United States Patent [19J
`Mayer et al.
`
`I 1111111111111111 11111 1111111111 1111111111 1111111111 lllll 111111111111111111
`US006030924A
`[11] Patent Number:
`[45] Date of Patent:
`
`6,030,924
`Feb.29,2000
`
`[54] SOLID FORMULATIONS
`
`5 679 618 10/1997 Kocur ...................................... 504/116
`
`[75]
`
`Inventors: Winfried Mayer, Bubenheim;
`Christian Wassmer, Niedersaulheim;
`Sandra Doerr, Bad Kreuznach, all of
`Germany
`
`[73] Assignee: American Cyanamid Company,
`Madison, N.J.
`
`[21] Appl. No.: 09/071,076
`
`[22] Filed:
`
`May 1, 1998
`
`Related U.S. Application Data
`[60] Provisional application No. 60/049,412, Jun. 11, 1997.
`
`[30]
`
`Foreign Application Priority Data
`
`May 7, 1997
`
`[EP]
`
`European Pat. Off. ………….. 97107521
`
`Int. CI.7 ..................................................... AOlN 25/12
`[51]
`[52] U.S. Cl. …………………….. 504/116; 504/134; 504/257;
`514/237.5; 514/436; 514/476; 514/494
`[58] Field of Search .. …………· ………………· … 504/116, 134,
`504/257; 514/237.5, 436, 476, 494
`
`[56]
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`FOREIGN PATENT DOCUMENTS
`
`3/1992 Canada .
`2091746
`0184 582 11/1984 European Pat. Off ..
`0447 004 A2
`3/1991 European Pat. Off ..
`1388924
`3/1975 United Kingdom .
`WO 88/05630
`8/1988 WIPO .
`WO 89/00079
`1/1989 WIPO.
`WO 97/5777
`2/1997 WIPO .
`
`Primary Examiner----S. Mark Clardy
`Attorney, Agent, or Firm-Barbara L. Renda
`
`[57]
`
`ABSTRACT
`
`The novel solid formulations obtained by low pressure
`extrusion of a mixture comprising
`at least one active ingredient; and
`at least one defoaming agent and/or foam breaking agent
`from the
`group consisting of perfluoroalkylphosphinic acids and/or
`perfluoroalkylphosphonic acids and/or their salts,
`show foam breaking activities even after extrusion, drying
`and storage at elevated temperatures and are thus very
`suitable for preparing tank mixtures for use in crop protec(cid:173)
`tion.
`
`5,332,714
`
`7/1994 Albrecht et al. …………………… 504/116
`
`18 Claims, No Drawings
`
`1
`
`TIDE 1010
`
`

`

`1
`
`6,030,924
`
`2
`
`SOLID FORMULATIONS
`
`This application is based upon European Application EP
`97107521.3, filed May 7, 1997 and U.S. Provisional Appli(cid:173)
`cation 60/049412, filed Jun. 11, 1997. Priority of each is s
`hereby claimed under 35 U.S.C. §119.
`
`BACKGROUND OF THE INVENTION
`
`SUMMARY OF THE INVENTION
`
`35
`
`at least one active ingredient; preferably two different
`active ingredients, and
`at least one defoaming agent and/or foam breaking agent
`from the
`group consisting of perfluoroalkylphosphinic acids and/or
`perfluoroalkylphosphonic acids and/or their salts, which
`are produced by low pressure extrusion, show reduced
`foaming and dustiness.
`The active ingredient, which can be supplied in the form
`Many solid crop protection agents are currently supplied
`in the form of wettable powders and granules. Typically, the 10 of the solid formulation according to the invention include
`all suitable biologically active compounds for plant
`herbicidal, fungicidal or insecticidal active ingredients are
`used together with inert fillers, such as chalk or kaolin, in
`protection, preferably fungicides, herbicides, insecticides,
`acaricides, nematicides and repellents. Active ingredients
`particular surface active substances, in the preparation of
`which are solid at room temperature are preferred.
`such formulations so that the formulations are well wetted
`· 1 s Mixtures of different biologically active compounds can
`and dispersed in water. The inclusion of wettmg agents
`have a broader spectrum of activity than a single compound
`lowers the surface tension of the spray mix. As a result,
`alone. Furthermore, these can exhibit a synergistic effect
`uniform wetting of the leaf surface is achieved. However,
`compared with the single active ingredients. In a preferred
`due to this lowered surface tension, these spray mixtures
`embodiment, the formulation of the present invention can be
`also tend to foam.
`European patent application EP O 561 265 suggests reduc- 20 used with a mixture of active ingredients.
`Preferred fungicides for use in the compositions of the
`tion of the tendency of foaming of such solid formulation by
`present mvent10n are the commercially available com-
`the addition of certain defoamer agents selected from the
`pounds selected from the group consisting of
`group of perfluoroalkylphosphinic acids and/or perfluoro-
`anilazine, azoxystrobin, benalaxyl, benomyl, binapacryl,
`alkylphosphonic acids and/or their salts. The formulations
`bitertanol, blasticidin S, Bordeaux mixture,
`disclosed by this reference are prepared either by spray 25
`bromuconazole, bupirimate, captafol, captan,
`drying or flu心zed bed granulation of aqueous suspensions
`carbendazim, carboxin, carpropamid,
`containing the formulation ingredients. However, depending
`chlorbenzthiazon, chlorothalonil, chlozolinate, copper-
`on the ingredients, the solid formulations obtained by spray
`containing compounds such as copper oxychloride, and
`drying or fluidized bed granulation exh伽t higher tendency
`copper sulfate, cycloheximide, cymoxanil, cypofuram,
`to develop dust when added to water in the spray tank. This 30
`cyproconazole, cyprodinil, dichlofluanid, dichlone,
`results in end-users being exposed to higher dose rates of the
`邮hloran, diclobutrazol, diclocymet, diclomezine,
`active ingredient. The present invention provides solid for-
`diethofencarb, difenoconazole, diflumetorim,
`mulations for crop protection with reduced tendency of
`dimethirimol, dimethomorph, diniconazole, dinocap,
`foaming and dustiness.
`ditalimfos, dithianon, dodemorph, dodine, edifenphos,
`epoxiconazole, etaconazole, ethirimol, etridiazole,
`famoxadone, fenapanil, fenarimol, fenbuconazole,
`fenfuram, fenhexamid, fenpiclonil, fenpropidin,
`fenpropimorph, fentin, fentin acetate, fentin hydroxide,
`ferimzone, fluazinam, fludioxonil, flumetover,
`fluquinconazole, flusilazole, flusulfamide, flutolanil,
`flutriafol, folpet, fosetyl-aluminium, fuberidazole,
`furalaxyl, furametpyr, guazatine, hexaconazole,
`imazalil, iminoctadine, ipconazole, iprodione,
`isoprothiolane, kasugamycin, kitazin P, kresoxim(cid:173)
`methyl, mancozeb, maneb, mepanipyrim, mepronil,
`metalaxyl, metconazole, methfuroxam, myclobutanil,
`neoasozin, nickel dimethy 心 thiocarbamate,
`nitrothalisopropyl, nuarimol, ofurace, organo mercury
`compounds, oxadixyl, oxycarboxin, penconazole,
`pencycuron, phenazineoxide, phthalide, polyoxin D,
`polyram, probenazole, prochloraz, procym汕one,
`propamocarb, propiconazole, propineb, pyrazophos,
`pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,
`quinomethionate, quinoxyfen, quintozene,
`spiroxamine, SSF-126, SSF-129, streptomycin, sulfur,
`tebuconazole, tecloftalame, tecnazene, tetraconazole,
`thiabendazole, thifluzamide, thiophanate-methyl,
`血ram, toiclofosmethyl, tolylfluanid, triadimefon,
`triadimenol, triazbutil, triazoxide, tricyclazole,
`tridemorph, triflumizole, triforine, triticonazole, valida-
`mycin A, vinclozolin, XRD-563, zarilamid, zineb,
`z1ram.
`In addition, the formulations according to the invention
`65 may contain at least one compound of the following classes
`of biological control agents such as viruses, bacteria,
`nematodes, fungi, and other microorganisms hich are suit-
`
`40
`
`The present invention provides a novel solid formulation
`obtained by low pressure extrusion of a mixture comprising
`at least one active ingredient; and
`at least one defoaming agent and/or foam breaking agent
`from the
`group consisting of perfluoroalkylphosphinic acids and/or
`perfluoroalkylphosphonic acids and/or their salts.
`These formulations exhibit foam breaking activities even 45
`after extrusion, drying and storage of the formulation
`elevated temperatures and are thus advantageous for pre(cid:173)
`paring tank mixtures for use in crop protection. Moreover,
`the new formulations possess a reduced tendency to develop
`dust when added to water in the spray tank.
`The new formulations show an excellent activity and
`selectivity in various crops.
`It is an object of the present invention to provide novel,
`solid formulations for crop protection which exhibit
`decreased foaming and decreased dusting during their use. 55
`It is also an object of the invention to provide methods for
`controlling pests by contacting plants with a composition
`obtained by dispersing a solid formulation according to the
`invention.
`These and other objects and features of the invention will 60
`be more apparent from the detailed description set forth
`hereinbelow, and from the appended claims
`
`50
`
`DETAILED DESCRIPTION OF IBE
`PREFERRED EMBODIMENTS
`It has surprisingly been found that improved solid for(cid:173)
`mulations for crop protection comprising
`
`2
`
`

`

`3
`
`6,030,924
`
`4
`
`15
`
`they are solid. In the case of fluid active ingredients the
`able for the control of insects, weeds or plant diseases, or to
`induce host resistance in the plants. Examples of such
`formulation according to the invention contains as a rule a
`solid aux山ary with absorbing properties
`biological control agents are: Bacillus thuringiensis, Verti-
`The content of the active ingredient is, as a rule, 30 to 90%
`cillium lecanii, Auto graphic a californica NPV, Beauvaria
`5 by weight, preferably 50 to 87% by weight, and, in
`bassiana, Ampelomyces quisqualis, Bae 山s subt山s,
`particular, 70 to 85% by weight of total composition. Suit(cid:173)
`Pseudomonas fluorescens, Steptomyces griseoviridis and
`Trichoderma harzianum.
`able defoaming and/or foam breaking agents are perfluoro
`Moreover, the formulations according to the invention
`(C6-C12)alkylphosphinic acids and/or perfluoro(C6-立）
`may contain at least one chemical agent that induces the
`alkylphosphonic acids and/or their alkali metal salts, such as
`systemic acquired resistance in plants such as, for example, 10 sodmm or potasssium salts, their ammonium salts, and the订
`nicotinic acid or derivatives thereof, 2,2-dichloro-3,3-
`(C2心）alkylammonium salts. These defoaming and/or
`dimethylcylopropylcarboxylic acid or BION.
`foam breaking agents are commercially available, for
`.
`Also preferred compositions can include derivatives of
`example, Fluowet PP, a mixture of perfluoro(C三）
`triazolopyrimidines which are disclosed, for example, by
`alkylphosphinic acids and perfluoro(C6-C12)
`European patent application EP-A-0 550 113.
`alkylphosphonic acids, (commercially available from Clari-
`Another group of preferred fungicidal compounds are the
`benzoylbenzenes which are disclosed, for example, by Euro-
`ant GmbH, formerly Hoechst AG, Germany) or can be
`pean patent application EP-A-0 727 141.
`prepared by known methods (DE 21 11 167). Particularly
`preferred are aqueous solutions of mixtures of perfluoro
`Preferred herbicides are the commercially available com-
`pounds selected from the group consisting of:
`20 (C6-C12)alkylphosphinic acids and perfluoro(C6心）
`2,4-D, 2,4-DB, 2,4-DP, acetochlor, acifluorfen, alachlor,
`alkylphosphonic acids, which are commercially available as,
`for example, De foamer SF (commercially available from
`alloxydim, ametrydione, amidosulfuron, asulam, atrazin,
`azimsulfuron, benfuresate, bensulfuron, bentazon, bifenox,
`Clariant GmbH, formerly Hoechst AG, Germany). These
`bromobutide, bromoxynil, butachlor, cafenstrole,
`aqueous solut10ns can easily be incorporated into the for-
`carfentrazone, chloridazon, chlorimuron, chlorpropham, 25 mulation in the wetting step of the process
`chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron,
`The proportion of the antifoam or foam breaking agent in
`clomazone, clopyralid, cyanazin, cycloate,
`the formulation can be up to 10% by weight.As a rule, 0.05
`cyclosulfamuron, cycloxydim, daimuron, desmedipham,
`to 10% by weight, preferably 0.07 to 4% by weight, and, in
`山-methazone, dicamba, dichlobenil, diclofop, diflufenican,
`particular, 0.08 to 0.50% by weight are used
`dimethenamid, dithiopyr, diuron, eptame, esprocarb, 30
`Specific embodiments of the invention include:
`ethiozin, fenoxaprop, flamprop-M-isopropyl, flamprop-M-
`(a) A solid formulation obtained by a process which
`methyl fluazifop, fluometuron, fluoroglycofen, fluridone,
`comprises the steps of: wetting the powder base of the
`fluroxypyr, flurtamone, fluthiamid, fomesafen, glufosinate,
`glyphosate, halosafen, haloxyfop, hexazinone,
`active ingredient with a mixture of the defoaming agent
`imazamethabenz, imazamethapyr, imazamox, imazapyr, 35
`and/or foam breaking agent and water, in particular,
`imazaquin, imazethapyr, ioxynil, isoproturon, isoxaben,
`with an aqueous solut10n of the defoammg and/or foam
`isoxaflutole, lactofen, MCPA, MCPP, mefenacet,
`breaking agent;
`metabenzthiazuron, metamitron, metazachlor,
`extrusion of the wetted powder on an extruder, m
`methy心mron, metolachlor, metnbuzm, metsulfuron,
`particular, on a radial twin screw extruder, a basket
`molmate, mcosulfuron, norflurazon, oryzalm, oxadiargyl, 40
`extruder or a mono or twin dome extruder; and
`oxasulfuron, oxyfluorfen, pendimethalin, picloram,
`drying the resulting granules in a fluidized bed dryer
`pretilachlor, propachlor, propanil, prosulfocarb,
`(b) A solid formulation, wherein the powder base of the
`pyrazosulfuron, pyridate, qinmerac, quinchlorac,
`active ingredient comprises, in addition to the said
`quizalofopethyl, sethoxydim, simetryne, sulcotrione,
`constituents, further formulation auxiliaries selected
`sulfentrazone, sulfosate, terbutryne, terbutylazin, 45
`from the group consisting of dispersants, agglomera(cid:173)
`thiameturon, thifensulfuron, thiobencarb, tralkoxydim,
`tion aux山aries, stab山zers, wetting agents, disinte(cid:173)
`triallate, triasulfuron, tribenuron, triclopyr, trifluralin
`grants and fillers.
`Furthermore preferred are the derivatives of aryloxypi(cid:173)
`(c) A solid formulation essentially consisting of 25 to 90%
`colineamides which are disclosed, for example, by European
`by weight of at least one active ingredient, 0.05 to 10%
`patent application EP-A-0 447 004, in particular, N-(4- so
`by weight of said defoaming agent and/or foam break(cid:173)
`fl uorop hen y 1) 6-(3-trifl uoromethy lp henoxy)-pyrid-2-
`ing agent, 0 to 45% by weight of a filler;
`ylcarboxamide having the proposed common name picolin(cid:173)
`afen.
`5 to 50% by weight of one or more dispersants, agglom(cid:173)
`Preferred insecticides are the commercially available
`eration auxiliaries, one or more wetting agent, one or
`compounds selected from the group consisting of
`more disintegrants and/or one or more stabilizers.
`In a particular preferred embodiment the formulation
`pyrethroids such as deltamethrin, acrinathrin,
`according to this invention contain 0-5% by weight of a
`tralomethrin, permethrin and cypermethrin, benzoy(cid:173)
`filler and 10-25% by weight of solid dispersant.
`lureas such as diflubenzuron and teflubenzuron, and
`active substances such as endosulfan and pirimicarb.
`(d) A solid formulation wherein said active ingredient
`The active ingredients used in the formulation according 60
`comprises an E/Z mixture of an acrylic acid morpholide
`fungicide of the following structure:
`to the present invention may be solid or fluid, preferably
`
`55
`
`3
`
`

`

`勹
`N
`0
`\_J
`
`(R勺n
`
`厂—勹丿丫r , Ou—,,s,, "
`
`5
`
`6,030,924
`
`in which
`R1 and R2 each independently represent a hydrogen atom
`or an alkyl, alkenyl, alkynyl, alkadienyl, haloalkyl or
`alkoxy group, preferably a C1_6 alkoxy group, m par-
`ticular a methoxy group, and
`R3 and R4 each independently represent a hydrogen or a 20
`halogen atom or an alkyl or alkoxy group, preferably a
`hydrogen or chloro atom,
`in particular wherein said active ingredient is a dimetho-
`morph (coded DMM) or a mixture of DMM and
`mancozeb (coded MZ) and/or dithianon (coded DI).
`(e) A solid formulation wherein said active ingredient
`compnses an aryloxypicolinamide herbicide of the
`following structure:
`
`6
`Suitable extruders include axial and radial designs with
`single or twin screws, and roll-type extrusion presses. A twin
`screw extrusion has proven to be most useful. During the
`extrusion process, the extruder is preferably cooled to tern-
`5 peratures below 40°C., in particular, by a flow of cooling
`water at the extruder head with water temperatures being
`between and 25°C.
`The premix is extruded through a die or screen. The die
`holes range in diameter from 0.25 to 7 mm, and preferably,
`10 from 0.4 mm to 2 mm.
`As a rule, the extrusion takes place at a pressure of up to
`50 bar, preferably, up to 30 bar, and in particular, up to 20
`bar.
`The cylindrical granules formed during the extrusion
`15 process are dried to a water content less than 3% by weight,
`preferably less than 2.5%, and in particular about 2% by
`weight.
`The drying process is preferably carried out with a
`fluidised bed dryer at temperatures between 60°C. and 80°
`C., preferably, between 65°C. and 75°C., and, in particular
`at about 70°C.
`After drying, the product is preferably sieved on 0.4 and
`2.0 mm sieves.
`Suitable dispersants may be so-called water-soluble
`soaps, as well as water-soluble synthetic surface-active
`25 compounds. Soaps usually are alkali, earth alkali or option-
`ally substituted ammonium salts of higher fatty acids
`(C10一心）， e.g., the sodium or potassium salts of oleic or
`stearic acid or of mixtures of natural fatty acids which are
`30 prepared, for example, from coconut or tallow oil.
`Furthermore, methyl-taurine salts of fatty acids may be used.
`However, so-called synthetic surfactants are preferably
`used, especially fatty sulfonates, fatty sulfates or alkyl aryl
`sulfonates. The fatty sulfates or fatty sulfonates are normally
`used as alkali, earth alkali or optionally substituted ammo(cid:173)
`nium salts and have an alkyl moiety of 8 to 22 carbon atoms,
`whereby alkyl also means the alkyl moiety of acyl residues,
`such as the sodium or calcium salt of lignin sulfonic acid, of
`sulfuric acid dodecylate, or of a mixture of fatty alcohols
`in which
`40 prepared from natural fatty acids, in particular, sodium
`R讨nd R8 each independently represent a halogen atom or
`lignin sulfonate. This also includes the salts of sulfuric acid
`esters, sulfonic acids and adducts of fatty alcohols and
`an alkyl, or haloalkyl group, preferably a fluoro or
`chloro atom or a C1_6 fluoroalkyl group, in particular a
`ethylene oxide. Alkyl aryl sulfonates are, for example, the
`d.
`fluoro atom or a trifluoromethyl group, and
`so mm, calcmm or triethyl ammonium salts of dodecyl
`R6 represents a halogen atom or an alkyl or alkoxy group, 45 benzene sulfonic acid, dibutyl naphthalene sulfonic acid or
`of a condensate of naphthalene sulfomc acid and formalde-
`preferably a C1_6 alkyl or a C1_6 alkoxy group, in
`particular a methyl or methoxy group,
`hyde. Furthermore, phosphates, such as the salts of the
`R7 represents a hydrogen atom or an alkyl group, in
`phosphoric acid ester of a p-nonylphenol-(4--14)-ethylene
`particular a hydrogen atom or a methyl group,
`oxide adduct or phospholipids, may be used. In add山on,
`m and reach independently represent 1 2 or 3, preferably 50 non-ionic dispersants may be used. Preferred are block
`1 or 2, in particular 1, and
`polymers obtainable from propylene oxide and ethylene
`oxide, in particular, block polymers which consist of a
`n represents O or 1, in particular 0.
`polyoxypropylene core having a molecular weight of about
`Particularly preferred are the solid formulations wherem
`3,000 to about 3,500 and the remainder having a combined
`the active ingredient is picolinafen (coded PN), or a mixture
`of PN and cyanazine (coded CY) and/or pendimethalin 55 molecular weight of about 6,000 to 7,000 comprising eth-
`ylene oxide units
`(coded PD).
`In preferred embodiments, the dispersants are selected
`(t) The solid formulation which is water-dispersible gran-
`from the commercially available components:
`ules.
`Tensiofix LX special, a sodium lignin sufonate available
`Depending on the active ingredient used, the powder base
`from Omnichem S.A., 1348 Louvain-La-Neuve, Bel(cid:173)
`comprising the active ingredient is wetted with an aqueous 60
`gmm;
`solution of the defoamer and 10 to 35% by weight, prefer(cid:173)
`Ufoxane 3 A, a sodium lignin sufonate available from
`ably 12 to 30% by weight, in particular 14 to 29.5% by
`Borregaard;
`weight of water by spraying the solution on the agitated
`Borresperse NH, an ammonium lignin sufonate (available
`powder.
`from Borregaard);
`The wetted material is a non-dusty and flowable mass and 65
`Geropon TN72, a sodium polycarboxylate, (available
`is used as the feedstock for the granulation process in the
`from Rhod团， formerly Rhone-Poulenc);
`low-pressure extruder.
`
`4
`
`

`

`6,030,924
`
`8
`7
`75 to 85% by weight of one or a mixture of two
`Soprophor AS/222, an ethoxylated fatty alcohol adsorbed
`on silica, (available from Rhodia formerly Rhone(cid:173)
`fungicides,
`Poulenc); and
`0.05 to 0.30% by weight of a mixture of perfluoro
`Pluronic PE 10500, a block po~ymer obtained from pro(cid:173)
`(C6-C12)alkylphosphinic acids and perfluoro(C6-丘）
`pylene oxide and ethylene oxide, (available from BASF s
`alkylphosphonic acids,
`Corporation).
`The solid formulation according to the present invention
`7.5 to 15% by weight of a lignin sulfonate as dispersant,
`preferably comprises 5 to 25% by weight, in particular 7.5
`1 to 5% by weight of an alkali metal or ammonium sulfate
`to 15% of at least one dispersant.
`as disintegrant, and
`Suitable wetting agents are, as a rule, salts of long chained 10
`1 to 5% by weight of lauryl sulfate as wetting agent
`alkyl sulfates. The fatty sulfates are normally used as alkali,
`earth alkali or optionally substituted ammonium salts and
`In another preferred embodiment of the present invention
`have an alkyl moiety of 8 to 22 carbon atoms. Particularly
`the water dispersible granules obtainable by low pressure
`preferred is sodium lauryl sulfate, commercially obtainable
`extrusion essentially consist of
`as Tensiofix BCZ, a sodium alkyl sulfate, available from
`70 to 85% by weight of one or a mixture of two
`Omnichem S.A., 1348 Louvain-La-Neuve, Belgium or as 15
`herbicides,
`Rewopol NLS 90 available from Witco GmbH, Germany.
`The solid formulation according to the present invention
`0.05 to 0.35% by weight of a mixture of perfluoro
`preferably comprises 1 to 10% by weight, in particular, 2 to
`(C6-C12) alkylphosphinic acids and perfluoro(C6-卢）
`5% of at least one wetting agent.
`alkylphosphonic acids,
`The surfactants and wetting agents generally used for 20
`compositions of the invention are disclosed in publications
`5 to 10% by weight of a lignin sulfonate as dispersant,
`such as:
`0.5 to 5% by weight of a polycarboxylate as dispersant,
`"McCutheon's Detergents and Emulsifiers Annual", MC
`0.5 to 5% by weight of a propylene/ethylene oxide block
`Publishing Corp., Ridgewood, N.J., USA 1981;
`polymer as dispersant,
`H. Stache, "Tensid-Taschenbuch", 2nd ed., C. Hanser, 25
`Munich, Vienna, 1981;
`1 to 7.5% by weight of an alkali metal acetate as
`M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III,
`dis in te grant,
`Chemical Publishing Co., New York, N.Y., USA
`0.1 to 7.5% by weight of kaolin as filler, and
`1980-1981.
`1 to 5% by weight of lauryl sulfate as wetting agent
`Conventionally used fillers may be used in the solid 30
`Furthermore, the invention relates to a method of com-
`formulation according to the present invention. Preferably
`used are such solid matters, which are essentially insoluble
`bating pests at a locus which compnses treatmg the locus
`in water and have large surfaces and/or high absorbencies, in
`with a composition obtained by dispersing a solid formula-
`particular, natural mineral powders such as kaolin, argilla-
`tion according to the invention in water.
`ceous earth, talcum, chalk, quartz, atapulgite, montmorillo- 35
`Moreover, the invention relates to the use of a solid
`nite and synthetic mineral powders such as silicic acid,
`alumina, silicates, in particular kaolin, or Clay GTY, a
`formulat10n according to the invention for the preparat10n of
`liquid aqueous formulations or spray mixtures
`血xture of inorganic minerals, which is commercially avail-
`able from EEC Int. Ltd., UK.
`As commodities, the mventive solid formulat10ns may
`The solid formulation according to the present invention 40 preferably be in a pure, undiluted form whereas the end-user
`preferably comprises O to 45% by weight of at least one
`generally employs diluted compositions. Said compositions
`filler, in particular, 20 to 40% of Clay GTY and a content of
`may be diluted to a concentration of 0.001 % of active
`less than 7.0% by weight of a solid dispersant.
`ingredient (a.i.). The doses usually are in the range of about
`A major advantage of the solid formulations of the present
`invention results from the low amounts of kaolin required,
`0.01 to 10 kg a.i./ha, preferably in the range of 0.1 to 4.0 kg
`if the formulation comprises high amounts of active 45 a.i./ha.
`ingredients, preferably more than 60% by weight, in par-
`Said compositions may also comprise other aux山aries
`ticular 70 to 90% by weight and/or high amounts of a solid
`such as stab山zers, viscosity controlling agents, thickeners,
`dispersant, preferably 7.0-25.0% by weight, in particular
`adhesives, fertilizers or other active ingredients to obtain
`.
`8.0-15.0% b y weight. The inventive solid formulat10ns
`contain, as a rule, less than 10% by weight, and preferably so special effects.
`For a clearer understanding of the invention, the follow-
`less than 6% by weight of kaolin. In a highly preferred
`ing specific examples are set forth below. These examples
`embodiment, no kaolin is necessary at all.
`Conventionally used disintegrants may be used in the
`are merely illustrations and are not to be understood as
`solid formulation according to the present invention.
`limiting the scope and underlying principles of the invention
`Preferably, such solid matters, which are highly soluble in 55 in any way. Indeed, various modifications of the invention in
`water, m particular, salts such as potassmm sulfate, ammo-
`addition to those shown and described herein will become
`nium sulfate, potassmm carbonate, sodium hydrogencarbon-
`apparent to those skilled in the art from the following
`ate and sodium acetate trihydrate are utilized.
`examples and foregoing description. Such modifications are
`The solid formulation according to the present invention•
`also mtended to fall within the scope of the appended claims.
`preferably comprises 1 to 10% by weight, in particular, 1 to 60
`7.5% by weight of at least one disintegrant. In a preferred
`embodiment, the solid formulation of the present invention
`contains 2 to 5% by weight of an alkali metal or ammonium
`sulfate or an alkali metal acetate trihydrate as disintegrant.
`In a preferred embodiment of the present invention, the 65
`water dispersible granules obtained by low pressure extru(cid:173)
`sion essentially consist of
`
`Prior to the extrusion process different powder bases have
`been prepared consisting of:
`
`EXAMPLE 1
`
`Dimethomorph/Mancozeb 90/600 WG
`
`5
`
`

`

`9
`
`6,030,924
`
`mgred1ent
`
`d1methomorph
`Tens10fix BCZ
`Tens10fix LX special
`ammonmm sulfate
`
`Powder Base A
`quantity (g)
`
`Powder Base B
`quantity (g)
`
`450
`150
`to 1000
`
`450
`150
`to 1000
`100
`
`These Powder bases have been admixed with mancozeb
`as a second active ingredient as follows:
`
`mgred1ent
`
`quantity (g)
`
`Powder Mixture A
`
`powder base A
`mancozeb 85% w/w
`Tens10fix LX special
`Powder Mixture B
`
`powder base B
`mancozeb 85% w/w
`ammonmm sulfage
`Tens10fix LX special
`
`200
`706
`to 1000
`
`200
`706
`20
`to 1000
`
`5
`
`10
`
`15
`
`20
`
`25
`
`The resulting powder mixtures are wetted with water (20
`to 30% w/w) containing 1.8 g of a mixture of perfluoro(C。
`Cg, C10)alkylphosphinic acids and perfluoro(C6, Cg, C10) 30
`alkylphosphonic acids, which has been obtained by diluting
`Defoamer SF (obtainable from Clariant GmbH, formerly
`Hoechst AG, Germany) with water.
`The wetting process is carried out in a Drais annular mixer 35
`or, alternatively, a 丘dige mixer. The wetted material is a
`non-dusty flowable mass which is used without delay as the
`feedstock for the extrusion process.
`
`The granulation is carried out by means of extrusion
`technique using a Twin screw extruder with a throughput 40
`rate of 70 to 100 kg/h at a pressure of 0---30 bar. The extruder
`head is cooled with water to 20°C. The grid diameter is 1
`mm. The resulting extruded mass is dried with a fluidized
`bed dryer at a temperature of about 70°C. to achieve a water
`content of less than 2.5% by weight. After drying, the 45
`product is sieved on 0.4 and 2.0 sieves. The obtained
`yellowish solid product has a bulk density of 678 kg/m3. The
`cylindrical granules formed show a porous surface.
`
`Further physical properties of the resulting product are
`given in the following Tables I to VI. The formulation has
`been stored at different temperatures (20, 30 or 40°C.) in
`block bottom bags or at elevated temperature of about 54°C.
`under pressure.
`
`TABLE I
`
`Active Suspensibility
`
`Active suspensibilitv at a dilution of
`
`0 5% w/v
`
`0 2% w/v
`
`DMM
`
`MZ
`
`DMM
`
`MZ
`
`Initial
`2 weeks at 54°C
`8 weeks at 40°C
`26 weeks at 20°C
`
`93
`93
`93
`88
`
`99
`98
`95
`93
`
`92
`91
`93
`88
`
`96
`91
`95
`92
`
`50
`
`55
`
`60
`
`65
`
`10
`
`TABLE I-continued
`
`Active Suspensibility
`
`Active suspensibility at a dilution of
`
`0.5% w/v
`
`0.2% w/v
`
`DMM
`
`26 weeks at 30°C
`
`87
`
`MZ
`
`90
`
`DMM
`
`MZ
`
`87
`
`90
`
`TABLE II
`
`Dispersibilitv
`
`Initial
`2 weeks at 54°C
`8 weeks at 40°C
`26 weeks at 20°C
`26 weeks at 30°C
`
`Dispersibility [ % ]
`
`90
`87
`86
`92
`89
`
`TABLE III
`
`Wet sieving
`
`Residue on 75µm [% w/w]
`
`Initial
`2 weeks at 54°C
`8 weeks at 40°C
`26 weeks at 20°C
`26 weeks at 30°C
`
`0.06
`0.07
`0.05
`0.05
`0.03
`
`foam fmll
`
`after 1 mm
`1000
`<
`
`TABLE IV
`
`Persistent foammg
`
`directly
`
`15
`28
`30
`30
`
`TABLE V
`
`Dustiness
`
`[ mg] dust/30 g of granules
`521
`
`Initial
`8 weeks at 40°C
`26 weeks at 20°C
`26 weeks at 30°C
`
`Initial
`8 weeks at 40°C
`26 weeks at 20°C
`26 weeks at 30°C
`
`TABLE VI
`
`Dry sieve analysis
`
`Particle size [µm]
`
`Distribution[% w/w]
`
`>2000
`1000-2000
`500-1000
`
`0.0
`78.6
`20.3
`
`6
`
`

`

`”
`
`TABLE VI-continued
`
`Orv sieve analysis
`
`6,030,924
`
`12
`
`5
`
`mgred1ent
`
`Powder Base C
`quantity (g)
`
`Powder Base D
`quantity (g)
`
`Particle size [µm]
`
`Distribution[% w/w]
`
`250-500
`125-250
`<125
`
`0.2
`<0.1
`<0.1
`
`It can be seen from Table IV that the foam breaking
`activity of the defoaming agent is given directly after the
`preparation of the solid formulation, even after longer term
`storage at 20°C., 30°C. or 40°C.
`
`Lower concentrations of the defoamer in the composition
`result in similar activity. Solid water dispersible granules
`obtained by the same methods described above, but con(cid:173)
`taining 0.08% , 0.10% or 0.30% by weight of the same
`defoamer show similar foam breaking activities.
`
`10
`
`15
`
`20
`
`As seen from Table V, the water dispersible granules
`according to the present invention exhibit very low dusti-
`ness.
`
`Comparison-Example 1
`
`30
`
`d1methomorph (DMM)
`dithianon
`Rewopol NLS 90
`Clay GTY
`Borresperse NH
`ammomum sulfate
`
`600
`。
`200
`200
`。
`。
`
`。
`700
`。
`100
`150
`50
`
`These Powder bases are mixed together as follows:
`
`Powder Mixture A
`
`mgredient
`
`powder base C
`powder base D
`Borresperse NH
`Clay GTY
`
`quantity (g)
`504
`252
`0
`0
`55
`
`The resulting powder mixtures are wetted with water (15
`25 to 20% 10 w/w) containing 1.0 g of a mixture of perfluoro
`(C6, Cg, C10)alkylphosphinic acids and perfluoro(C6, Cg,
`卢）alkylphosphonic acids, which has been obtained by
`Dimethomorph/Mancozeb 90/600 WG
`diluting De foamer SF (obtainable from Clariant GmbH,
`Water dispersible granules are prepared accordmg to the
`formerly Hoechst AG, Germany) with water
`. d
`.
`method described in Example 1, in which the defoamer has
`The wetting process 1s carne out m a Dra1s annular mixer
`or, alternatively, a Lobdige mixer. The wetted material is a
`been replaced by different silicon based antifoam powders
`(Wacker ASP 13, 20, 30, commercially available from
`non-dusty flowable mass which is used without delay as the
`Wacker, Germany). These are far less active upon extrusion
`feedstock for the extrusion process
`The granulation is carried out by means of extrusion
`as can be seen from Table VII, which shows the in山al foam
`formation achieved with these products 1 minute after 35 technique using a Twin screw extruder with a throughput
`rate of 70 to 100 kg/h at a pressure of 0---30 bar. The extruder
`血xmg:
`head is cooled with water to 20°C. The grid diameter is 1
`mm. The resulting extruded mass is dried with a fluidized
`bed dryer at a temperature of about 70°C. to achieve a wa