AU641528B2

AU641528B2 - Solid formulations

Info

Publication number: AU641528B2
Application number: AU81303/91A
Authority: AU
Inventors: Stefan Dutzmann; Dieter Feucht; Peter Feyen; Uwe Priesnitz; Wolfgang Thielert; Ulrike Wachendorff-Neumann; Raphael Wieschollek
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1990-08-24
Filing date: 1991-07-23
Publication date: 1993-09-23
Anticipated expiration: 2011-07-23
Also published as: EP0473003A3; PT98682A; JPH04279502A; CA2049644A1; DE4120694A1; EP0473003A2; BR9103631A; EP0757891A3; PT98682B; AU8130391A; EP0757891A2

Description

Our Ref: 401688 P/00/011 Regul~ation 3:2 64 152r-W8

AUSTRALIA

Patents Act 1990

ORIGINAL

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Applicant(s): Address for Service: Invention Title: Bayer Aktiengesellschaft D-5090 Leverkusen Bayerwerk

GERMANY

ARTHUR S. CAVE CO.

Patent Trade Mark Attorneys Level 10, 10 Barracix Street SYDNEY NSW 2000 Solid formulations The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 The present invention relates to new solid formulations based on agrochemical active compounds, to processes for the preparation of the solid formulations and to their use as agents for treating plants.

It has already been disclosed that agrochemical active compounds can be used in the form of solid formulations, such as granules or powders. However, the activity of such preparations is not always entirely satisfactory.

For example, it is in some cases less powerful than that (of corresponding emulsifiable concentrates.

S In particular, it has already been disclosed that 1-(4chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-l-yl-methyl)-pentan-3-ol has fungicidal properties and can be S converted into customary formulations (cf. EP-OS (Euro- 20 pean Published Specification) 0,040,345). Thus, solid formulations, such as granules or powders, which contain the above-mentioned active compound, can also be produced. The activity and the compatibility of these con- Sventional solid formulations, howev r, is not always S 25 entirely satisfactory, e Furthermore, the production of granules containing agrochemical active compounds by the fluidised-bed process has also been described (cf. EP-OS (European S* 30 Published Specification) 0,163,836). Thus, it is also 0 .o possible using this method, to obtain granules in which 1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-ylmethyl)-pentan-3-ol is present as the active component.

However, the activity of these formulations too, leaves ,c something to be desired in some cases.

2 New

A)

solid formulatio~ns of at least onte agrachemical active compound, at least one additive from the groups comprising polyethoxy-isotridecylalcohol having an average of 6 ethylene oxeide units per molecule, or alkylaryl-polyethoxyethanol phosphoric acid esters, or 0 0 "0 the N-alkyl-lactamns of the formula (CH2)nN

N-R

C-/

11 0

(II)

in which R represents alkyl having 6 to 18 carbon atoms and n represents the numbers 3, 4 or 5, or the N,N-dimethyl-alkylcarboxamides of the formula 4* 55 S S

U

05 0 a.

S@

,-CH

3

(III)

3 in which

R

1 represents alkyl having 5 to 11 carbon atoms, C) at least one dispersant, D) at least one carrier and E) if appropriate, further active compounds and/or additives, 15 have now been found.

Furthemore, it has been found that the new solid formulations can be prepared by either S* 20 a) introducing a solution of at least one agrochemical active compound and, if appropriate, additives in at least one additional compound from amongst the groups mentioned under and 25 a mixture of at least one dispersant and at least one carrier and, if appropriate, further agrochemical active compounds and/or additives, 4 r 4 separately into a fluidised-bed granulator, granulating the mixture until a granular product has formed, and discharging the granules from the fluidised-bed granulator, if appropriate after spraying with water followed by drying, or b) introducing a mixture of at least one dispersant and at least one carrier and, if appropriate, Sagrochemical-active compounds and/or additives'into So* 15 a mixer, 4 spraying into the mixer a solution of at least one agrochemical active compound and, if appropriate, additives in at least one additional compound from 20 amongst the groups mentioned under until a product having the desired particle size is formed and discharging the resulting solid formulation from 25 the mixer, if appropriate, after previously spraying with water followed by drying, and, if appropriate, subsequently grinding the resulting solid formulations.

Furthermore, it has been found that the solid formulations according to the invention can be employed very successfully as agents for treati'ng plants and have excellent biological properties.

I J1 5 Finally, a new device for preparing the new granules has been found. The device essentially consists of a fluidised-bed granulator which comprises S one or more feed pipes for feeding a solid phase to the fluidised bed, one or more two-fluid nozzles for feeding and for atomising a liquid phase, one or more feed pipes for feeding fluidising gas 15 and a *e one or more counterflow gravity classifiers for discharging granules.

0

S

It must be considered extremely surprising that the solid formulations according to the invention in all cases have superior biological properties to the corre- ,,sponding solid formulations hitherto known. Thus, for 2 example, the solid formulations according to the in- 25 vention, based on 1-(4-chlorophenyl)-4,4-di>;ethyl-3- (1,2, 4 -triazol-1-yl-methyl)-pentan-3-ol can be used S*considerably more effectively for combating phytopathogenic fungi than the solid formulations known from the prior art and which also contain the same active com-

S

30 pound.

S Agrochemical active compounds which can be contained in the solid formu7/ations according to the invention are all those substances which are conventionally suitable 6 for treating plants. Suitable active compounds are not only substances which are solid at room temperature but also those which are liquid at room temperature. The only precondition for the use of liquid components is that they must be capable of being applied to solid carrier substances, if appropriate, with powdering. The active components can be soluble or insoluble in water.

They must have such stability that they do not undergo any major decomposition while the process according to the invention is being carried out or during the use of the resulting solid formulations.

In the present case, agrochemical active compounds are o. to be understood to be active compounds which are customarily usable in crop protection. They preferably n include insecticides, acaricides, nematicides, fungi- 20 cides, herbicides, growth regulators and fertilisers.

The following may be mentioned as specific examples of such active compounds.

1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl- 25 methyl)-pentan-3-ol (tebuconazole), 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1,2,4-triazol-1yl)-butan-2-ol (triadimenol), l-(4-chlorophenoxy)-3,3-dimethyl-l-(1,2,4-triazol-1-yl)butan-2-one (triadimefon), S* 1 A, -7 1-(4-phenyl-phenoxy)-3,3-dimethyl-(l,2,4-triazol-1-yl)butane-2-oi (bitertanol), I-phenyl- (N I-f luorodichloromethylthio) sulphamide (dichiofluanid), N,N-di-methyl- (W -f luorodichloronethylthio) 4-methylpheny2l)-sulphamide (tolyifluanid), N-trichloromethylmercapto-4-cyclohexene-l1, 2-dicarboxamide (captan), N- 112,2 -tetrachloroetliyl-sulphenyl) -cis-4-cyclohexene- 1,2-dicarboxainide (captafol), N-trichloromethylthio-phthalinide (folpet), K:'."N-dodecyl-guanidine accetate (dodine), tetrachloro-isophthalonitzile (chiorothalonil), -tetrachlorophthalide, zinc ethylene-bis-dithiocarbamate (zineb), manganese ethylene-bis-dithiocarbaniate (maneb), *zinc ethylene -bi s-dithioc arbainate /mangane se ethylene-bis- 0~20 dithiocarbainate (mancozeb), zinc propylene-i, 2-bis-dithiocarbamate (propineb), 1,12-diiethylethyl) -phenyl) -2-methyipropyl]piperidine (fenpropidin), N-tridecyl-2,6-dixnethyl-morpholine (tridemorph), N-dodecyl-2, 6-dimethyl-miorpholine (aldimorph), (2,4-dichlorophenyl)-2- (2-propenyloxy) -ethyl]imidazole (imazalil), 6-trichiorophenoxy) -ethyl) -N-propyl-lH-imidazole (prochloraz), 30 N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-l,2- *.:dicarboximide (procymidone) 2-methoxycarbainoy1-benzimidztzole (carbendazim), 8methyl 1-(butylcarbamoy1)-2-benzimidazoleca-bamaLe Cbenomtyl), 2,4-cOichloro-6- (21-chlorophenyl-amino)-1 ,3,4-Lriazine bis-(8-guanidino-octyl)-aiine triacetate (guazatirie), 1- chlox-oberizyl -cyclopentyl-3--phenyl-urea (pencycuron), 6-rnety-2-oxo-1,3--dithiolo-E4,5-bJ-quinoxaline (chinoxnethionat), Lrans-4-(4-chlorophenyl)-N-cyclohexyl-4-meLhyl-2-oxo-3thiazolidin-carboxanide (hexythiazox), 15 1-(4-fluorophenyl )-l-(1,2,4--triazol-1-yl-methyl)-2-(2chloropheiyl )-oxirane, :4f o -24 d c lo-h n l -12 4 tr a o -l -e t n 9 (penconazole), Goes 1-t2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl- 20 rnethyl3-11--(1,2,4-triazole) (propiconazole), 1-(2-t2-chloro-4-(4-chlorophenoxy)-phenyl-4-nethyl- (1,3-dioxolan-2-yl)-rnethy1)-1H-i1,2,4-Lriazole), 1-(2,4-dichloropheriyl)-4,4-dimethyl -2-(I,2,4-triazol-1f yl)-pentan-3-J. (cdiclobuLrazole), 25 1-(2-chlorophenyl)-2-(l-chloro-cycloprop-1-yl)-3-(1,2,4triazol-1-yl )-propari-2-ol, 1-cyclohexyl-4,4-dianethyl-3-hydroxy-2-(1,2,4-Lriazol-1yl)-pent-1-ene (triapenthenol), 2-Lsopropoxy-phenyl-N-riethyl-carbaiate, 30 4-arin-6-(1,1-dimethyl-ethyl)-3-methylthio-1,2,4- 0* triazin-5(4Hi)-on (nmetribuzin), 3-methyl-4-amino-6-pheny-1,2,4-triazin-(4'i)-on (inetamitron), V 1 N-bernzthi azoIy -N-meth,ylI-N 1 -me thy I -urea, 3-methoxycarbonyl -aminophenyl (3 -methyl -phenyl) carbamate, N- (4-trifluoromethoxy-phenyl (2-chloro-benzoy ureas 1-[4-(2-chloro-1,1,2-trifluoroethoxy)-.phenyl]-3-C4phenyl-1,2,5-oxadiazol-3-yl )-urea, 2-ethoxy-2, 3-dihydro-3,3-dimethyl-5-benzofuranylmethansul fonate.

1-(4-Chlorophenyl)-4,4-di methyl-3-(1,2j4-triazol-l-yl- 15 rethyl)-pentan-3-ol of the formula set* 69 "e se b 06 1 20

CH

2 eithe ihe patoulrl preferecmoeto.n ditr ir thrarohmia active compoundanitusas.afnicd r 10 In the solid formulations according to the invention, at least .ane of the substances mentioned under is contain'od as an additional substance. The following Eire preferably suitable: polyethoxyt-iso-tridecyl alcohol having an average toQ of 6 ethylene oxide units per molecule, alkylaryl-polyethoxyethanol phosphoric acid ester, commercially t-vailable under the name "Blendex®o, 15 N-alkyl-lactams of the formula (II) in which R represents alkyl having 8 to 14 carbon atoms and 0 n represents the numbers 3, 4 or 5, and moreover, ind vidual N ,N-dimethyl-alkylcarboxamides of the formula (III), or mixtures thereof.

25 Particularly preferred N-alkyl-lactams are those substances of the formula (11) in which 0 00 R represents alkyl having 8, 10 or 12 carbon atoms and n0 r represents the numbers 3, 4 or S.

The foll.owing may be mentioned as examples of N-alkyllactams of the formula (II): N-dodecyl -caprolactam N-decyl -caprol actarn N-octyl -caprolactam N-dodecyl-pyrrolidone N-decyl-pyi olidone N-octyl-pyrrol idone N-dodecyl -val erol actam N-decyl-valerolactam 15 N-octyl-valerolactan, too* Also particularly preferred is th, mixture of N,N-di- *methyl-alky'.,-,rboxamides4 of the formula (711) which is known under the tradenama Mllcomid and which comprises, on average, 5% N,N-dimethy.-hexaneca~boxanide, 50% N,Ndimethyl-octanecarboxamide, 40% N,N-dimnethyl-decanecarboxamide and 5% N,N-dimethyl-dodecanecarboxamide.

The additional substances present in the solid 25 formulations according to the invention are known (cf.

J. Org. Chem. 8 1087 (1953); Ann# Chem. 596 203 los J.iS5;3 Amer. Chem. Soc. 69, 715 (1947); DE-AS (German Published Specification) 1,160,268; EP-0-S (European Published Specification) 0,077,078, WO 30 88100 184 and Farm Chemicals Handbook 1990, C 44).

Suitable dispersants in the case of solid formulations according to the invention are all substances which have appropriate ,5urface-active properties and which can 12 customarily be employed for such purposes. The following are preferred; ligninsulphonates such as lithium salts, sodium salts, potassium salts, magnesium salts, calcium salts and ammonium salts of ligninsulphonic acid, furthermore condensation products of aryl- or alkylarylsulphonic acids and formaldehyde, such as condensation products of sulphonated ditolyl ether and formaldehyde, and salts thereof, as well as addition products of ethyleneoxide and fatty acid esters and salts thereof.

Suitable carriers in the case of the solid formulations 15 according to the invention are all solid substances which have a large surface area and/or high absorbency and which can customarily be used in granules and powders. The following are preferred: ground natural minerals such as kaolins, clays, talc, chalk, quartz,

O.

0 20 attapulgite, montmorillonite or diatomacious earth, and ground synthetic minerals such as highly-disperse silica, alumina and silicates, and furthermore salts such as potassium sulphate, potassium carbonate and sodium hydrogen carbonate, Suitable additives which can be contained in the solid formulations according to the invention are binders, preservatives, colorants, acids and granulation liquids.

tr 13 Binders which can be contained are all binders (tackifiers) which are customarily present in waterdispersible solid formulations. The following are preferably suitable in this context: methylcellulose, sugars, dextrin, jtarch, alginates, glycols, polyvinyl pyrrolidone, ligninsulphonate, gum arabic, polyvinyl alcohol and polyvinyl acetate.

Examples of preservatives which can be contained in the solid formulations according to the invention are 2hydroxybiphenyl, sorbic acid, p-hydroxybenzaldehyde, 15 methyl p-hydroxyblnzoate, benzaldehyde, benzoic acid and propyl p-hydroxybenzoate.

f Colorants which may be mentioned as suitable additives are inorganic pigments such as iron oxide, titanium *e 20 dioxide and Prussian blue, and organic dyestuffs such as alizarin, azo and metal phthalocyanine dyestuffs.

An example of an acid which may be mentioned as a suitable additive is p-tolyl-sulphonic acid, Examples of granulation liquids which can be contained in the solid formulations according to the invention are water, organic solvents or mixtures of water and organic solvents. Preferred organic solvents which are suitable S* 30, in this context are alcohols such as ethanol and glycol, halogenohydrocarbons such as methylene chloride, and ethers such as dioxane and tetrahydrofuran. Water is particularly preferred as granulation liquid, 14 In the solid formulations according to the invention, the percentage contents of the components can be varied within substantial range. In general, the content of agrochemical active compounds is between 5 and 90% by weight, preferably between 10 and 50% by weight. The amount of additive is generally 5 to 75% by weight, preferably 10 to 70% by weight. The amount of dispersant is generally between 1 and 30% by weight, preferably between 5 and 25% by weight; and the amount of carrier is generally between 10 and 50% by weight, preferably between 15 and 45% by weight. The additional compounds 15 are generally contained in amounts of between 10 and by weight, preferably between 20 and 50% by weight, and the a.nount of granulation liquid is generally between 4 0 and 3.5% by weight.

20 When carrying out the process according to the invention by means of variants or all those components can preferably be used as being preferred which have already been mentioned in connection with the descrip- S* tion of the solid formulations according to the in- 25 vention.

For carrying out the process according to the invention by means of variant a solution of at least one agrochemical active compound and, if appropriate, addi- 30 tional substances in at least one additive is first prepared. For this purpose, the components are stirred with each other at temperatures between 10 0 C and 1000C, preferably between 20°C and 90 0 C, so that a liquid phase results. Accordingly, the liquid phase is a melt or a true solution.

0 w 15 Furthermore, a solid mixture is prepared by mixing at least one dispersant and, if appropriate, one or more agrochemical active compounds and/or additives with at least one solid carrier in such a ratio that the resulting mixture is in the solid phase. This mixture of solid substances is homogenised using customary processes.

For carrying out the process according to the invention by means of variant the liquid and the solid phase are introduced separately into a fluidised-bed granulator. In general, a procedure is followed in which the solid, finely pulverulent phase is passed into the granulator through one or more inlets and fluidised with S* the aid of a stream of gas. The liquid phase is also sprayed into the granulator through one or more separate 20 nozzles. The liquid phase is preferably added via one or more two-fluid nozzles which are constructed in such a way that the liquid phase is transported through a first line and a stream of gas (atomising gas) is fed in through a second line. Both streams meet each other 25 at the end of the nozzle in such a way that, with the 5 aid of the atomising gas, the liquid phase is sprayed into the fluidised bed in the form of small droplets, and there meets the particles of the solid phase.

30 If appropriate, post-granulation can be carried out by 4 Sspraying on water. To remove water and/or other solvents, the granules can be dried with the aid of the stream of gas for fluidisation.

16 When carrying out the process according to the invention by means of variant the temperatures can be varied within a substantial range. For example, the process is carried out using a liquid phase whose temperature is between 10 0 C and 100 0 C, preferably between 20 0 C and 0 C. The solid phase is fed in at temperatures between 10 0 C and 500C, preferably between 20 0 C and 400C. The temperature of the stream of gas for fluidisation is between 20°C and 250°C, preferably between 40 0 C and 2000C, *The temperature of the stream of gas for Satomisation, which enters through the Lwo-fluid nozzle, 15 is between 0°C and 100°C, preferably between 0 0 C and 900 C.

To produce the fluidised bed, all gases which are customarily employed for such purposes can be used. Air 20 or nitrogen are preferably suitable.

For spraying in the liquid phase via one or more twofluid nozzles, it is also possible to use all gases which are customary for such purposes. Air or nitrogen 25 are preferably suitable, The finished granules can be discharged from the granulator via customary withdrawal devices. Countercurrent gravity classifiers are preferably used.

a. 0 3 The product obtained can subsequently be postgranulated and/or dried and/or ground.

When variant is used, the process according to the invention can be carried out continuously or batchwise.

17 The device for preparing the granules according to variant of the invention is a fluidised-bed granulator which differs from the previously known apparatuses of this type essentially by the fact that the liquid phase and the finely pulverulent solid phase are fed separately into the fluidised bed.

One or more feedpipes for the solid phase are located in the lower area of the fluidised bed, preferably in the side wall of the apparatus, slightly above the inlet-flow bottom. To feed the liquid phase, there exist 15 one or more two-fluid nozzles which are preferably arranged at the inlet-flow bottom. The two-fluid nozzles are constructed in such a way that the liquid phase is transported through the first feedpipe and a stream of a gas (atomising gas) is fed through a second feedpipe.

20 One or more feedpipes for introducing fluidised gas are ar-anged below the inlet-flow bottom. Finally, the device contains one or more counterflow gravity classifiers for discharging granules. The counterflow gravity classifiers are preferably built into the inlet-flow 25 bottom. Preferred counterflow gravity classifiers which are suitable are so-called zig-zag classifiers.

Variant of the process according to the invention is preferably carried out in a fluidised-bed granulator 30 as shown in Figure 1 in the form of a diagram. In this figure, 18 1 2 3 4 6 7 8 9 denotes denotes denotes denotes denotes denotes denotes denotes denotes denotes the the the the the the the the the the wall of the granulator vessel, feed for the solid phase, feed for the liquid phase, feed for the atomising gas, two-fluid nozzle, feed for the fluidised gas, fluidised bed, settling zone in the fluidised bed, counterflow gravity classifier, and withdrawal device for the granules.

o. so 4u 0 *r S 0 For carrying out the process according to the invention by means rf variant a solid mixture is first prepared by mixing at least one dispersant and, if appropriate, one or more agrochemical active compounds and/or additional compounds with at least one solid 20 carrier in such a ratio t\at the resulting mixture is in the solid phase. This mixture of solid substances is homogenised and ground using customary processes.

0 0 000 O 4 Sq..

0 OS S Furthermore, a solution of at least one agrochemical 25 active compound and, if appropriate, additional substances in at least one additive is prepared. For this purpose, the components are stirred with each other at temperatures between 10 0 C and 1000C, preferably between 0 C and 90 0 C, so that a liquid phase results. Accordingly, the liquid phase is a melt or a true solution.

e* 19 For carrying out the process according to the invention by means of variant the solid, finely pulverulent phase is passed into a mixer and sprayed with the liquid phase. In general, a procedure is followed, in which the liquid phase is sprayed into the mixer through one or more separate nozzles, The liquid phase is preferably 'led via one or more two-fluid nozzles which are constructed in such a way that the liquid phase is transported through a first line and a stream of gas (atomising gas) is fed in 15 through a second line, Both streams meet each other at .the end of the nozzle in such a way that, with the aid of the atomising gas, the liquid phase is sprayed into the mixer in the form of small d,oplets, and there meets the particles of the solid phase.

If appropriate, a post-treatment can be carried out by spraying on water. To remove water and/or other solvents, the resulting solid formulation can be dried by customary methods.

When carrying out the process according to the invention by means of variant the temperatures can also be varied within a substantial range. For example, the process is carried out using a liquid phase whose 30 temperature is between 10 0 C and 1000C, preferably between 20 0 C and 90 0 C. The solid phase is kept at temperatures between 10 0 C and 50 0 C, preferably between 0 C and 40OC, The temperature of the stream of gas for atomisation, which enters through the two-fluid nozzle, is between OOC and 100 0 C, preferably between 10 0 C and 900 C.

20 For spraying the liquid phase into the mixer via one or more nozzles, it is again possible to use all gases which are c:ustomary for such purposes. Air or nitrogen are preferably suitable.

For carrying out the process according to the invention by means of variant all mixers are suitable which are customiry for such purposes. The resulting solid formulation can be discharged from the mixer via customary withdrawal devices. The pulverulent or granular product obtained can subsequently be subjected to custo- 15 mary grinding or granulation.

u When using variant the process according to the invention can also be carried out continuously or discontinuously. In general, the process is carried out a.

20 discontinuously by introducing the required components into the mixer in batches.

When carrying out the process according to the invention by means of variant uniformly shaped granules are 25 obtained, whereas pulverulent or granular products are obt.ined when using variant These products can be comminuted by grinding by using devices which are customary for this purpose, a 30 The solid formulations according to the invention have I a high stability. They have a compact, microporous structure and are nevertheless spontaneously dispersible or soluble in water or other solvents. By spontaneous dispersibility, or solubility, is to be understood in the present case that the particles disperse, or dissolve, completely in generally 0.1 to 5 minutes, preferably in 0.2 to 3 minutes.

'V

21 The solid formulations according to the invention contain one or more agrochemical active compounds and can therefore be employed using customary methods for the treatment of plants in agriculture and horticulture, The solid formulations according to the invention are, for example, dispersed in water. The dispersions formed in this process can be applied by customary methods to the plants and/or their environment, that is to say, for example, by spraying, atomising or pouring, if appropriate after previous dilution. The application rates in this context depend on the concentration of the dis- 15 persion, on the particular indication and on the active components ermployed.

Boe@ The preparation and the use of the solid formulations according to the invention are illustrated by the 20 examples which follow.

B@

B.

B

B CC S If 22 Preparation examples Exam~nle 1 To prepare a liquid phase, 930 g of l-(4-chlorophenyl)- 4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol are dissolved completely at 60'C in 2700 g of polyethoxyisotridecyl alcohol having an average of 6 ethylene oxide units per molecule, with stirring.

Moreover, a finely pulverulent, solid phase is prepared by mixing 1200 g of a formaldehyde-crosslinked alkylarylsulphonace with 1170 g of highly disperse silica in a small plough-bar mixer at room temperature, and the mixture is homogenised.

w The preparation of granules which follows is carried out in a fluidised-bed granulator. For this purpose, the a solid phase is introduced into the granulator and fluid- 20 ised by blowing in air at a temperature of 25*C in an amount of 300 to 500 m 3 At the same time, spraying of the liquid phase at 60°C into the fluidised bed via a two-fluid nozzle with the aid of air commences. After 25 minutes, spraying-in of the liquid phase is complete.

After this, a post-granulation is carried out by spraying on 1600 g of water at 50°C, followed by drying to a residual moisture of 1% by weight of water by heating the air which is passed in at 70 0 C. The granules formed are classified. In this way, 5 kg of granules of particle 0. sizes in the range between 200 and 1500 pm are obtained.

!When 1 kg of these granules, which contain 1.5% by weight of active compound, are added to 200 1 of water, spontaneous wetting takes place, and the granules are dissolved completely within 10 seconds.

v* I 23 Examole 2 To prepare a liquid phase, 1550 g of 1-(4-chlorophenyl)- 4,4-dimethyl-3-(1,2,4-triazol-l-yl-methyl)-pentan-3-ol are dissolved completely in a mixture of 900 g of polyethoxy-iso-tridecyl alcohol having an average of 6 ethylene oxide units per molecule and 1200 g of alkylaryl-polyethoxy-ethanol phosphoric acid ester, which is commercially available under the name "Blendex®", at withi stirring.

15 Moreover, a finely pulverulent solid phase is prepared by mixing 1200 g of a formaldehyde-crosslinked alkylarylsul- *060 phonate with 1150 g of highly disperse s'lica in a small plough-bar mixer at room temperature and homogenising the 9 mixture.

a The preparation of granules which follows is carried out in a fluidised-bed granulator. For this purpose, the solid phase is introduced into the granulator and fluid- G ised by blowing in air at a temperature of 25"C in an 25 amount of 300 to 500 m 3 At the same tmne, spraying of the liquid phase at 60 C into the fluidised bed via a two-fluid nozzle with the aid of air commences. After S" minutes, spraying-in of the liquid phase is complete.

After this, post-granulation is carried out by spraying 30 on 1600 g of water at 50*C, followed by drying to a residual moisture of 1% by weight of water by heating the air which is passed in at 70*C. The granules formed are classified. In this way, 5 kg of granules of particle sizes in the range between 200 a'-r 1500 pm are obtained.

24 When 1 kg of these grcanules, which contain 2.5% by weight of active compound, are added to 200 1 of water, spon- Staneous wetting takes place, and the granules are dissolved completely within 10 seconds.

Example 3 To prepare a liquid phase, 4640 g of l-(4-chlorophenyl)- 4,4-dimethyl-3-(1,2,4-triazol-l-yl-methyl)-pentan-3-ol are dissolved completely in 13.360 g of polyethoxyisotridecyl alcohol with &n average of 6 ethylene oxide units per molecule, at 60°C with stirring.

15 Moreover, a finely pulverulent solid phase is prepared by mixing 6000 g of a formaldehyde-crosslinked alkylarylsul- *OeO phonate with 6000 g of highly disperse silica in a small o" **plough-bar mixer at room temperature and homogenising the mixture.

a.

0 i B Granulation which then follows is carried out in a granulation apparatus of the type represented in Figure 1. For this purpose, the solid phase is fed pneumatically to the fluiised-bed reactor via feedpipes 2 and fluid- S* 25 ised by blowing in nitrogen at a temperature of 80°C, in a.

an amount of 50 kg/h, via line 6. At the same time, the liquid phase at a temperature of 60°C, is sprayed in via (s the two-fluid nozzle 5 with the aid of nitrogen as the atomising gas. The streams of product are controlled in such a way that the solid phase is fed to the reactor in an amount of 1.2 kg/h and the liquid phase in an amount of 1.8 kg/h. From the fluidised bed 7 which forms, 3 kg/h 25 of granules of an average particle size of 0.4 mm are continuously discharged via the counterflow gravity classifier 9 and the withdrawal device 10, In this manner, 28 kg of granules of a content of 15,0% by weight of 1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4triazol-1-yl-methyl)-penlan-3-ol are obtained.

Example 4 To prepare a liquid phase 130 g of 6-methyl-2-oxo-1,3are dissolved completely 15 in 2500 g of polyethoxy-isotridecyl alcohol with an average of 6 ethylene oxide units per molecule and 2500 g c, of N-octyl-pyrrolidonF, at 60 0 C with stirring.

*e 0 Moreover, a finely pulverulent solid phase is prepared O* i0 by mixing 1000 g of rice starch and 1900 g of a formaldehyde-crosslinked alkylarylsulphonate with 1900 g of highly disperse silica in a small plough-bar mixer at room temperature and homogenising the mixture.

Granulation which then follows is carried out in a granulation apparatus of the type represented in Figure a 1. For this purpose, the solid phase is fed pneumati- (o o cally to the fluidised-bed reactor via feedpipes 2 and fluidised by blowing in nitrogen at a temperature of 80°C, in an amotnt of 50 kg/h, via line 6. At the same time, the liquid phase at a temperature of 600 C, is sprayed in via the two-fluid nozzle 5 with the aid of S* nitrogen as the atomising gas. The streams of product *m O 2/; 26 are controlled in such a way that the solid phase is fed to the reactor in an amount of 1.2 kg/h and the liquid phase in an nmount of 1.8 kg/h. From the fluidised bed 7 which forms, 3 kg/h of granules of an average particle size of 0.4 mm are continuously discharged via the counterflow gravity classifier 9 and the withdrawal device 10. In this manner, 9 kg of granules having a content of 1.3% by weight of 6-methyl-2-oxo-1,3-dithiolo-[4 ,5-bl-quinoxaline are obtained.

15 Example To prepare a liquid phase, 101.56 g of 1-(4-chloropentan-3-ol and 7.54 g of 6-methyl-2-oxo-1,3-dithiolo- 4,5-b]-quinoxaline, 104.5 g of a mixture of N,Ndimethyl-alkylcarboxamides which con~sists, on average, 0 of 5% of N,N-dimethyl-hexanecarbovkmide, 50% of N,Na. dimethyl -octanecarboxamide, 40% of N,N-dimethyl -decanecarboxamide and 5% of N,,N-dimethyl-dodecanecarboxamide, 52.5 g of polyethoxy-isotridecyl alcohol with an average of 6 ethylene oxide units per molecule and 5 g of ptolyl-sulphonic acid are completely dissolved with stirring at 800 C, (0 seeIn additions a finely pulverulent solid phase is prepared by mixing 156.5 g of highly disperse silica, 52,5 g of a diphenylsulphonic acid formaldehyde con- *0 densate and 19.9 g of sodium dialkylnaphthyl-sulphonate in a plough-bar mixer at room temperature anc; homogenising the mixture.

27 The 'preparation of the solid formulation wh.,.n then follows is carried out in such a manner that the liquid phase is sprayed at 80 0 C via a nozzle into the mixer onto the solid phase, which has a temperature equal to ruom temperature, while stirring. In this manner, 500 g of a granular solid formulation is obtained, which is ground to a powder.

Example 6 To prepare a liquid phase, 136.64 g of 3-methyl-4-amino- 15 6-phenyl-1,2,4-triazin-5(4H)-one and 30.0 g of polyethoxy-isotridecyl alcohol with an average of 6 ethylene oxide units per molecule ore dissolved completely at 800C with stirring.

S

S* 20 In addition, a finely pulverulent solid phase is prepared by mixing 18.32 g of 2-ethoxy-2,3-dihydro-3,3-

SO

dimethyl-5-benzofuranyl sulphonate, 18.60 g of 3methoxycarbonyl-aminophenyl-N-(3'-methylphenyl)carbamate, 60.0 g of a diphenylsulphonic acid formaldehyde condensate, 30.0 g of highly disperse silica and 6.44 g of kaolin in a plough-bar mixer at room temperature and homogenising the mixture.

The prseparation of the solid formulation which then follows is carried out in such a manner that the liquid phase is sprayed at 80°C via a nozzle into the mixer onto the solid phase, which has a temperature equal to room temperature, while stirring. In this manner, 300 g of a granular solid formulation is obtained, which is ground to a powder.

28 Example 7 To prepare a liquid phase, 53.2 g kg of 1-(4-chlorophenoxy)- 3 3 -dimethyl-l-(1,1,4-triazol-1-yl)-butan-2-one, kg of polyethoxy-isotridecyl alcohol with an average of 6 ethylen, oxide units per molecule, 20 kg of Noctyl -pyrrol idone and 20 kg of a mixture of N,Ndimethyl-alkylcarboxamides which consists, an average, of 5% of NN-dimethyl-hexanecarboxamide, of N\,Ndimethyl-octanecarboxamide, 40% of N,N-d~imethyl-decanecarboxamide and 5% of N, N-d imethyl -dode cane carboxaml de, are dissoved completely at 90 0 C with stirring.

In addition, a finely pulverulent solid phase is prea 9 pared by mixing 4 kg of a wetting agent based on alkyl- :061060aryl-sulphonate, 20 kg of a diphenyl-sulphonic acid P es 20 formaldehyde condensate and 62.8 kg of highly disperse 00 silica in a plough-bar mixer at room temperature and .9 homogeni.aing the mixture.

The preparation of the solid formulation which then follows is carried out in s-ich a manner that the liquid ee**0 0 phase is sprayed at 90 0 C via a nozzle into the mixer .onto the solid phase, which has a temperature equal to 9' room temperature, while stirring. In this manner, 200 kg

V.

ee of a granular solid formulation is obtained, which is ground to a~ powder.

29 Example 8 To prepare a liquid phase, 26.3 kg of 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1,1,4-triazol-1-yl)-butan-2-ol, kg of polyethoxy-isotridecyl alcohol with an average of 6 ethylene oxide units per molecule, 1Q kg of Noctyl-pyrrolidone and 10 kg of a mixture of N,Ndimethyl-alkylcarboxamides which consists, on average, of 5% of N,N-dimethyl-hexanecarboxamide, 50% of N,Ndimethyl-octanecarboxamide, 40% of N,N-dimethyldecanecarboxamide and 5% of N,N-dimethyl-dodecane- 15 carboxamide, are dissolved completely at 90 0 C with stirring.

*0 In addition, a finely pulveruleI\t solid phase is 0@ .o prepared by mixing 2 kg of a wetting agent based on 20 alkylaryl-sulphonate, 10 kg of a diphenyl-sulphonic acid formaldehyde condensate and 31.7 kg of highly disperse silica in a plough-bar mixer at room temperature and homogenising the mixture.

The preparation of the solid formulation which then 9 0***0t follows is carried out in such a manner that the liquid phase is sprayed at 90 0 C via a nozzle into the mixer onto the solid phase, which has a temperature equal to room temperature, while stirring. In this manner, 100 kg of a granular solid formulation is obtained, which is ground to a powder, e 9 .9* 30 Example 9 To prepare a licquid phasr., 25.5 kg of 1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-nethyl)pentan-3-ol, 10 kg of polyethoxy-isotridecyl alcohol with an average of 6 ethylene oxide units per molecule, 10 kg of N-octyl-pyrrolidone and 10 kg of a mixture of N,N-dimet.,,yl-alkylcarboxarm-ldes which consists, on average, of 5% of N,N-d'b,-thyl-hexanecarboxamide, of N,N-dimethyl-octanec a-boxamide, 4 0% of N,N-dimethyldecan,-carboxamide arnd 5% of N,N-dimethyl-dodecanecarboxamide, are dissolved completely at 90 0 C with stirring.

IS In addition, a finely pulverulent, solid phase is 2* 0 prepared by mnixing 2 kg of a wetting agent based on 6 e 2 alkylaryl-sulphonates 10 kg of a diphenyl-sulphonic acid formraldehyde condensate and 32.5 kg of highly disperse a. silica in a plough-bar mixer at room temperature and homogenising the mixture.

The preparation of the solid formulatiopn which then follows is carried out in such a manner that the liquid Mae:*.

G. a phase is sprayed at 90 0 C via a nozzle into the mixer onto the solid phase, which has a temperature equal to a* **.room temperature, while stirrin,. In this manner, 100 kg of a granular solid formulation is obtained, which is ground to a powder.

31 Example To prepare a liquid phase, 10 g of 1-[4-C2--chloro-1,1,2trifluoroethoxy)-phenyl)-3-(4-phenyl-1,2,5-oxadiazol-3yl,,-urea, 30 g of an emulsifier based on alkylary-vi polyglycol ether, 6 g of an ethyleneoxide-dimethylsiloxane block copolymer with Si-C-bonds, 6 g of the sodium salt of coconut fatty acid 2-sulfethylester containing 10% of free coconut fatty acid are dissolved completely at 90 0 C with stirring.

In addition, a finely pulverulent sol'i'd phase is prepared by mixing 12 g of a diphenyl-sulphonic ac-,.d formaldehyde condensate and 36 g of highly disperse silica in a mixer at room temperature and homogenising 4,4 the mixture.

5 The preparation of the solid formulation which then 9 follows is carried out in such a manner that the liquid phase is sprayed at 9000 via a noz2,,le into the mixer onto the solid phase, which has a temperature equal to r'oom temperature, while stirring. In this manner, *0o* 100 g of a granular solid formulation is obtained, which is ground to a powder.

32 Comparison example A A mixture of 2630 g of l-(4-chlorophenyl)-4,4-dimethyl- 3-(l,2,4-triazol--l-yl-methyl)-pentan-3-ol, 2000 g of a formaldehyde-crosslinked alkylarylsulphonate, 300 g of phospholipid and 5070 g of sodium hydrogen carbonate is comminuted in a plough-bar mixer to a particle size of about 1 mm, and the mixture is homogenised. The mixture is then ground with the aid of an air-jet mill to an average particle size of about 7 pm and remixed.

The resulting premix is processed in a commercially available fluidised-bed granulator to give granules by 15 moistening batches of 48 kg of powder in the fluidised bed with 1.5 liters of water in the course of 21 minutes S* .at room temperature and subsequently drying the granules warming the inlet air to 70°C in the course of 11 *t minutes, so that the -Idciial water content in the 0 granules is about I% by weight. The temperature of the granules in this procedure remains below 40°C. The resulting granules aro classified using a cascade of vibzating screens. In this manner, 4.5 kg of granules having particle sizes in the range between 200 and 1500 pm 25 are obtained per batch.

eoo*** The suspension stability of the granules, measured by CIPAC method MT 168, is 84%. The wet-screen test on a ea screens with mesh size 315, 250 and 160 pm, respectively, carried out by CIPAC method MT 167 gives screening residues of less than 0.005%.

*4 @0 0 6

S

S* 00 Si. 33 Comoarison example B X mixture of 2630 g of l-(4-chlorophenyl)-4,4-dimethyl- 3 -(l,2,4-triazol-l-yl-methyl)-pentan-3-ol, 2000 g of a formaldehyde-crosslinked alkylarylsulphonate, 300 g of phospholipid and 5070 g of sodium hydrogen carbonate is stirred into 10 kg of water with the aid of a tootheddisk stirrer and the mixture is precomminuted with a toothed colloid mill. It is then ground finely on a bead mill whose throughput is 25 kg/h. An aqueous suspension of a solids content of 50% by weight is obtained. At a shear gradient of 1000/sec, the viscosity of the suspension is approx. 65 mPas; the average particle diameter is approx. 4 unm.

In an amount of 7 kg/h, the resulting suspension is sprayed through nozzles into a fluidis..d-bed reactor with 20 continuously classifying product discharge. A stream of nitrogen in an amount of 92 kg/h is used for fluidising.

The temperature of the stream of nitrogen is 90*C. In the fluidised bed which forms, a product temperature of below 0 C is established. The granules discharged have a 25 particle size of approx. 0.4 mm. The residual moisture of 4 4 the granules is 2.1% by weight of water.

The suspension stability of the granules, measured by CIPAC method MT 168, is 98%. The wet-screen test on screens with mesh size 315, 250 and 160 pm, respectively, carried out by CIPAC method MT 167, gives no screening residues.

34 In the use examples which follow, the granules prepared were tested for their biological effectiveness.

Use Example A Erysiphe Test (barley)/curative To prepare a suitable preparation of active compound, 1 part by weight of the particular granules is mixed with water, and the resulting concentrate is diluted with water to the desired concentration.

15 To test for curative effectiveness, young plants are dusted with spores of Erysiphe graminis f.sp. hordei. 48 B. 00 hours after the inoculation, the plants are sprayed with the preparation of active compound until dew-moist.

0 The plants are placed in a greenhouse at a temperature of Sapprox. 20 0 C and a relative atmospheric humidity of approx. 80% to allow the development of mildew pustules.

The evaluation is carried out 7 and 14 days after the inoculation.

The formulations and concentrations of active compound, O a 3 35 and, the test results, can be seen from the table below.

A

Erysiphe Test (barley)/curative Granules of Example Active compound concentration in the spray mixture in rng/l Degree of effectiveness in of the untreated control 7d 14d Known: Example 150 0 0 15.0 0 0 According to the invent ion Example (1 )f 150 150 l'1 0 80 49 88 (31) *9 99 0 9 9 9 999.

9 99*9 9. 99 9. 9 9 99999 9 9.

9 9 9 9 ooo9 ***to 09 9I r

Claims

1. Solid formulations consisting of A) at least one agrochemical active compound, B) at least one additive from the groups comprising polyethoxy.-isotridecylalcohol having an average of 6 ethylene oxide units per molecule, or alkylaryl-polyethoxyethanol phosphoric ac-id esters, or S' SO I a A S.. S 0 S *04 0S~ o SO S S Sd the N-al}kyl-lactams of the formula 0 (11) in which R represents alkyl. hav,'-g 6 to 18 carbon atoms and n rapresents the numbers 3, 4 or 5, or the N,N-dimethyl-alkylcarboxamides of the formula so 51 0 S S. S OS *e RI 1 -CO-N 3II N%-CH 3 (111) -37 in which' E~repres-erits alkyl having 5 to 11 carbon atoms, C) at least onc disp~rsant, D) at least one carrier and E) if appropriate, further active compoundr-e and/or additives

2. Process for the preparation of' solid formulations according to tlaim 1, characterised in that either a) a solution of at least one agrochemical active *compound and, if,-;appropriate, aoddftives in at. least o~ne additional comp und from amongst the groups mentioned under and a mixture of at least one disper-sant and at least one carrier ;ad, if appropriate, further agro- chemical active compc~unds and/o~r additives, *.aare niit'oduced separately into a fluidised-bed granulat.or, the mixture is granulated until a granular, product has formed, and the granules are discharged fromn the fluidised-bed granulator, if appropriate aOer spraying with water foi-lowed by drying, or S38- b) a mixture of at least one dispersant and at least one carrier and, if appropriate, agrochemical active compounds and/or additives are initially introduced into a mixer, a solution of at least one agrochemical active compound and, if appropriate, additives in at least one additional compound from amongst the groups mentioned under is sprayed into the mixer until a product is obtained having the desired particle size and the resulting solid formulation is discharged from the mixer, if appropriate, after previously spraying with water followed by drying, and, if appropriate, the resulting solid formulations are subsequently ground.

3. Use of solid formulations according to claim 1 as agents for treating plants.

4. Solid formulations consisting of at least one agrochemical active compound and at least one dispersant substantially as herein described. DATED this 12th day of July, 1993 BAYER AKTIENGESELLSCLCAFT by its Patent Attorneys DAVIES COLLISON CAVE s **a *a i' d ii; .t930712,p:\oper\hje,81303-91.rsp,38