfactant, 5-15% ethylene glycol and 0.1-1% antifoam is prepared, wherein the anionic polyelectrolyte is lignin sulfonate and cresol / formaldehyde or naphthalene / formaldehyde condensate and ethylene oxide / propylene oxide condensate as non-component. After the fine grinding, the premix is diluted with an aqueous solution containing 2-5% surfactant, 0.1-0.25% polysaccharide (xanthan gum) and 0.5-2% foaming agent. The non-ionic surfactant used in the preparation of the diluent is nonyl phenol polyglycol ether and the ionic sulfonated fatty acid derivative in a 1: 1 weight ratio.

The process according to the invention has the advantage that it can be used to produce aqueous suspension concentrates of excellent colloidal chemistry stability, which can be stored for long periods of time without any change in quality due to easy pouring, low spontaneous dispersibility in water and easy redispersibility of the resulting sediment. The spray liquors prepared from the compositions by diluting with water have excellent floatability over a wide temperature range. Spray broths made for their use are compatible with other pesticides and foliar fertilizers.

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The compositions of the present invention exhibit a biological activity superior to that of the prior art.

The invention is illustrated by the following non-limiting examples.

Example 1

An active ingredient is prepared as a premix using 96% pure Fenarimol and 97% pure Nuarimol. Their composition is shown in Table 1.

200-200 ml of the premixes are ground in a Molinex PE 075 bead mill. Grinding was carried out for 1 hour at 2000 rpm with 200 ml glass beads of 1 mm diameter.

Aqueous dilution solutions of the composition given in Table 2 are prepared.

The premixes with the dilution solutions are shown in Figure 3.

Mix according to the mass ratios shown in Tables Ιθ and 4. Test results for the quality of the aqueous suspension concentrates thus prepared are given in Tables 3 and 4.

Table I: Composition of the premixture

components THE B C D Composition E F G H I (TZ) J K L M fenarimol 42 42 - - 31 31 - 52 - 63 63 - - nuarimol - - 41 41 - 31 - 52 - - 62 62 Ethylene glycol 10 8 9 6 15 5 - 10 8 - 5 6 TENSIOFIX LX Special 4 - - 4 20 1 - - - - 3 - - ULTRAZINE NA - 2.5 - - - 2 - 4 3 - 3 - HOE S 1494 1 - 4 2 - - - - - 2 - - TAM0L-NN0 - 2 - - - 1 12 3 - - 3 - TENSIOFIX B 7425 3 - 2 PLURI0L PE 10500 - 1.5 - - - - - 2 - 3 - EMULSOGEN EL - - - 3 - - - - - - - 3 SAPOEGENAT T 180 - - - - - 15 - - - - - - TENSIOFIX P0-132 - - - - 1 - 2 - 3 - - - RENEX 650 - - - - 2 - - - 6 - - - SILICON SRE 0.5 0.5 - 0th , 5 1.5 - 1 1.5 1 1 .5 1 0.5 0.5 Distilled water 39.5 43.5 44 43rd , 5 44.5 52 45 32.5 28 15.5 28 26.5 28.5

Table 2: Composition of Dilution Solutions

components 1 2 3 4 Composition (w / w) 10 11 12 5 6 7 8 9 ethylene glycol 22.2 35.7 60 22.2 35.7 60 22 60 25 5 80 36 ARKOPAL N-130 1.3 1.4 ι. 6 1.7 2.1 2 2 - - - - - PLURIOL PE 10500 - - - - - - - - - 3 - - TENSIOFIX LX Special - - - - - - - - - - 1 4 NETZER IS 1.3 1.4 1.6 1 7 2. 1 2 20 - - - - - TINOVETIN B - - - - - - - 2 TENSIOFIX CG- 21 - - - - - _ - '- - - - 3 TENSIOFIX LS - - - - - - - - 2 - - - RHODOPOL 23 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.3 1.3 0.2 0.2 0.3 SILICON SRE 1.1 1.1 1.6 1.1 1.1 1.6 8.5 1.5 - 1.3 - 1.8 water 73.9 60.2 35 73. 1 58.8 34.2 47: 3 38.2 71.7 88.5 18.8 54.9 Table 3: The preparations. qualitative examination The investigated A: 1 THE 2 THE 3 B: 4 B: 5 B: 6 C: 5 D: 6 E: 7 E: 7 E: 8 specific 1: 9 3: 7 1: 1 1: 9 3: 7 1: 1 3: 7 3: 7 1: 9 1: 1 3: 7 ^d 50 2.1 2.0 2.1 2.0 2.1 2.0 2.0 2.2 2.3 2.0 Second 1 T 103 106 84 87 92 95 96 90 83 89 86 L 99.0 99.0 99th 5 99.6 99.2 99.3 99.2 99.6 98.9 99.7 98 .0

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Table 4: Qualitative testing of preparations

The investigated F: 9 G: 10 G: 8 H 4 1: 3 Jr 2 Q: 11 Q: 11 L: 10 L: 10 Mn: 12 M: 12 specific 2: 8 1: 1 6: 4 1:11 2: 8 1 14 3: 7 2: 8 1:14 2: 8 1:14 3: 7 ^d 50 2.9 3.1 2.6 2.2 1.9 2.0 1.8 2.3 2.0 1.7 2.2 1.8 T 104 99 97 84 82 16 81 85 91 93 87 88 L 97.9 99.3 98.9 99.5 99.6 99.1 98.9 99.0 99.3 99.5 99.2 98.8

Notations used in Tables 3 and 4 are: d ₅₀ : mean particle diameter in micrometer, measured with Coulter-Counter TA-11.

T: Penetration performance of erosion / load of sediment formed in 100 ml of preparation at 4000 rpm / 100 times the load acceleration, measured with a Dynometer 1910 instrument. / For red-dispersible sediment, T is greater than 150 erg / min.

L: buoyancy,% stability of 0.2% FENARIMOL suspension in WHO standard hardness water.

Example 2: For the purpose of comparison, aqueous suspension concentrates according to the data in Table 5 are prepared. The composition of the two models (N and O) is exactly the same as the A: l = 1: 9 and A: 3 = l: I-V1 formulations in Table 3, respectively. The other two models (P and R) differ from them only in that they contain only anionic polyelectrolyte (P) or only nonionic component (R) corresponding to the combined amount of anionic polyelectrolyte and nonionic component in the original formulations. material.

Comparative compositions are prepared by a conventional method. These formulations are prepared in a single step, i.e., the components are ground together using the conditions described in Example I.

The results of the comparative model quality studies are presented in Table 6. Comparing these data with Tables 3 and 4, the aqueous suspension concentrates of the present invention exhibit advantageous properties over conventional formulations.

Table 5: Composition of Comparative Formulations

Components Composition (t%)

N 0 P R FENARIM0L 4.2 21.0 4.2 21.0 ethylene glycol 21.0 3 5.0 21.0 35.0 TENSIOFIX LX Special 0.4 2.0 1.6 - TENSIOFIX B 7425 0.3 1.5 - 2.0 HOE S 1494 0.1 O.5 0.4 - ARKOPAL N-130 1.2 O8 - 2.8 NETZER IS 1.2 0.8 1.2 0.8 RHODOPOL 23 0.2 0.1 0.2 0.1 SILICON SRE 1. 1 1 .1 1. 1 1.1 Distilled water 70.3 37.2 70.3 37.2

Table 6: Qualitative study of comparative formulations

The analyzer j is analyzed N 0 P R ^d 50 11 7 13 9 T 132 119 175 243 L 81 89 83 78

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Claims (3)

1. A process comprising 4 to 20% by weight of an active ingredient, at least 2% by weight of surfactant - including at least one surfactant anionic polyelectrolyte and at least one nonionic component and optionally an ionic component, at least 5% by weight of antifreeze or spray-drying For the preparation of aqueous suspension concentrates containing from 1 to 1% by weight of a thickening agent and optionally excipients, characterized in that: (a) 30-60% by weight of the active substance 2,4-dichloro-α- (pyrimidin-5-yl) diphenylmethanol, lignin sulphonate and / or cresol / formaldehyde and / or naphthalene / formaldehyde condensate as surfactant anionic polyelectrolides and / or or ethylene oxide / propylene oxide condensate and / or alkylaryl polyglycol ether and / or ethoxylated fatty alcohol and / or ethoxylated fatty acid as nonionic component and optionally ionic component of sulfonates of aliphatic, aromatic or aliphatic-aromatic hydrocarbons, - grinding of the desiccant retardant, in the presence of water, to a particle size of less than 5 micrometers; (b) a thickening agent, antifreeze or spray-suppressant and optionally anionic polionic surfactants such as lignin sulphonate and / or cresol / formaldehyde and / or naphthalene / formaldehyde condensate and / or ethylene oxide / propylene oxide / non-ionic component / or alkylaryl polyglycol; ether and / or ethoxylated fatty alcohols and / or phosphate esters of polyglycol ethers of aliphatic, aromatic or aliphatic-aromatic hydrocarbons and / or polyglycol ethers of ethylene oxide with fatty alcohols and / or alkyl phenols and optionally antifoaming agent in water) and the aqueous solution prepared according to b) in a weight ratio (1:14) to (1: 1). (priority: 29.07.1983) 2. Process 4 to 20% by weight of active ingredient, at least 2% by weight of surfactant - including at least one surfactant anionic surfactant and at least one nonionic surfactant 5 component, and optionally ionic komponenst-, at least 5% by weight of antifreeze agent, and spray droplet-clogs retarder, C 1-1 aqueous suspension containing% of a thickening agent and optionally auxiliary substances ¹⁰ penziókoncentrátumok preparation, characterized in that a) 30 to 60% by weight of the pyrimidinyl methanol derivative of the formula I as active ingredient, wherein X and Y are Independently selected from the group consisting of halogen atoms, lignin sulfonate and / or cresol / formaldehyde and / or naphthalene / formaldehyde con2θ densates and / or ethylene oxide / propylene oxide condensate and / or alkylaryl polyol glycol as nonionic components. or ethoxylated fatty alcohol and / or ethoxylated fatty acids and, optionally, ionic constituents of sulphonates of aliphatic, aromatic or aliphatic-aromatic hydrocarbons, antifreeze and spray-suppression agents, 30 antifoam is ground in the presence of water to a particle size of less than 5 micrometers, b) a thickening agent, anti-freeze or spray droplet-clogs retarder ^35, optionally, surface active anionic polielektrolitként ligninsulfonate and / or cresol / formaldehyde and / or naphthalene / formaldehyde condensate ₄ θ condensate and / or non-ionic surfactant with ethylene oxide / oxide / propylene oxide condensate and / or alkylaryl polyglycol ether and / or ethoxylated fatty alcohol and / or aliphatic aromatic as ionic component Aqueous solution obtained in 45, or aliphatic-aromatic hydrocarbons, sulfonates and / or the mixture of fatty alcohols and / or alkyl phenols skilled polyglycol ethers foszfátésztereit and optionally antifoam water at ⁵⁰ was dissolved and a) ethylene oxide, and b) by (1:14 ) (1: 1). (priority: May 16, 1986)