EP1465484A1

EP1465484A1 - Powder formulations

Info

Publication number: EP1465484A1
Application number: EP02791865A
Authority: EP
Inventors: Hanns-Peter Müller; Horst Gruttmann; Hilmar Wolf; Anne Suty-Heinze; Uwe Priesnitz
Original assignee: Bayer CropScience AG
Current assignee: Bayer CropScience AG
Priority date: 2002-01-10
Filing date: 2002-12-23
Publication date: 2004-10-13
Also published as: WO2003056921A1; JP2005513163A; US20050054537A1; AU2002358174A1; BR0215503A; DE10200603A1; KR20040080445A

Abstract

The invention relates to powder formulations, which consist of at least one agrochemical active ingredient, at least one biodegradable polyester containing hydroxyl groups, optionally blended with one or more additional biodegradable polymer(s), in addition to optional additives. Said formulations have a particle diameter of less than 125 νm. The invention also relates to a method for producing the novel powder formulations and to the use thereof for applying agrochemical active ingredients to plants and/or their environment.

Description

Powder formulations

The present invention relates to new powder formulations containing agrochemical active ingredients and polymers, a process for the preparation of these formulations and their use for the application of agrochemical active ingredients.

Microparticles are already known from WO 99-00 013, which contain certain polymers in a mixture with agrochemical active substances. These preparations are prepared by dissolving polymers and agrochemical active ingredients in a water-immiscible organic solvent, then dispersing this solution in water using emulsifiers, then evaporating the solvent and removing the microparticles thus produced by decanting and / or filtration separated from the aqueous phase and then dried. However, a disadvantage of this method is that many and complex measures have to be carried out and the use of relatively large apparatus is required when working on an industrial scale. It is also unfavorable that the organic solvents required to dissolve the components must subsequently be removed again.

Furthermore, methods for producing polymer microparticles in which agrochemical active substances are present have also been described in US Pat. No. 5,725,869. However, these processes are also very complex and are therefore hardly suitable for use on an industrial scale.

New powder formulations have now been found that are made from

at least one agrochemical active ingredient, at least one biodegradable, hydroxyl-containing polyester optionally mixed with one or more other biodegradable polymers and

- if necessary additives

exist and have a particle diameter below 125 μm.

Furthermore, it was found that the powder formulations according to the invention can be produced by mixing a mixture

at least one agrochemical active ingredient,

at least one biodegradable, hydroxyl-containing polyester optionally in a mixture with one or more further biodegradable polymers and

optional additives

homogenized in the melt at temperatures between 50 ° C and 180 ° C and

After cooling, the mixture is crushed so that a powder is obtained in which the particles have a diameter below 125 μm.

Finally, it was found that the powder formulations according to the invention are very well suited for the application of the agrochemical active ingredients contained to plants and / or their habitat.

It can be described as extremely surprising that the powder formulations according to the invention are better suited for applying the agrochemical active ingredients contained than the constitutionally most similar, known preparations. inexperience What is particularly important is that the active components are released in the desired amount over a relatively long period of time.

It was also to be assumed that when the process according to the invention was carried out after cooling the melt, soft resins which would stick at room temperature would result, because mixtures of polyesters and agrochemical active substances generally have low melting points. Contrary to expectations, however, there are products that are so brittle that they can be broken down into non-clumping, free-flowing powders with the help of conventional mills without additional cooling.

The powder formulations according to the invention contain one or more agrochemical active ingredients.

In the present context, agrochemical active ingredients are all for

To understand plant treatment usual substances. Fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, plant nutrients and repellents may preferably be mentioned. Solid agrochemical active ingredients are preferred.

Examples of fungicides are:

2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ^, 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1, 3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -otolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate

(Quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,

Cymoxanil, Cyproconazole, Cyprofuram, Caφropamid,

Dichlorophen, diclobutrazole, dichlofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine,

Dipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon,

Edifenphos, epoxyconazole, ethirimol, etridiazole,

Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpro- pimoφh, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Aluminum, Flutolanolet, Folutriaflilil, Folut Fuberidazole, furalaxyl, furmecyclox, fenhexamide,

guazatine,

Hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, Iprobefos (IBP), iprodione, isoprothiolan,

iprovalicarb,

Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate,

Copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, oxadixyl, oxamocarb, oxycarboxin,

Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,

Probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilone,

Quintozen (PCNB), Quinoxyfen,

Sulfur and sulfur preparations, spiroxamines,

Tebuconazole, Tecloftalam, Tecnazen, Tetraconazole, Thiabendazole, Thicyofen, Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemoφh, Trififolumol, Trififolumol, Trififolumol

trifloxystrobin, Validamycin A, vinclozolin,

Zineb, Ziram, and

2- [2- (1-chloro-cyclopropyl) -3 - (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro- [1, 2,4] - triazol-3-thione.

Examples of bactericides are:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin,

Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofalam, copper sulfate and other copper preparations.

Examples of insecticides, acaricides and nematicides are:

Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz,

Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,

Bacillus thuringiensis, 4-bromo-2- (4-chloro-phenyl) -1 - (ethoxymethyl) -5- (trifluoromethyl) -lH-pyrrole-3-carbonitrile, bendiocarb, benfüracarb, bensultap, betacyfluthrin,

Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chloretoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl-ethanimidamide , Chloφyrifos, Chloφyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,

Deltamethrin, Demeton-M, Demeton-S, Demeton-S-methyl, Diafenthiuron, Diazinone, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat,

Dimethylvinphos, dioxathione, disulfoton,

Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos,

Etrimphos,

Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipro- nil, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathione, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, Nitenpyram, Omethoat, Oxamos, Oxamyl, Oxydemyl, Oxydem

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Prome- carb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetroos, Pyri- phllos daphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temefos, Terbam, Terbufos, Tetrachlorvinphos, Thiacloprid, Thiafenox, Thiamethoxam, Thiodicarb, Thiofanox, Thiomethon, Trioniazin, Triniazin, Triniazin, Trioniazin

Trimethacarb, Vamidothion, XMC, Xylylcarb, Zetamethrin.

Examples of herbicides are: anilides, such as diflufenican and propanil; Aryl carboxylic acids such as dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones such as chloridazon and norflurazon; Carbamates, such as, for example, chloropropham, desmedipham, phenmedipham and propham; Chloroacetanilides, such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, Pretilachlor and propachlor; Dinitroanilines such as oryzalin, pendimethalin and trifluralin; Diphenyl ethers, such as, for example, acifluorfen, bifenox, fluoroglycofen, fomafeen, halosafen, lactofen and oxyfluorfen; Ureas, such as, for example, chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; Hydroxylamines such as alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; Imidazolinones, such as, for example, imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles such as bromoxynil, dichlobenil and ioxynil; Oxyacetamides such as mefenacet; Sulfonylureas such as amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbates such as butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines such as atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; Triazinones such as hexazinone, metametron and metribuzin; Others, such as, for example, aminotriazole, benfu- resate, bentazone, cinmethylin, clomazone, clopyralide, difenzoquat, dithiopyr,

Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane. Furthermore, 4-amino-N- (l, l-dimethylethyl) -4,5-dihydro-3- (l-methylethyl) -5-oxo-lH-l, 2,4-triazole-l-carboxamides and Benzoic acid, 2 - ((((4,5-dihydro-4-methyl-5-oxo-3-propoxy-lH-l, 2,4-triazol-l-yl) carbonyl) amino) sulfonyl) methyl ester.

Chlorcholine chloride and ethephon are examples of plant growth regulators.

Examples of plant nutrients are customary inorganic or organic

Fertilizer for supplying plants with macro and / or micronutrients called.

Examples of repellents are diethyl tolylamide, ethylhexanediol and butopyronoxyl. The following active ingredients are mentioned as examples of insecticides, which can preferably be contained in the powder formulations according to the invention:

Imidacloprid, thiacloprid, thiamethoxam, acetamiprid, clothianidin, beta-cyfluthrin, cypermethrin, transfluthrin, lambda-cyhalothrin and azinphosmethyl.

The following active substances are mentioned as examples of herbicides, which can preferably be contained in the powder formulations according to the invention:

Propoxycarbazone sodium, flucarbazone sodium, amicarbazone and dichlobenil as well as phenyluracils of the formula

wherein the substituents R ¹ , R ² and R ^{3 have} the meanings given below.

The powder formulations according to the invention contain one or more biodegradable, hydroxyl-containing polyesters, optionally in a mixture with one or more further biodegradable polymers.

Preferred polyesters are corresponding esters which are derived from aliphatic, cycloaliphatic, aromatic and / or heterocyclic saturated or unsaturated carboxylic acids, which can be substituted by halogen atoms. Examples include:

Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, glutaric acid, maleic acid, - accessible fumaric acid or - if available

furthermore dimeric and trimeric fatty acids, such as oleic acid, optionally in a mixture with monomeric fatty acids,

also dimethyl terephthalate, bis-glycol terephthalate,

also cyclic monocarboxylic acids, such as benzoic acid, p-tert-butylbenzoic acid or hexahydrobenzoic acid. The alcohol components from which the polyesters are derived are preferably polyhydric alcohols, such as ethylene glycol, propylene glycol (1,2), propylene glycol (1,3), butylene glycol (1,4), butylene glycol (2nd , 3), di-ß-hydroxyethyl-butanediol, hexanediol (1,6), octanediol (1,8), neopentyl glycol,

Cyclohexanediol, 1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, 2,2-bis (4- (β-hydroxyethoxy) phenyl) propane, 2-methyl- 1, 3-propanediol, glycerol, trimethylolpropane, hexanetriol- (1,2,6), butanediol- (1,4), tris- (ß-hydroxyethyl) -isocyanurate, trimethylolethane, pentaerythritol, quinite, mannitol and Sorbitol, formitol and their hydroxyalkylation products, methyl glycol,

Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, polybutylene glycols and xylylene glycol.

Mono- or polyesters from lactones, such as ε-caprolactone, or from hydroxycarboxylic acids, such as hydroxypivalic acid, hydroxydecanoic acid or hydroxycaproic acid, and also polyesters from the above-mentioned polycarboxylic acids or their derivatives and polyphenols, such as hydrocarbons, may also be present in minor amounts. quinone, bisphenol-A, 4,4'-dihydroxybiphenyl or bis (4-hydroxyphenyl) sulfone; polyesters modified with fatty acids (olalkydes) and naturally occurring saturated or unsaturated polyesters, their degradation products or transesterification products with polyols, such as castor oil, tall oil, soybean oil, linseed oil; Polyesters of carbonic acid made from hydroquinone, diphenylolpropane, p-xylylene glycol, ethylene glycol, butanediol or 1,6-hexanediol and other polyols by conventional condensation reactions, for example with phosgene or diethyl or diphenyl carbonate, or from cyclic carbonates, such as glycol carbonate or Vinyl carbonate, available through polymerization; Polyesters of silica, polysiloxanes, such as the products obtainable by hydrolysis of dialkyldichlorosilanes with water and subsequent treatment with polyalcohols, or the products obtainable by addition of polysiloxane dihydrides to olefins, such as allyl alcohol or acrylic acid. Suitable polyesters are also reaction products of mono-, di- or polycarboxylic acids and glycidyl compounds, as are described, for example, in DE-A 24 10 513.

Examples of glycidyl compounds are esters of 2,3-epoxy-1-propanol with monobasic acids which have 4 to 18 carbon atoms, such as glycidyl palmitate, glycidyl laurate and glycidyl stearate; Alkylene oxides having 4 to 18 carbon atoms, such as butylene oxide and glycidyl ether, such as octylglycidyl ether.

Examples of di- and polycarboxylic acids are the substances mentioned in the following list under point 2.

Examples of monocarboxylic acids are the substances mentioned in the following list under point 3.

In the case of the powder formulations according to the invention, preferred polyesters are also monomeric esters, such as dicarboxylic acid bis (hydroxyalkyl) esters, furthermore monocarboxylic acid esters of polyhydric polyols and also oligoesters, which can be prepared by condensation reactions of alcohols and carboxylic acids, as they are are listed in the following compilation.

Compilation of possible starting components.

1. alcohols having 2 to 24, preferably 2 to 10 C atoms, and having 2 to 6 OH groups bonded to non-aromatic C atoms, e.g. Ethylene glycol,

Propylene glycols, diethylene glycol, dipropylene glycol, butanediols, neopentyl glycol, hexanediols, hexanetriols, perhydrobisphenol, dimethylolcyclohexane, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol; 2. Di- and polycarboxylic acids with 4 to 36 carbon atoms and 2 to 4 carboxyl groups, as well as their esterifiable derivatives, such as anhydrides and esters, for example phthalic acid (anhydride), isophthalic acid, terephthalic acid, alkyl tetra-hydrophthalic acid, endomethylene tetrahydrophthalic anhydride, adipic acid, amber acid , Maleic acid, fumaric acid, dimer fatty acids, trimellitic acid,

Pyromellitic acid, azelaic acid;

3. Monocarboxylic acids with 6 to 24 carbon atoms, e.g. Caprylic acid, 2-ethylhexanoic acid, benzoic acid, p-tert-butylbenzoic acid, hexahydrobenzoic acid, monocarboxylic acid mixtures of natural oils and fats, such as coconut oil fatty acid, soybean oil fatty acid, recine fatty acid, hydrogenated and isomerized fatty acids, such as "conjuvandol" fatty acid, and mixtures thereof the fatty acids can also be used as glycerides and can be reacted with transesterification and / or dehydration;

4. monohydric alcohols with 1 to 18 carbon atoms, e.g. Methanol, ethanol, isopropanol, cyclohexanol, benzyl alcohol, isodecanol, nonanol, octanol, oleyl alcohol, octadecanol.

Particularly preferred are hydroxyl group-containing terephthalic acid polyesters with an average molecular weight between 1,000 g / mol and 20,000 g / mol, preferably between 1,500 g / mol and 15,000 g / mol, based on the number average molecular weight.

The hydroxyl group-containing polyesters present in the powder formulations according to the invention generally have an OH functionality of> 2 to <7, preferably 2.1 to 4.5, hydroxyl numbers between 20 and 120 mg KOH / g, preferably between 30 and 100 mg KOH / g, viscosities <100,000 mPa.s, preferably <40,000 mPa.s at 160 ° C and melting points from> 65 ° C to <130 ° C, preferably 75 ° C to 100 ° C. The polyesters present in the powder formulations according to the invention are known or can be prepared in a simple manner by customary methods. Such polyesters are obtained, for example, by condensation of the corresponding starting components under an inert gas atmosphere at temperatures between 100 ° C. and 260 ° C., preferably between 130 ° C. and 220 ° C., in the melt or at

Use of solvents with azeotropic removal of water (cf. Houben-Weyl "Methods of Organic Chemistry", vol. 14/2, pages 1 to 4, 21 to 23 and 44 to 46, Georg Thieme Verlag, Stuttgart 1963, and CR Martens "Alkyd Resins", pages 51 to 59, Reinhold Plastics Appln. Series, Reinhold Publishing Comp., New York 1961).

Additional polymers that can be contained in the powder formulations according to the invention are acrylate resins, such as those obtained from the monomers mentioned below, for example by homo- or co-polymerization.

Esters of acrylic acid and methacrylic acid with dihydric, saturated, aliphatic alcohols with 2 to 4 carbon atoms, e.g. 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and the corresponding methacrylic acid esters; Acrylic acid and methacrylic acid ester with 1 to 18, preferably 1 to 8

C atoms in the alcohol component, e.g. Methyl acrylate, ethyl acrylate, propyl acrylate, sopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and the corresponding methacrylic acid esters, acrylic acid and methacrylic acid cyclohexyl esters; Acrylonitrile and methacrylonitrile; Acrylamide and methacrylamide; N-methoxymethyl (meth) acrylamide.

Preferred acrylate resins are copolymers of

a) 0 to 50% by weight of monoesters of acrylic or methacrylic acid with dihydric or polyhydric alcohols, such as butanediol (1,4) monoacrylate, hydroxypropane pyl (meth) acrylate; also vinyl glycol, vinylthioethanol, allyl alcohol, butanediol-1,4-monovinylether;

b) 5 to 95% by weight esters of acrylic acid or methacrylic acid with monohydric alcohols containing 1 to 12 carbon atoms, e.g. Methyl methacrylate, ethyl acrylate, n-butyl acrylate or 2-ethylhexyl acrylate;

c) 0 to 50% by weight of aromatic vinyl compounds, such as styrene, methylstyrene or vinyltoluene;

d) 0 to 20% by weight of other monomers with functional groups, e.g. Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, maleic acid semi-ester, acrylamide, methacrylamide, acrylonitrile or Ν-methylol (meth) acrylamide and glycidyl (meth) acrylate, the proportion of group a) and / or d) at least 5

% By weight.

The aforementioned acrylate resins are known or can be produced in a simple manner by customary methods. Such acrylate resins are obtained, for example, by solution, suspension, emulsion or precipitation polymerization, but preferably by bulk polymerization, which in turn can be initiated by UN light or other polymerization initiators. Peroxides or azo compounds, such as e.g. Dibenzoyl peroxide, tert-butyl perbenzoate or azodiisobutyronitrile. The molecular weight can e.g. with sulfur compounds, such as tert-dodecyl mercaptan, are regulated.

Mixtures of several substances can of course be used as the polyhydroxyl compounds.

Suitable esterification catalysts are inorganic oxides and salts of tin,

Zinc, Manganese, Titanium and Bismuth. Organic tin compounds Solutions such as tin (II) acetate, tin (II) octoate, tin (II) laurate, dibutyl tin diacetate, dibutyl tin dilaurate, dibutal tin maleate or dioctyl tin diacetate are used as catalysts. The catalysts are generally used in an amount between 0.01 and 0.5% by weight, based on the total amount of the reactants used.

Particularly preferred polyesters which are present in the powder formulations according to the invention are esters which are derived from the acids and alcohols mentioned below.

Particularly preferred alcohols are glycols, such as ethylene glycol, 1,2-propanediol, 1,4-butanediol and isomers, furthermore neopentyl glycol, 1,6-hexanediol and isomers, 4,4'-dihydroxydicyclohexyl-propane-2,2, cyclohexanediol, 1 , 4-bis (hydroxymethyl) - cyclohexane, and also polyols, such as trimethylolpropane, hexanetriol and pentaerythritol.

Particularly preferred acids are di- or polycarboxylic acids, such as terephthalic acid, tetrahydrophthalic acid, phthalic acid, isophthalic acid, trimellitic acid and adipic acid.

Particularly preferred are hydroxyl-containing polyesters which consist of approximately

50 to 65% by weight of aromatic polycarboxylic acids, 30 to 45% by weight of aliphatic glycols and 0 to 5% by weight of aliphatic triols

are built up.

Suitable polymers which may additionally be present include copolymers having hydroxyl groups, such as those obtained by copolymerizing hydroxyalkyl acrylates or hydroxyalkyl methacrylates with acrylic acid esters or Methacrylic acid esters and optionally other unsaturated monomers are formed. Unsaturated monomers are, for example, substances which can be obtained from styrene / maleic acid copolymers by partial esterification of the acid groups with ethylene oxide (cf. DE-A 21 37 239).

The softening temperatures of the preferred hydroxyl-containing polyesters, measured according to the differential thermal analysis (= DTA), are generally between 40 ° C. and 140 ° C., preferably between 45 ° C. and 100 ° C. The hydroxyl numbers of these substances are generally between 25 and 200, preferably between 30 and 130. The molecular weight of these substances which can be calculated from the functionality and the hydroxyl group content is generally between 400 and 10,000, preferably between 1,000 and 5,000.

Additives which can be present in the plant treatment compositions according to the invention are all substances which are customarily used in such polymer preparations. Fillers, lubricants, lubricants and stabilizers known from plastics technology are preferably considered.

Examples of fillers are: titanium dioxide, barium sulfate, furthermore aluminum oxides, silicas, clays, precipitated or colloidal silicon dioxide, and

Phosphates.

Examples of lubricants and lubricants are: magnesium stearate. Stearic acid, talc and bentonite.

Antioxidants and substances which protect the polymers against undesired degradation during processing can be used as stabilizing agents.

The concentrations of the individual components can be varied within a substantial range in the powder formulations according to the invention.

That's the salary of agrochemical active ingredients in general between 1 and 50% by weight, preferably between 5 and 40% by weight,

- Polyesters containing hydroxyl groups, optionally in a mixture with additional polymers, generally between 50 and 99 wt .-%, preferably between 55 and 95 wt .-% and

of additives generally between 0 and 30 wt .-%, preferably between 0 and 20 wt .-%.

When carrying out the process according to the invention, the procedure is generally such that the polymer components are melted at temperatures between 50 ° C. and 180 ° C., preferably between 120 ° C. and 180 ° C., particularly preferably between 140 ° C. and 170 ° C. then one or more agrochemical active ingredients and optionally additives are added with stirring. The resulting liquid and homogeneous mixture is transported on cooling belts or cooling rollers using conventional discharge devices. After cooling, the solidified product is removed from the cooling device and broken. The resulting raw granulate is then comminuted and sieved using conventional grinding equipment in such a way that a powder is formed in which the particles have a diameter below 125 μm.

All mills which are usually used for such purposes can be considered as grinding devices. Pin mills, ball mills, jet mills or classifying mills can preferably be used, a mill of the ACM 2 type from Hosokawa Mikropul being mentioned as an example.

The powder formulations according to the invention can be used as such or after the addition of further formulation auxiliaries for the application of agrochemical active ingredients in crop protection both in agriculture and forestry and in horticulture be used. All customary components which can be used in plant treatment compositions are considered as formulation auxiliaries, such as, for example, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, components which delay drying, antifreezes, secondary thickeners, solvents and, in the case of the preparation of mordants, also Glue.

Suitable dyes which can be used for the further preparation of the powders according to the invention as plant treatment agents are all dyes customary for such purposes. Both are not very soluble in water

Pigments and water-soluble dyes can be used. Examples include the dyes known under the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.

Suitable wetting agents which can be used for the formulation of the powders according to the invention are all substances which are customary for the formulation of agrochemical active compounds and which promote wetting. Alkyl naphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates, can preferably be used.

Suitable dispersants and / or emulsifiers which can be used to formulate the powders according to the invention are all nonionic, anionic and cationic dispersants customary for formulating active agrochemicals. Nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants are preferably usable. Particularly suitable nonionic dispersants are ethylene oxide

Propylene oxide block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers and their phosphated or sulfated derivatives. Suitable anionic dispersants are, in particular, lignin sulfonates, polyacrylic acid salts and aryl sulfonate-formaldehyde condensates. Defoamers which can be used to formulate the powders according to the invention are all foam inhibitors which are customary for formulating active agrochemicals. Silicone defoamers and magnesium stearate can preferably be used.

Suitable preservatives which can be used for the formulation of the powders according to the invention are all substances which are customary for such purposes for the formulation of agrochemical active compounds. Examples include dichlorophene and benzyl alcohol hemiform.

All components which can be used for such purposes in agrochemical compositions are suitable as components which delay drying and as anti-freeze agents which can be used to formulate the powders according to the invention. Polyhydric alcohols, such as glycerol, ethanediol, propanediol and polyethylene glycols of different molecular weights are preferred.

Secondary thickeners which can be used to formulate the powders according to the invention are all substances which can be used in agrochemical compositions for such purposes. Cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and highly disperse silica are preferred.

Suitable solvents which can be used to formulate the powders according to the invention are all organic solvents which can be used in agrochemical compositions. Ketones, such as methyl isobutyl ketone and cyclohexanone, furthermore amides, such as dimethylformamide, furthermore cyclic compounds, such as N-methyl-pyrrolidone, N-octyl-pyrrolidone, N-dodecyl-pyrrolidone, N-octyl-caprolactam, N- Dodecyl-caprolactam and γ-butyrolactone, in addition strongly polar solvents, such as dimethyl sulfoxide, also aromatic hydrocarbons, such as xylene, also esters, such as propylene glycol monomethyl ether acetate, adipic acid dibutyl ester, acetic acid hexyl ester, acetic acid heptyl ester, citric acid tri-n-phthalate diethyl ester and di-n-butyl phthalate, and further alcohols, such as ethanol, n- and i-propanol, n- and i-butanol, n- and i-amyl alcohol, benzyl alcohol and l-methoxy-2-propanol. Water can also be used as a diluent.

If the manufacture of mordants is intended, adhesives can also be used to formulate the powders according to the invention. As such, all conventional binders that can be used in pickling agents are suitable. Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose are preferred.

Dispersions of biodegradable are also particularly preferred as adhesives

Polyester-polyurethane-polyureas in water. Such dispersions are known (cf. WO 01-17347).

The powder formulations according to the invention can be used as such or after mixing with other formulation auxiliaries and / or plant treatment agents and, if appropriate, after further dilution with water. The application is carried out according to conventional methods, for example by scattering, pouring, spraying or spraying.

The powders according to the invention can be converted particularly advantageously by adding appropriate formulation auxiliaries and, if appropriate, diluents into dressing agents with which seeds of the most varied types can be treated. Such dressings are suitable for dressing the seeds of cereals, such as wheat, barley, rye, oats and triticale, as well as the seeds of rice, corn, rapeseed, peas, field beans, cotton, sunflowers and beets or also vegetable seeds of the most varied of natures. The seed dressing formulations can also be used for dressing seeds of transgenic plants. In cooperation with the substances formed by expression, synergistic effects can also occur. For the treatment of seeds with the seed dressing formulations, all mixing devices that can usually be used for dressing come into consideration. In detail, the dressing is carried out by placing the seed in a mixer, adding the desired amount of dressing formulation either as such or after prior dilution with water and mixing until the formulation is evenly distributed on the seed. If necessary, a drying process follows.

The powder formulations according to the invention and the formulations which can be prepared therefrom by further mixing with formulation auxiliaries and / or plant treatment agents are outstandingly suitable for the application of agrochemical active ingredients and / or their habitat. They ensure the release of the active components in the desired amount over a longer period of time.

The application rate of the powder formulations according to the invention and of the preparations which can be prepared therefrom by further mixing with formulation auxiliaries can be varied within a substantial range. It depends on the agrochemical active substances present, on their content in the plant treatment products, on the respective indication and the field of application.

The preparation and use of the powder formulations according to the invention is illustrated by the following examples. Preparation Examples

A) Preparation of polyesters containing hydroxyl groups

Examples 1 to 4

Manufacture of terephthalic acid polyester.

The starting components - terephthalic acid (TS), dimethyl terephthalate (DMT), 1,6-hexanediol (HD), neopentyl glycol (NPG), 1, 4-dimethylolcyclohexane (CMC) and trimethylol propane (TMP) - were placed in a reactor and using a Oil bath warmed. After most of the substances had melted, 0.05% by weight of di-n-butyltin oxide was added as a catalyst at a temperature of 160 ° C. The first elimination of methanol occurred at a temperature of approx. 170 ° C. The reaction was completed within 6 to 8 hours. The

Polyester was cooled to 200 ° C. and largely devoid of volatile components within 30 to 45 minutes by applying a vacuum (10 mbar). The bottom product was stirred throughout the reaction time and a gentle stream of nitrogen was passed through the reaction mixture.

The composition of the polyesters obtained and their physical and chemical characteristics are listed in Tables 1 and 2 below.

Table 1

Composition of the polyesters according to Examples 1 to 4

Table 2

Chemical and physical characteristics of the polyesters according to Examples 1 to 4

Example 5

503 g (3.03 mol) of terephthalic acid, 587.8 g (3.03 mol) of dimethyl terephthalate, 58 g (0.4 mol) of adipic acid, 686.4 g (6.6 mol) of neopentyl glycol and 32 g were placed in a four-necked flask stirring apparatus (0.24 mol) trimethylolpropane under

Nitrogen warmed up slowly. At 160 ° C., 1 g of dibutyltin oxide was added to the melt with stirring. Then methanol and water were distilled off within 7 hours at 170 to 220 ° C. and 14 hours at 220 ° C. to 230 ° C. The resulting polyester had an acid number of 4.7. The melt was cooled to 200 ° C. and devolatilized within 11 minutes at 11 mbar.

It was then cooled to 160 ° C and the polyester was poured onto a Teflon sheet. The clear, yellow, tack-free resin thus obtained has an acid number of 4.4 and a glass transition temperature of 55 ° C. (DTA).

B) Preparation of powder formulations according to the invention

Example 6

490 g of the polyester known under the name CRYLCOAT® 240 (company UCB Chemicals / Belgium) are dissolved in a four-necked flask stirring apparatus

Heated to 150 ° C and melted. 210 g of imidacloprid are introduced in portions into the melt at 140 ° C. to 150 ° C. The mixture is then stirred at 150 ° C. to 160 ° C. until a clear melt and poured onto a Teflon sheet. The tack-free resin, which is clear at room temperature, is crushed and finely ground with a jet mill without cooling. Scanning electron microscopy shows particles with a particle size of approx. 0.2 to 20 μm. The powdery, polymer-bound plant treatment composition consists of 30% by weight imidacloprid and 70% by weight polyester. Example 7

68.5 g of the polyester known under the name CRYLCOAT® 240 (company UCB Chemicals / Belgium) and 1.5 g of the emulsifier known under the name Atlox® LP 6 (company Uniqema) are heated to 150 ° C. in a four-necked flask stirring apparatus and melted. 30 g of imidacloprid are introduced into the melt at 140 ° C. to 150 ° C. The mixture is then stirred until a clear melt at 150 ° C to 160 ° C and poured onto a Teflon sheet. The tack-free resin, which is clear at room temperature, is pulverized in a ball mill within 20 hours and sieved to particles <125 μm.

Example 8

68.5 g of the polyester known under the name CRYLCOAT® 240 (company UCB Chemicals / Belgium) and 1.5 g of the emulsifier known under the name Agrimer® 22 (company ISP) are heated to 150 ° C. in a four-necked flask stirring apparatus and melted. 30 g of imidacloprid are introduced into the melt at temperatures between 140 ° C. and 150 ° C. with stirring. The mixture is then stirred until a clear melt at 150 ° C to 160 ° C and poured onto a Teflon sheet. The tack-free resin, which is clear at room temperature, is pulverized in a ball mill within 20 hours and sieved to particles <125 μm.

C) Examples of use

Example 9

Release of active ingredient

3531.5 mg of the powder according to Example 6 are 500 ppm water in 1 liter of Cipac

(= Standard water C) stirred at 25 ° C. The powder used consists of 28.9% by weight of imidacloprid. The amount of imidacloprid weighed is accordingly 1020.6 mg. Imidacloprid has a water solubility of about 700 mg / liter at 25 ° C.

Samples are taken from the stirred mixture after the stirring times given in Table 3 below, which are filtered through a 0.2 μm microfilter. The concentration of imidacloprid is determined in each case in the filtrate. The active substance concentration is determined by means of HPLC:

Table 3

The measurement results show that the active ingredient is released from the powder formulation according to the invention in a controlled manner over a long period of time. Example 10

Rice pickling

3.34 g of the powder formulation according to Example 6 are made more aqueous with 12 g of water, 0.4 g of adhesive (Impranil DLN D50, Bayer AG) and 1 g of 1% by weight

Solution of the dye LEVANYL RED BB-LF (Bayer AG) mixed to a pickling liquid. This is applied to 200 g of rice grains of the KOSHIHIKARA variety dehusked. The rice grains treated in this way are then moved by hand in a bowl until the individual rice grains no longer adhere to one another. The seed is then dried at 40 ° C for 16 hours. All rice grains are coated. There is no abrasion.

Example 11

Rice pickling

1.67 g of the powder formulation according to Example 6 and 2.5 g of a commercial Caφropamid formulation with a Caφropamid content of 40 wt .-% are mixed with 4 g of water, 0.2 g of adhesive (Impranil DLN D50, Bayer AG) and 1 g of a 1% by weight aqueous solution of the dye LEVANYL RED BB-LF (Bayer AG) to a pickling liquid. This is based on 100 g rice grains

Koshihikara variety applied dehusked. The rice grains treated in this way are then moved by hand in a bowl until the individual rice grains no longer adhere to one another. The seed is then dried at 40 ° C for 16 hours. All grains of rice are coated. There is no abrasion.

Example 12

Rice pickling

In three different batches, 18.5 g rice grains of the variety are used

Koshihikari dehusked in a pickling shaker, each 200 μl of water applied. Then 55.5 μl of adhesive (Impranil DNL D 50, Bayer AG) are added. Immediately afterwards, the batches treated in this way are separated and with rotation

a) with 123.3 mg, b) with 246.7 mg or c) with 616.7 mg.

Powder formulation mixed according to Example 6. In this way, seed is obtained in which the active ingredient concentration

a) 200 g per 100 kg of seed, b) 400 g per 100 kg of seed or c) 1000 g per 100 kg of seed

is. All rice grains are coated. There is no abrasion.

Example 13

compatibility test

It will

18.5 g of pickled rice grains from each of the three samples produced according to Example 12 or

18.5 g rice grains each, which were treated in the same way with a commercial liquid imidacloprid pickling formulation, each seeded evenly in 17 cm x 13 cm bowls, the bottom of which is filled to a height of 4 cm with sifted and steamed soil. The rice grains are then covered with a 1 cm layer of earth.

The trays are then placed in a chamber in which the relative

Humidity is 90% and the temperature is 24 ° C during the day and 15 ° C at night.

The plants are examined for damage after the periods of sowing given in Table 4 below. Necrosis, yellowing, growth disorders and deformations are determined. The sum of all damages is expressed in percent. 0% means that no damage occurs, while 400% means that the plants have all the damage.

The preparations used, application rates of active ingredient and the test results are shown in the table below.

Table 4

compatibility test

Claims

claims

1. Powder formulations made from

at least one agrochemical active ingredient,

at least one biodegradable, hydroxyl-containing polyester optionally mixed with one or more other biodegradable polymers and

optional additives

exist and have a particle diameter below 125 μm.

2. Powder formulations according to claim 1, characterized in that at least one hydroxyl group-containing terephthalic acid polyester is contained as polyester.

3. Powder formulations according to claim 1, characterized in that imidacloprid and / or Caφropamid are contained as agrochemical active ingredients.

4. Powder formulations according to claim 1, characterized in that the content

of agrochemical active ingredients between 1 and 50% by weight,

of hydroxyl-containing polyesters, optionally in a mixture with additional polymers between 50 and 99% by weight and of additives between 0 and 30% by weight

lies.

5. A process for the preparation of powder formulations according to claim 1, characterized in that a mixture of

at least one agrochemical active ingredient,

- At least one biodegradable, hydroxyl-containing polyester, optionally in a mixture with one or more further biodegradable polymers and

optional additives

homogenized in the melt at temperatures between 50 ° C and 180 ° C and

6. Use of powder formulations according to claim 1 for applying the agrochemical active ingredients contained to plants and / or their habitat.

Process for the production of plant treatment agents, characterized in that powder formulations according to claim 1 are mixed with extenders and / or surface-active substances. Plant treatment agent, characterized by a content of powder formulations according to claim 1 in addition to extenders and / or surface-active substances.