DE1567138A1 - Pesticide composition and process for their preparation - Google Patents

Description

Jose "Antonio Serrallach Julia . Barcelona (Spain)

Pesticide composition and process for their preparation

The present invention relates to a liquid pesticide composition in which in a liquid pesticid a surfactant is dissolved, the solubility of the surfactant in the liquid pesticide is at least so large that when the liquid pesticidal composition is emulsified in water a certain fineness of the emulsified particles of the pesticide.

It is known that pesticidally active agents,

which are currently used in agriculture, for example, must be in the appropriate formulation for them to be effective. In general, the active component becomes a Pesticide after micronization / finely divided or it is in suitable solvents and then with one or more Surface-active agents or emulsifiers, tackifying agents and / or stabilizers mixed and these materials are then marketed as emulsifiable concentrates or emulsifiable solutions, or they are mixed with an inert material, in which case dust or wetting

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form bare powders. As a result, the active component in foinverteilter Shape · is applied, the following advantages can be obtained.

a) The result is an enlarged surface

of the pesticide whereby a greater coverage of the substrate to be treated, for example leaves or fruits, is achieved, if you use the product and thereby a better estimate of the substrate against the pests is achieved.

b) There is an even distribution of the

active component within the mixture in the event that wettable Powder or StMu.be available.

c) Stable emulsions are formed for 2s when the pesticidal agent is an enulsifiable concentrate or an emulsifiable solution of the active component.

To date, pesticidal compositions have been formulated as indicated below:

1. Sprays

Si * who the. diluted with water before use and can be in the following forms:

a) Wettable powders that are dispersible in water are.

b) Concentrated emulsions and solutions that are dispersible in water.

c) Self-emulsifiable mineral oils in water and

d) Solutions of organic solvents which can be emulsified in water.

As a solvent have hitherto been used for materials of class d) organic substances such as pine oil, cyclohexane, lower alcohols, alcohol ethers, petroleum derivatives, vegetable oils, acetone and mixtures of these materials are used. The pesticidal formulations of classes a) and b) also generally contain a solvent.

2. Dusts

The pigeons were applied with the aid of air nozzles and they were made using finely divided solid

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Carrier materials produced, such as 2.3. Talc ;, clay, «" ag Magnesiumcarbo.-nat, Diatomaceous earth, pyrophylilite, lignocellulose, -. Flour and kicchugen such pests. The dusts generally contain about 0.5 to 10 wt. # Of pesticidally active component.

All of the above-mentioned heretofore known pesticidal agents have been generally taken at room temperature solid pesticidally active components are used, and a surface active agent and a solvent are used in addition to them used. Also in the event that the pesticide-active component is liquid, both a solvent and a surface-active Γ-lubricant have almost always been used for the formulation. Nevertheless, it is already known 'become a liquid pecticide-active Component only to be used in combination with a surface-active agent, i.e. without solvents. Furthermore it is too already known to use the last-mentioned pesticidal agents in such a way that they are absorbed onto a solid carrier material i.e. in the form of dusts or wettable powders.

Nevertheless, so far with pesticidal gowns,

which is a liquid pesticic. and contain a surfactant solvent heretofore generally not obtained satisfactory results because the reproducibility has been rather poor. It has now turned out to be these relatively poor results can be attributed to the fact that in the event that such Agents in the application dose are mixed with water. the pesticide-active component either insufficient or is emulsified in an uneven or unpredictable manner, and that the particle size of the emulsified particles in the so Sprühmischur.g obtained is large and irregular. This insufficient or unpredictable dehydration also occurred with liquid pesticides, which in addition to a liquid pesticide-active component and a surface-active, «suffer! also contained a solvent. However, in this case occur when the concentration of solvents is relatively high, there are additional disadvantages.

So far, the "'"' was the obsession with compliance

a certain particle size for the emulsified particles liquid Pesticides ir. the aqueous emulsion not yet recognized, and it was also richt be.-rzr-r.t, d? .cs a Zusanmer.hr.r.r BAD ORiGWAt -? - 009839/2144

ψ 1S67138

between the activity of the pesticide-active component and the particle size which it has in the aqueous ionic ion. In addition, no systematic investigations at all have been undertaken so far in the direction of which type of emulsifiers and which concentrations of the same t & X the peetioid-active components in question are most suitable. Also, it has not yet been investigated how the size of the pond in the emulsion affects the resistance of the pesticide when it is used, and no field tests have been carried out in this regard. If one takes into account how great the amount of work and research in technology has been in the last few years and also now that, among other things, new and better peetid-active components have been found, then it is surprising that so little research has been carried out in the field as one for already known and proven pesticide-active components can achieve significantly improved modes of action through an improved formula.

It has now been found that the particle size, which has a liquid pesticide when emulsified in lasser is essential.

As already mentioned, this importance of the particle size has so far not been recognized by the manufacturers of surface-active agents, nor by the industry that supplies ready-formulated pesticides. For example, the manufacturers of pesticides indicate the application dose and the percentage of active material contained in the pesticide, but they do not say anything about it from what particle size the active component in the spray liquid will have when this is prepared, wherein Of course, the condition would also have to be taken into account, whether the preparation of the spray liquid with cold or soft Water takes place. But only information regarding the size of the pesticidally active component allows the active component To assess the surface of the pesticide and to estimate the results that can be achieved in the field.

When the self-emulsifiable liquid pesti- SAD, ORIGINAL

If both solutions of the active component are in organic solvents (see, for example, the pesticides described in British patent specification No. 896 942), there are additional disadvantages.

In general, the solvents have one

low boiling point so they evaporate before the water the spray liquid has evaporated; This leaves little Iröpfchen or. Irregular spots of pesticide-active material distributed auf.dem treated substrate, for example the Leaves or fruits back, and these spots or (droplets lead to uneven coverage of the substrate with the active component and in some cases can even lead to lead to phytotoxic phenomena. In the pesticides, which contain solvents, namely becomes the surface-active Agents normally selected to disperse the solvent in which the pesticide is dissolved in the water of the spray and not the pesticide itself, so that after the solvent has evaporated, the pesticide-active component in is not emulsified or not sufficiently emulsified in the water.

However, it was also used in cases where liquid. pesticidal compositions containing no or little solvent have been used, none heretofore Efforts have been made that these materials are sufficiently self-emulsifiable, i.e. that certain minimal Requirements regarding the particle size to be achieved are made will. There are also pesticide agents known, the special phosphoric acid ester as the active component and special Contain emulsifiers, and it is mentioned that these agents, when mixed with water, are very finely divided emulsions or provide colloidal solutions. However, it has never been made clear what the expression "very finely divided emulsion" is actually meant. Moreover, it has never been said before what precautions must be taken so that these finely divided emulsions are actually achieved.

In British Patent No. 682332, for example, such pesticidal compositions have been described,

BADORlGtMAL ~ ⁵ ~ 009839/2144

the, then, when they are mixed ait lasser, feiA Eeailions deliver and those called pestioidactive aatic Ister of dialkylthiophosphoric acid and as medium contain certain polyglycol ethers. However aäaii iö this one

British patent specification says nothing about the emulsion actually has to be, and furthermore 4 & aaire is latent on a certain combination of pestioid-active ^ Eü. In other words, the pesticides described in the British patent specification are limited in terms of the results obtained, i.e. in terms of the size that the pesticidally active ingredient should have in emulsion, and also in terms of the conditions and conditions used to produce such pesticide compositions, completely allgesst ^ t _f the pesticidal ZusanmensetzuRgeia described therein are with respect to the accurately specified eingesetztenjoberflächenaktiven means and the pesticidaktiven means employed, that is, "limited to a specific combination of ingredients pesticidaktiven UTTD surfactants.

The aim of the present invention was to improve & b öie.lPor-ÄUlierungstechnik and thereby improve the active diet of known liquid pesticides and to clarify conditions that make it possible to achieve the above-mentioned goals. These conditions are intended to be independent of a particular combination of pesticidally active ingredient and surfactant.

The present invention relates to a liquid pesticidal agent comprising a liquid pesticide and a anionic, cationic or nonionic surfactant dissolved therein, the surfactant Agent is selected so that it is soluble in the liquid pesticid> at least to such an extent that, if an amount of this solution of the surface-active agent in the pesticide, which corresponds to the maximum application dose, with! Mix 100 liters of water and stir the mixture to obtain an emulsion of the pesticide in the water, at least $ 28 of the volume

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of the added peticidal composition are in the form of colloidal particles which have a maximum particle size of 1 μ . ·

The surface-active agent should preferably be soluble in the liquid pesticide to such an extent that the turning of the surface-active agent in the pesticide is when it is mixed with 100 liters of water in an amount corresponding to the maximum application dose and the mixture is stirred forms a Enulsion of the liquid in Pesticide free water, of the added liquid Pesticide in the form of colloidal particles wherein at least 87 i "of the total volume, which have a maximum TeilchengrSsse of 1 μ. Preferably, 87 vol. 56 of the added liquid pesticide are present in the emulsion in the form of colloidal particles which have a particle size of less than 1 yu, these particles then being invisible under a 40-fold magnifying microscope.

Below the maximum application dose of the pesticide, becomes the application dose in the so-called application in large Volume understood, the solubility of the surfactant in the pesticide should preferably be so great that even in the case of so-called application in small volumes, at least 28 volumes, preferably at least 87 volumes, of the liquid pesticide Form particles which have a maximum particle size of 1 yu.

The terms "high volume application" or "application in small volume" (low volume application) are familiar to those skilled in the art. Until a few years ago, pesticides were only produced using the usual spraying methods using the method of * application in large volume "to control pests. The usual Fuel «devices used. Only recently has the so-called application in small volumes been developed only about 1/5 to l / lO of the amount of water used when applying is used in large volume, is used to produce the emulsion. In this case it is due to the lesser Amount of water more difficult to produce an emulsion

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BAD ORiGINAL

The at least 28 vol. £ of the added liquid ptetlid composition are present in the form of particles of a maximum size of 1 ax than is the case for the application of the large volume. If only about 1/5 to 1/10 of the amount of waeeer is added when using in small volumes, of course 5 to 10 times the pestioid composition, based on the amount when using in large volumes, must be used in the preparation of the spray liquid will. In this case, of course, the requirements for emulsifiability are more difficult to achieve than when used in large volumes. This can be seen clearly from Examples 5 and 6 of Table II given below, the results given there showing that when the amount of the pesticide-active ingredient (Dinocap) is increased to twice that, i.e. from 23 g to 46 g, fewer invisible particles and fewer particles with a maximum particle size of 1 Ai are formed. Special sprayers are required when a peaticide is to be used in the low volume application form.

The inventive pesticidal agents contain generally less surfactant than the previously known pesticides and preferably the level is less than 50 vol. # of surfactants, in particular less than 30 vol. #, based on the volume of the pesticide-active Compound in the pesticidal agent. In the preparation of the liquid pesticidal agents according to the invention, preferably not more than .50 vol. # Of one or more surface-active agents Agent dissolved in the liquid pesticidally active components or the liquid mixture of several pesticidally active components and the solution is then poured into 100 liters of water. The maximum application dose corresponds, as can be seen from the tables can be seen, generally a volume from? 0 to §6 ml of the solution of pesticide-active component and surface-active component Medium, i.e. 20 to 56 ml of this solution are mixed with 100 liters of water and then form the emulsion in which at least 28 percent by volume of the pesticide-active component or components in the form of particles of a maximum particle size

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BATH 0 & G1NAL

. of 1 ax are available. J

By the means according to the invention

Guaranteed precisely defined emulsifiability, ie through the • guarantee of a minimal appearance! of colloidal particles with a maximum particle size of 1 / a. the following before r

parts achieved? *

a) rapid preparation of the spray liquid

b) excellent resistance of the spray liquid

c) very good and even coverage of the treated substrate, for example the plants

d) good adhesion to the substrate

e) Greatly increased effectiveness due to the colloidal particle size of the active component, which is necessary for an even distribution.

f) significant reduction of the application dose to achieve the same effectiveness as i when using emulsions with lower proportions of fine particles.

Because the surfactant is in

the liquid pesticide is actually in dissolved form the storage stability of this emulsion is outstandingly good, i.e. no settling of any component can occur.

According to a special embodiment of the invention the solution of pesticide and surface-active Agents adsorbed on a solid carrier material, so that a wettable powder or dust is formed. Even in this form • contributes to the good emulsifiability of the pesticide-active component significant advantages. Namely, when the wettable powder or dust is brought into contact with water, as is the case for example in the preparation of a spray liquid from a wettable powder, or in the case of dusts that come in a dry form The substrates to be treated are applied, when rain sets in or as a result of dew, then this sets Dust or the wettable powder the particles of the liquid pesticide

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The wettable silver the dust * »;

Carrier material contain sulfur and this will change beneficial if the peeticid is a fungicide,

Pie according to the invention pesticide »

Before they can be used, they do not have to be washed with water ^ but they can also be used undiluted! Bringing £ β * "" are used. Recently, methods have been developed which allow the use of unverdttmft £ & CIDEN and in this case ^ j Pesticide be applied to the plants very fine, application beispielsweiee of aircraft. If the novel Pestti If they arrive in this form or in the form of dryly applied disturbances for use, the substrates treated in this way, for example plants, immediately after their treatment have stains of the pesticidal composition or dust particles which contain them now the treated plants with ifasser, such as rain water or dew, come into contact _f Act "is the left on the plant pesticide means in the form of colloidal particles dispersed in the water and thereby occurs a uniform distribution of the Pesticide about oehandelte plant on. These good and even distribution is only possible if the pesticides according to the invention are present preferably at least 87 vol. # of the liquid pesticide colloidal particles form which have the mentioned maximum particle size of

1 have Ai . In contrast to this, this uniform distribution cannot be achieved with a pesticide which forms fewer colloidal particles than those according to the invention.

The liquid pesticidally active component can be a single liquid pesticide or a mixture of at least

2 different pesticides that are liquid. If the liquid pesticide is a mixture, then it can ent-f components hold, which are solid in their pure form at room temperature, which, however, when mixed with one another in the desired ratio, represent a liquid at room temperature, for example a eutectic mixture. If desired,

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the liquid pesticide composition can be further liquid ' Components ^ in addition to the pesticide and the dissolved therein surfactants ^ contain. These liquid components For example, small amounts of solvents can be used to reduce the viscosity of the liquid pesticide or sticking agents and / or stabilizers.

The liquid pesticides according to the invention are neither on the use of any special liquid active material nor any particular surfactant but it can be any combination of these two materials can be selected provided that the solubility of the surfactant in the pesticide is sufficiently high that the above-mentioned colloidal emulsions are obtained when the finished agent is mixed with water will. The nature and the minimum concentration that the surfactant is in any liquid Pesticid needs to be dissolved can be easily determined by you mix the maximum dosage with 100 liters of water and that Volume of the liquid pesticide, which is present in the form of colloidal glow, is determined. It should be noted ^ that the Water that is usually used by the farmer to produce spray liquid is used, is generally not softened water but average hard or even hard Water. Therefore, the 100 liters of water used to test the pesticidal agent should also be hard water be, preferably water, of at least 34 French degrees of hardness having.

■ The maximum arm end dose is understood to mean

the dose at which at least 98 % of the pests to be controlled, for example insects, fungi or weeds, are killed. Of course, this maximum application dose depends on which type of plant is to be treated or which type of pest is to be controlled. For example, when the pesticide-active liquid is an insecticide, the insecticidal gowns thus obtained can generally be used for controlling various kinds of insects

009839/2144

BATHROOM ORIGINAL - 11 -

be sucked. In this case, the maximum application dose that must be taken into account in the preparation of the compositions according to the invention is that which is required to control that particular species of insect which is most resistant to the pesticide in question. The same issue $ ^Γ £ ^ course, other types of pesticidal compositions, such as herbicides and fungicides on.

Of course, pesticides can also be used in a dosage that is higher than the maximum dosage mentioned, If, however, a higher dosage than the maximum is used, then in general no or almost no better control results are achieved with regard to the pests to be controlled than with. the maximum dosage, so it in general It is not recommended to use a certain pesticide in a dose higher than the maximum dose. The one mentioned "Maximum application dose" is therefore consistent with the "optimal application dose" in most cases, although in some Cases the optimal application dose may be less than that maximum application dose.

It is also known that 2 pesticidally active components have an eynergistic effect, ie if these two components are used together, then they can have a significantly better activity than either of the components alone. A further aim of the invention was to increase the activity of such synergistic combinations and to produce a synergism between 2 components which either have no or only a very small amount. It is assumed that this synergistic effect between 2 different pesticidal components that form a solution is due to the fact that the pests, for example Mijbe / i or insects, are not able to defend themselves against 2 different gods, that are located on the same microscopic spots or cells. In contrast, is «? it is possible that such pests will survive if they are affected only by sJv- ^ m of these two poisons . One suspects that ms <■ ''. I ο Sehy.dlirige are not able to

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BATH ORIGINAL

to form 2 different enzymes at the same time and in the same places, which decompose each of the two pesticides. In order to achieve a synergism between 2 components, it is necessary that these two active components actually attack the pest at the same time in the same place. It has now unexpectedly been found that the liquid pesticidal compositions according to the invention, in which both active ingredients and the surface-active agent form a uniform solution which then provides the above-mentioned emulsion when mixed with water, have better synergistic properties than liquid pesticidal agents who have the same active. Contain ingredients which, however, do not form as fine emulsions as the agents according to the invention * If a synergistic effect is to be achieved using 2 different pesticide-active components, for example 2 and fungi-active components, and if a very fine colloidal emulsion is not guaranteed in which each colloidal particle contains both pesticide-active components dissolved in each other, then it may be possible that the two components are present in different colloidal parts and that the same cell of the pest to be controlled is not attacked by both components at the same time, so that possibly for this reason there is not such a good synergistic effect. In any case, it has been found that for the case that _f the inventive pesticidal compositions comprise at least SWEi active component having a synergistisehen effect, this synergestischer effect is significantly large, as it was determined for respective pesticide means providing with water less fine dispersions »'>

While it is so desirable that the pesticide active component form a fine emulsion with water, it is . not advantageous if this pesticidally active component is in Water dissolves. It is intended to ensure an emulsion in which as many particles of the pesticide as possible one Have particle sizes of about a micron or less, it however, it is not intended to be a real solution to the active pesticide Manufacture component in water. A pesticids found in BADOFiIGINAL 009839/2144

If water is dissolved, a lot of light * runs off the substrate, for example the plant _/ on which the water containing the pesticide was sprayed. In order to achieve only an emulsification but not a solution of the pesticide-active component in the water, the content of the surface-active agent is preferably less than 50 vol. $ And in particular less than 30 vol based on the total volume of the solution of liquid pesticide and surface-active dissolved therein Middle. It should also be pointed out that excessively high concentrations of surface-active agent can generally also bring the risk of phytotoxic damage to the plant, because excessively large amounts of surface-active agent can lead to a dissolution of the waxy protective layers of the leaves and fruits.

The liquid pesticides behave like oils.

When the inventive liquid pesticidal agents are poured into water, and 28 ^ Vol.9, in particular 87 vol. I »colloidal Teilchenjbilden .., consisting of the solution of the surface active agent in the pesticide, the following advantages have been achieved!

a) Through the colloidal particles, the effective contact of the surface with the pest, for example the fungus, the insect or the weed, incredibly enlarged.

b) The colloidal particles ensure a more uniform coverage of the treated substrate, whereby for this less liquid pesticide than with previously known Mittelxybe- ' is required.

c) Since most liquid pesticides are sticky materials or self-adhesive materials and because in the inventive agents either no organic solvent is present at all or only small amounts of the same was After the spray water has evaporated, the liquid pesticide adheres well to the treated substrate, for example the plants, guaranteed, and moreover "is the coverage is even and this increases the durability of the * • 'Treatment increased.

The pesticidal compositions according to the invention are preferably made according to the following scheme

_ ₁₄ J) O983.97-2.1-44

BAD 0RK3ttiAl

manufactured λ »

• Baa Pesticid is placed in a container, preferably a stainless steel container, which is provided with a heater and a stirrer. Depending on the type of liquid pesticide, different levels of heating are applied to accelerate the dissolution of the surfactant, and this is added slowly with stirring. After the addition is complete, stirring is continued for 15 minutes until a uniform solution is achieved. This solution is generally mixed with the desired amount of water before spraying. In the following, various objectives and formulations of pesticides that can be used in agriculture are given in order to determine which factors influence the quality of fat-emulsifiable liquid pesticides, i.e. how one has to proceed in order to produce a pesticide which then supplies the required particle size in the injection liquid .

As has already been mentioned, the liquid pesticides that have been used up to now contain larger amounts of GTgsffrkki & hmi Sösiiagssiittelo. Therefore, so far, ÄeBerrti ^ 'äa Kditol s © has been selected to ensure that there is a good ueqs znQ ^^ mi orgu-nissliQa LüsuagBffli'ötels

borrowed des iiyöripliilsa- = hydrophobic equal geniöiii'is siaes cb.r - SrliigSieHaktivOii ö.lotcls KnteraoiMiön was _P dae sur Esiulgierung © ϊϊή; 33 beotiid ^ -i-iiij L * ^ sssntliohen l

'P-3 VIiS ⁸ G -; - ri τ.ύΐΊ erstraalo Ysrsüciie ύ urehgefUhJp ^- G ₅

vsi * l es standΐ · ΐ> DJlt - ;: from ^; ? i iiarayf _s that for ώΐώ KQis'bcsii liquid pestieidakti ^ uö 'LonyCtier- ■' -. <$ &üz-'u Si seimig '': = ^! / o ^ liquid

ii.Q oia

yilEilläJ ^ ö ^ I ^

Mittol gQkü ^ enj, Kcmäei; S3, 'ii & iisproduktg a-ig Ag

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and propylene oxide with phenols, alcohols or fatty acids, for example alkyl, aryl or aralkyl ethers of polyethylene oxide or polypropylene oxide. The molecules of these copolymers of polyoxyethylene can also contain ether or azide groups or both Contain.de The number of ethylene oxide groups is variable and depending depending on their number, surface-active agents can be obtained which have a different hydrophilic-lipophilic balance (also referred to as the "hydrophilic-lipophilic balance ** (HLB)" will have).

The HLB number is an apirical expression for the behavior of a surfactant, and it generally ranges from 1 to 40. The lower this number, the stronger The emulsifier or surface-active agent is oil-soluble and the higher the HLB number, for example in the range of 11 - 49, the more water-soluble is this surface-active Middle. The HLB number indicates the emulsification properties and for a specific oil or solvent, the HLB an emulsifier8 can be found, the sur S emulsification the oil or solvent in water is particularly suitable is.

It is known that surface active agents

with an HLB in the range of 10 to 11 are best suited for emulsifying mineral oils.

It has now been found that for the.

most pesticide-active ingredients are those surface-active Agents having an HLB in the range of 9 to 15 give the most beneficial results.

Some examples of nonionic surfactants are:

- ( _{Ethylene oxide) n} -octylphenol condensation product in which η is 1 to 40.

- (Ethylene or propylene oxide) lauryl alcohol, condensation products in which η is 1 to 40.

- Polyoxyethylene sorbitan laurate

- (Aethylenoxyd ^ -alkyl-alcohol-condensation products

- (Ethylene oxide) g-para-nonylphenyl condensate products

- glycerine monostearate

- Propylene glycol monooleate. 009839/2144

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The surface-active agents of the nonionic type are generally not very sensitive to the hardness of water and, furthermore, are generally compatible with all kinds of other surface-active agents. The ether type nonionic surfactants generally have better stability than those of the ester type. Sometimes it is beneficial to dissolve surfactants in butanol, ethanol, or isopropanol to increase their solubility. The above-mentioned surface-active agents generally have a relatively low critical mycella concentration and this is, for example, 0.01 % for phenylphenol-polyoxyethylene (10) -j . ether and the means are usually very little phytotoxic.

Specific examples of suitable nonionic. Surfactants are as follows - "Spans" (manufacturer Atlas), such as Span 20

(Sorbitol monolaurate, HLB 8.6), Span 40 (sorbitol monopalmitate, HLB 6.7) »Span 60 (sorbitol monostearate _t HLB 4.7)» Span 80 (sorbitol monooleate, HLB 4.3).

"Tweens" (Atlas Powder). ■;. "-

The "tweens" are monoalkylene derivatives of the "spans" Examples are: Tween 80 (sorbitol monooleate polyoxyalkylene derivative, HLB 15.0) j Tween 60 (sorbitol stearate polyoxyalkylene derivative, HLB 14.9); Tween 40 (sorbitol monopalmitate polyoxyalkylene derivative, HLB 15.6) I Tween 20 (sorbitol laurate polyoxyalkylene derivative, HLB

16.7).

"Tritons" (manufacturer Rohm & Haas Co.) - "Tritons" are alkylene phenol polyethylene oxide ethers

with 5 to 40 alkylene oxydginips.

"Igepals" (manufacturer Antara). These are alkyl

phenoxypolyäthylenäthano1e, ζ.B,

CO 43Ο nonylphenoxypolyoxy
ethylene ethanol BAD ORiGWAL Ethylene HLB Igepal CO 53Ο (4) 8.9 • ι co 63Ο (6) _ 10, .9 It (9.5) 13.1- 00 9839/2 HA

Continuation / 1 '* J ·' - '.': * $ & Χΐί

b) Aniopic surfactants

The anionic surfactants are Esters or salts of fatty acids, or condensates of sulfuric acid with fatty alcohol. The most common of these agents are the soaps. In these agents the hydrophilic end is straight or via intermediate bonds with a large hydrophobic group connected and the entire molecule forms a negative ion.

Some examples of suitable axionic surfactants Means are:

Sodium stearate, sodium palmitate, resin soaps, sulfated oils, sulfonated esters of ricinoleic acid, lauryl alcohol sulfonate, Dodecylbenzenesulfonate as well as those in the sodium, calcium or ammonium salts of these materials. * Are also mentioned the sodium salt of dibutylnaphthalenesulfonic acid, the sodium salt the dioctyl ester of the sulfobernary sodium salts of Alkyl polyoxyethylene sulfate and salts of sulfonated aliphatic and aromatic hydrocarbons such as the sodium salt of tetradecylbenzenesulfonic acid.

Most of the fatty acid esters form insoluble precipitates with hard water and these materials are slightly alkaline in aqueous solution.

Other anionic surfactants are hard water compatible and show a neutral reaction. Of course, all anionic surfactants are incompatible with canonical surfactant. The anionic Surfactants are compared to the non-

009839/2144

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Ethylene- ·. '·' 'V "' orvdMruppen

Igepal CO 710 Nonylphenoxypolyoxy- ' 4 * " ^ß

ethylene ethanol (10.5) 11.5 ^ S'i

CO 730 ^w (15) _ ,, .-

CO 850 ^w (20) l $ _t Q ■

CO 880 - (3O)

j · ■

ionic EeaktivF., form easily breaking emulsions, have higher critical micelle concentrations (sodium dodecyl sulfonate 0 _f 2 >, sodium _{dioctyl sulfosuecinate O 1} O? #) and bind in general also more phytotoxic «

Specific examples of anionic surfactants are as follows:

"Aerosol 0Ϊ" (manufacturer Ans «Cyanamid), which consists of bioctyl sodium sulfosuccinate. .

"Igepon ©" (manufacturer Antara ^ these are fatty acid esters of various structures, such as Igepon AF 78, oleyl sodium isethionate) »Igepon GN 42 {fesrium-N-cyelohexyl-N-palmityltaurate), Igepon T 77 (sodium N-ms δ'ίjl-H-oleoyl taurate).

"Arctic Syntex L" (manufacturer Colgate), which a sodium as a sulfonated monoglyoaride of coconut oil fatty acids represents »

Cationic surfactants normally contain nitrogen in the form of ammonium or amine groups and. this is diyskt © of the bonds lying over alaswiBcfeea with eimer lijdröphoben group ipsteMene Some examples of such means sinös

fet ^^ aethylsEmoniiafficlilorid, Ostadecylaminy.

Hydrochloric »Beäecylbensyltrimetfeylammoiiiumchlorid !, laurylaminy Kydrachloride and Stearylmonoätfeanol & miitihyöroehlorid «

. This type of surfactant

ionized »whereby a negatively charged ion, for example a HalQgenionj and elzi-positively charged hydrophobic ion, is formed. Phosphonium \ md Svä.fon ± umBslz & also belong to this group.

Spexiolls Example® for cationic surfactants Smocks are the following:

"ArquacE 12" (manufacturer Armor), which is a lauryl-triaethyl-ammoBiumcliloria »and ^M Ammonex 6 ^M (manufacturer Onyx), which consists of Getyl-Äimethyl-benzylammoniumchlcird *

Bs can be a mixture of beneficial

BADORiGINAL -19-009839 / 2144

a nonionic surfactant with either an anionic or a cationic surfactant use. In any case it must be the selected surfactant. Agent or mixture of surfactants as above have defined required solubility in the liquid pesticide.

The "most manufacturers of surfactants

Means do not guarantee the exact composition of their products. Of course, when combating pests, you should use '·. plants only those surface-active agents are used which have minimal or no pbytotoxic properties the plants to be treated.

Examples of usable liquid pesticides are given below;

Pesticide "

Examples of liquid pesticides are fungicides, insecticides, nematocides, acaricides, herbicides, sterilants, Means that prevent feeding, for example insect damage, and means that attract certain pests.

Examples of sterilizing agents, in particular chemically sterilizing agents, are products which sterilize either the male or the female or both of the pests to be controlled, for example insects, when the animals come into contact with these agents.

Antifouling Products Bind those that

when they are sprayed onto a substrate, they make it inedible for the pest, i.e. products that, for example Getting insects not to suckle or eat leaves or fruits treated in this way.

Attractants are products that are used either as sexual attractants or as appetite inducers Products that attract pests such as insects. For this reason, attractants are generally not the only ones Pesticides but used in combination with other pesticides, with a mixture of insect attractant with insecticide as an example should be mentioned.

Specific examples of liquid pesticides are

- 20 - 009839/2144

BATH ORIGINAL

the following products:

hydro-4,7-methano-indane ("chlordane"); 0,0-dimethyl-0- (2,2-dichlorovinyl) -phosphate ("DDVP"), 0, O-diethyl-O- (and S) -2- (ethylthio) ethyl phosphorothioate ("Deraeton"), 0, 0-diethyl-0- (2-isopropyl-6-methyl-4-pyrimidinyl) -phosphorothioate ("Diazinon"), 0,0,0 ', 0'-tetraethyl-S, S' -methylene bisphosphorodithioate ("Ethion "), 0,0-dimethyl-S '- (1,2-dicarbethoxyethyl) -phosphorodithioate (" malathion "), 0,0-dimethyl-S-2- (ethylsulfinyl) -ethylphosphorthioate (" Meta Systox "), 0 , 0-Diethyl-S- (p-chlorophenylthiomethyl) phosphorodithioate ("trithione"), ethyl 4,4'-dichlorobenzilate ("chlorobenzilate"), isomer mixtures of 1,3-dichloropropene and 1,2-dichloropropane ( ¹¹ DD "), 1,2-dibromo-3-chloropropane (" Nemagon "), 2,4-dinitro-6- (2-octyl) phenyl crotonate (" Karathane "), nonyl dinitrophenyl butyrate and derivatives thereof which are liquid.

If solutions of liquid or solid pesticides are to be used in liquid pesticides, there are numerous possibilities. For example, you can use “Dinocap” with “M _a lathion”, solid “Dimethoate” (methyldimethyldithiophosphorylacetamide) with “Malathion” or solid “Chlorfenson” (p-chlorophenyl-p-chlorobenzenesulfonate) and solid “Dimethoate” in “Malathion”, and like that.

The solid pesticides like "Dimethoat", "Lindan",

Dichlordiphenyltrichloräthanol and "DDT", can be used in the liquid pesticides, such as malathion, dinocap, chlordane, and the like generally in amounts of about 7 -. 50 percent by 1 ° are dissolved (depending on 'the particular mixture), and the thus obtained liquid solutions can then be converted into the self-emulsifiable concentrates according to the invention without the addition of solvent.

If desired, they can be more liquid.

pesticidal compositions use lower amounts of liquid diluents contain, which serve to reduce the viscosity. Examples of liquid thinners are! Water, chlorinated hydrocarbons, xylene, petroleum products such as naphtha, tetralin, ketones such as cyclohexanone, and alcohols. These Diluents can be water soluble or insoluble in water. However, in order to avoid the difficulties that arise, BATH ORIGINAL -21- 009839/2144

if larger amounts of solvents are present, the amount of the same should preferably not exceed 10% by weight, based on the finished pesticide composition _/ .

Inert carrier materials

Inert carrier materials can be used in combination

with the liquid pesticidal compositions according to the invention be used. When the liquid pesticidal compositions are mixed with a solid carrier material and then that powder thus obtained or the dust thus obtained mixed with water then it can sometimes be difficult to determine the particle size of the particles of the liquid pesticide in the emulsion because sometimes it is quite difficult to decide whether something has been observed from a microscopic assessment Particle is a liquid particle or a particle of the solid support material. For this reason, the liquid pesticide composition is first tested to determine if it is the desired amount when mixed with water of particles with a maximum particle size of 1 / U. if If a liquid pesticide composition has been found that meets these requirements, it is mixed with the solid carrier material mixed and then "no further investigations have to be carried out on the end product obtained in this way.

The following inert carrier materials can be used, for example, to produce dust: Kaolin, talc, earth fillers, synthetic silicates and so on. The structure of the carrier materials, namely whether they are round, flat, are porous or non-porous affects the action of the active material that is mixed with them. When the support materials Are round, non-porous and have a small particle size, then they put the colloidal particles of the liquid Pesticides free faster than when the carrier materials are porous or have a larger particle size. Thus can

the release rate by the selection of the carrier material to be influenced.

Since, as already mentioned, first of all the testing of the solution of the surface-active agent in the

- 22 -

009839/2144 _, _{ir! NAL}

BATHROOM OBlGlNAL

Peaticid needs to be made, it is clear that when manufacturing from dusts this solution must be prepared first and that it is not permissible to mix any of the two components with the solid carrier material beforehand,

Liability3verbeaserer

Adhesion improvers or adhesives are not surfactants. If they are added, their effect is to improve the adhesion of the insoluble phase dispersed in the spray to the substrate, for example leaves, trunks or fruits , and thereby prevent washing off by rain and blowing off by wind.

These adhesives are generally protective colloids that are soluble or dispersible in water, such as casein, blood albumin, gelatin, synthetic polymers such as polyvinyl chloride and alcohol resins and methyl cellulose. Oils are also often suitable as adhesives.

Those contained in the means according to the invention liquid pesticides are insoluble in water and have a sticky consistency, so that in general η no additional Adhesives are required. In addition, as already mentioned good distribution was achieved with the aid of the agents according to the invention guaranteed on the substrate. When cationic surfactants If funds are used, then these can also act as adhesion-improving gowns, because they are positive charged, while the plants have negative charges.

In general, the smaller the particle size of the particles of the emulsified, the better the adhesion liquid pesticide is.

Stabilizers : two types of stabilizers are generally used, namely on the one hand chemical stabilizers that protect the pesticide against the effects of light, oxygen and changes in the pH value, and on the other hand physical stabilizers. It is known that plant fluids excrete, for example alkaline substances, which cause pesticides to decompose which are on the leaves or other parts of the plant. In yours. Fall can use the stabilizers

bad original ²³ Ίθ 0 9 8 3 9/21 4 4

also be buffers or acidic compounds.

Films or certain surfactants,

which is at the intermediate stage of two immiscible components act as electrical or mechanical barriers that prevent the Prevent particles from coagulating. Substances that form hydrophilic colloids act in a similar manner.

The invention is now based on the liquid fungicide "Dinocap" and the liquid insecticides "Malathion" and "Chlordane" as well as based on solutions of "Dimethoate" in "Malathion" and based on solutions of "Dimethoate" and "Chlorfenson" explained in "Malathion".

"Dinocap" is a good fungicide against various diseases called oidium species. It is also effective against mites. This pesticide has the advantage over the usual compounds with anti-oidium effectiveness, that it not only protects against the infestation, but also cures a disease.

This material has an application dose of

20 to 40 g per 100 liters. "Dinocap" is a viscous dark liquid mm at a pressure of 0.05 mercury acid has a boiling point of 135 to 14O ⁰ C. Many surfactants, as well as other liquid and solid pesticides, dissolve in them easily. The material has a specific weight of 1.13 and is therefore heavier than water.

"Dinocap" is from Rohm and Haas, Philadelphia; May and Baker, Dagenham (England); Theodore St. Just, 'Manchester manufactured. Ee is commercially available at the following farms:

a) as a 25% wettable powder

b) as a 48 $ liquid concentrate and

c) as 1 # dust.

Thus we see that make up the product in wettable powder surfactant and diluent together 75 i ° and liquid concentrate still more than 5O $. If you make a spray liquid of the recommended concentration from these agents, you get emulsions with these commercial products, the particles or droplets of which are larger than semi-colloidal.

- 24 -

009839/2 UA

BAD OfUGlNAL

As a result, the physico-chemical data

and the pesticidal effectiveness of formulations according to the invention indicated in comparison to formulations not according to the invention. The products that appear in the table are the following:

a) Product A, an emulsifiable concentrate that

72% by volume of '! Dinocap' and is a product according to the invention (see Example 3 of Table I). '

. Product A 'a product that contains 25 $> "Dinocap" and is a mixture of Product A with 64 1 ° sawdust.

b) Product B, a commercial product, namely a 48% emulsifiable concentrate.

_o c) Product C, a commercial product, namely a 25 ^ iges wettable powder.

d) Product D, a commercial product, namely a 25% wettable powder.

It should be noted that the tables 1, 2, 3 and 4 each extend over two pages, i.e. from the left end of one page the examples are numbered and the column most right on this page, "Number", is followed by the column most left, "cm the next page.

In the "cm of agent" column, the cm x ^{3 of} the solution of pesticide plus surface-active agents ... are listed, which are poured into 100 liters of water. In the column "g Dinocap", the g are listed which are contained in the specified amount of pesticidal agent.

Both the visible and the invisible particles which form in the emulsion are listed in the table and the size distribution (1 to 4 m) is also given for the visible particles. For the respective particle size, the number of particles present is also given and the volume of the added liquid pesticide, which is present in the form of particles of a certain size order in the 100 liters of water, is given, both in cm and also as a percentage based on the total volume of liquid pesticide that was stirred into the 100 liters of water. It should be mentioned that the invisible particles

BATH ORIGINAL

- 25 -

009839/2144

are listed in the table as particles with a diameter of 0.5 λχ , while the particles with 4 yu also include the even larger particles and non-emulsified fractions.

The investigation of the particle size will now be explained using Example 6 in Table 2. Is were 42 cra ^ of a liquid pesticide made from £ 0 vol. # Dinocap un>! 10 Vol./ «of the specified surface-active agent, stirred into 100 liters of water. In the process, 23.1 χ 10 layerable particles are formed with a particle size of up to and including one / u, which corresponds to 25 ^a / ° of the total number of visible particles. A calculation of the total volume that is present in the form of such particles shows that 1.2 O 1 cm of the liquid pesticide or 2.9 1 ° of the total volume. (42 cirr) of the added liquid pesticide. Moreover, are 14 ° / ° of the total volume of the added liquid Pesticids in the form of particles which are no longer visible in a 400-magnification microscope, and which are therefore finer than 1 / U. Now you calculate the total volume of the added liquid Pesticids that is provided by particles having a maximum particle size of 1 M and even smaller particles available, the result is 2.9 plus 14 * = L6,9%. This shows that example 6 is only a comparative example, because the pesticidal compositions according to the invention must provide at least 28 vol. $, Preferably 87 vol. $ (See example 7), of particles which have a maximum particle size of 1 Ai .

The above calculations are now also made for Example 5 in Table 2 and it can be seen that In this case, 21 cnr of the liquid pesticide are poured into 100 liters of water, and that there are 12 χ 10 particles of one particle size of 1 / rev, which is 0.624 cm of the total added 21 cm, i.e. 3 $ of the total volume of added liquid Pesticids equivalent. There is also 25 vol. $ Of the total volume present in the form of invisible particles, so that the total volume of particles with a maximum particle size of 1 / U 3 + 25 = $ 28 vol. You can see that in example 5 described pesticides is a pesticide according to the invention, however

-M-009839 / 2U * _BAD0WGINAL

not the preferred one described in Example 7.

Table 1 also shows the only

commercially available concentrates of "Dinocap" are those commercially available are listed. These materials contain solvents and more surfactant than those of the present invention Medium (see Examples 1, 2 and 3t where in the examples 1 and 2 (product B) the commercial products and in example 3 (product A) a product according to the invention is illustrated.

It can also be seen that in the commercial products (Example 1 and 2) due to the poor emulsions and the irregular particle size of the emulsified particles number error have occurred so that the calculated total particle volume is a little too high in both cases.

Tables 2, 3 and 4 also show the influence the chemical structure and concentration of various surface-active substances. Average on the particle size in the emulsification visible from "Dinocap".

The analysis of the particle size is carried out according to the following scheme:

Liquid particles which have been emulsified pass the quickest determination using a 10 chamber (THOMA) and a microscope, using a suitable dilution factor. This determination method is suitable for particles with a diameter in the range from 0.5 to 20 M. With an objective of 40 χ and an ocular of 10 χ (with micrometer), the size of up to 0.5 mm can easily be recognized, which corresponds to a true particle size of 1.25 / rev. The grading of the counting chamber used corresponded to 50 microns.

For particles less than 1 micron in diameter, the count is due to Brownian motion difficult, The hemacytometer counting chamber (Thoma) used is usually used to determine erytrocytes and occasionally bacteria or fungal spores.

The counting in the hemaytometer described above is done with a special slide and cover glass according to the Neubauer rule, where one mm is set up in 400 squares and each field of 16 squares is represented by a double

ürrg is separated. The depth of the chamber, i.e. the distance BAD OWiÖiWÄt. 009839 / 2U4

1 b 6 V 1 3 8 _u

between the slide and the cover slip is 1/10 mm. the Liquid with the particles dispersed therein is located. between the slide and the coverslip and the number of Particles in each field (16 squares) are counted under the microscope. The number of particles per dose volume is made from based on the data given on the counting chamber. The accuracy of determining the number of particles is proportional the dilution and the number of squares in which the particles were counted.

Regarding the size distribution of the particles

the accuracy of the determination depends on the shape of the particles and the number of counts. The procedure for determining that part of the total volume of the added liquid, which is in the form of particles of a certain particle size will now be described in detail:

With the help of a 1 cm injection syringe, an appropriate proportion of the concentrate to be emulsified, (one 200 part of the amount provided for 100 liters of water) is introduced into 500 cnr * of water, the water being standardized Has a hardness of 34 French degrees. The bearded water is chosen because it is probably the most unfavorable Illustrates conditions which may then arise in the actual use of the pesticide in agriculture. After the addition of one cnr of the solution of The surfactant in pesticide is stirred with a glass rod at 4 revolutions per minute for 60 seconds.

Immediately thereafter, a few drops of the emulsion are introduced into the counting chamber , and after placing the cover glass, all visible particles, which are located in three fields of the 16 squares (48 squares), are counted using a microscope magnified 400 times .

The frequency of certain sizes is determined with the aid of a micrometer eyepiece , the number of particles with different diameters being counted.

In the tables, ranges from 1.2 and 4. Ai , which in fact correspond to the following areas:

- 28 -

009S39 / 2U4 '^

αχ (Tab.

1 2 4

'U area

0.8 to 1.2 1.2 to 2 ', 8 2.8 to 5.2

The particles with a particle size of over 5.2 yu quickly settled on the bottom of the counting chamber, since the emulsified pesticide always had a density of over 1. The volume of the particles so settled can easily be determined using a conical graduated cylinder. In the tables, the volume of the settled liquid is determined and the value obtained in this way is added to the value of the particles of 4 / u determined in the counting chamber and this sum is then given in the table in line 4 / u.

Calculation of the number of visible particles Total number of particles per 100 1 Sprav-LIQUID: -

speed = n.lO ^{1: L} / l2

N = number of particles / mm ³ = ηχ4χ10 ^3/48 η = number of particles in 48 squares

Frequency: - S " diameter Total 1 d / u = 0, 8th - i, 2 / ^U ?! 2 / U = 1, 2 - 2, 8th / ^U • t 4th / U = 2, OO - 5, 2 / ^U 2 = n.d 2 * 10 ¹¹ Total d _x - n.

12th

Volume:

^V 3 ⁼

Diameter 1 / u

Diameter 2 / u

4 / u

1 ml = ΙΟ ¹² yu ³

0.52 / u
4.19 / u
33.44 /

BATH ORIGINAL

- 29 -

00 9839 / 2U4

Volume = ( ^to ^ ^al ά _χ χ ν _χ ) + (total d _? X V ₃ ) + (total d, χ νJ

ΙΟ ¹²

. ,., Total volume determined by 100 counts visible = °

Dose per 100 liters

Surface (assuming thin layer coverage - r / 7 ")

2 S- = diameter 1 / U = ■ 0.79 yu

S. = ·· 4 / U = 12.56 / u

Im ² = 10 ¹ ^ f

Calculation of the invisible particles (colloidal particles )

It is based on the assumption that the mean diameter of the invisible colloidal particles is 0.5 / u amounts to. However, this value may be higher than the real one, however, this is irrelevant for the intended comparisons.

mitt. -Diameter 0.5 λχ

Volume - 0.067 / u ³

Surface 0.2 / VT

' 3

invisible volume = dose per 100 1 in cm - ·,

visible volume in cm

Surface = ml invisible volume

χ 2.98 in.

In Table 1 correspond to those in the columns

"Invisible" volumes indicated the total volume of the added liquid pesticide minus the volume of all visible particles. Thus, when present in an emulsion no invisible particles, then the total volume of the visible corresponds - *, the total volume of the added particles Pesticids. Indeed

- 30 -

009839 / 2U4

BAD OFUGINAL

however, there may be slight differences depending on the is due to inaccuracies in the counting methods.

Examples 1 and 2 listed in Table 1

are not emulsions according to the invention but commercial products and you can see that these materials still contain more than 50 vol. $ solvent (xylene). The spray liquids of Examples L and 2 produced using these commercially available products form a sediment after 15 minutes which makes up 24 1 ° or 19% of the volume of the emulsion concentrate added. So you can see that these two commercial products are poorly formulated. Examples 3 and 4 of Table 1, in which 99.28 or 94.42 i "of the volume of the added liquid Pesticide in the form of invisible particles present are inventive pesticide agents. In Table 2, the pesticidal agents according to the invention described in Examples 5 and 7 are pesticidal agents in which 25 »35 and 87 # of the added volume are in the form of invisible particles, while the pesticide described in Example 6 is at which is only 14 Vol. # in the form of invisible particles, is not a pesticide according to the invention.

OHiUiNA ϊ - 31 -

6 00

Table 1

composition

Dosage / 100 1

example

No.

Dinocap

shape

v / v

surfactant

Art

solution
middle

Art

cnr of means

Grams of dinocap

Total number of
Particles

/ U

number

48

unknown

Xylene

42

22.75

χ 10

¹¹

0.5
1
2
4th

71 18 11

7IxIO

lSxio

llxlO

¹¹

48

unknown

Xylene

84

45, 50

χ 10

¹¹

0.5

207XlO 28XlO 2IxIO

^{11 11 11}

At

Tech nik

72

72

Nonylphenol polyethylene glycol (6Grup pen) Nonylphenol polyethylene glycol (8.5 groups)

23

17.8

0.75X10

¹¹

0.5

1
2
4th

54, 45,

0.4IkIO ¹¹ O, 34xlO ^iJ "

46

35.6

0.5

1
2

52, 17, 30,

1.2 XlO

o, 4 xio

0.7 X10

¹¹

Tabel

ο ο co OO CaJ CO

visible cm ■ y eweiI s totally surface * invisible number volume * surface fr Surface of the
Pesticids in m ² per 100
liter
spray Particles in the emulsion Size distribution ³ ' ⁷
7.5.5
36.8 8.7
18, -
87.7 114.4 m ~ 22.35
22.50
55.15 -j cc. - m ² ■ - per cm
middle 25.07 volume 10.8
11.8
70.2 12.8
14.00
83.6 110.4 5.60
'5.65
13.82 31.74
17.06
51.20 - - - - - 0.59 51.51 0.022
0.143 0.10
0.62
MM 0.72 16.35
8.79
26.37 0.04
0.16 34.9x1013 - 99.28 - 99.80 0.61 68.19 MM
0.066
0.168
2,340 0.14
0.36
5.08 5.58 taää
0.03
0.11 0.05
0.15
0.60 66.4x1013 22.84 94.42 68.05 99.20 '2.96 130.51 0.09
0.13
0.88 43.43 329.41 2.83

+ Density «1.13 ++ density» 1.0

Table 2

example

No.

Zus ammenpe t κ u η fc

Dinocap

shape

/ v

> surface active agent

Art

ν / ν

Dosage / 100 1

cm
at
middle

Grams of dinocap

Total number of
Particles

ΛΑ *

number

Technically

90

90

80

Nonylphono'J polyMtliy 1 en glycol (7 groups)

10

10

21

42

23

20.3

40.6

19.75

0x10

11

2x10

11

2.5x10

11

0.5
1

0.5
1
2
4th

0.5

60
? 0
? 0

55
23
22nd

30th
40
30th

4x10 4x10

11 11 11

23.1x10 9.7x10 9.2x10

0.75x10-

11

1x10 o, 75xlO

11 11

0 cm visible Particle in 97 1· total surface i t 12th the Tabel .2 emulsion number IxIO ¹³ volume 25, 35 surface surface per cm
middle • ?, 65 - of _? tn 61.01 1 98 _- m ² mm 45 invisible 8th, cc. m ² Pesticide in m σ>
• j
__k
Ui
Ύ) 13th , 624 Size distribution 70 4, 73 6.324 15.87 3 1.10 , 676 volume 0.95 5, per 100
liter
spray 34.22 · , 376 1.26 21 ] »90 74.65 5.02 20th l _X 10 ¹³ 14, _m ? i 10 4th respectively , 70 ~ " 9, V 5) , 201 , 40 5. 80 6,970 17.79 0.81 , 064 2. 1.82 9, , 765 7, 3.05 33 53, 86.00 11.56 0
0 , 20
, 90 , 10
, 50 6xlO ¹³ 87 _ I.
JI
I. 2 , 90 , 55 30, , 039
, 419 ? _ 0
0 20.034 69.7C O , 508 9 0.06
0.31 1 «Ο 73 13, - 0.94 «9 (O ro 68.70 0
1 10 52.00 97.85

(+) Density - 1.13

Z
r * ■ Rpi ·. - ■ Il - v / v ^; * 70 · • but surface active
middle • Il * * Il ' v / v Tabel Gram
Dinocap Total number of
Particles * 0.5 * number CTi
cn game
No. Art 1
2
4th - - CjO
OO composition 80 Il 20th 39.5 4.75XlO ¹¹ 37
42
21 1.75XlO ¹¹
2XlO ¹¹
ixlO ¹¹ 8th Dinocap : 2 0.5
1
2 Shape ' 70 30th ■ 21 IXlO ¹¹ ■ 4 75
25th 0.75XlO ¹¹
0.25XlO ¹¹ 9 - - ■ - It Dosage / 100 1 cm
at
middle 0.5
1
2 ti 30th 42 2XlO ¹¹ 4th 50
40 · • IXlO ¹¹
0, SxIO ¹¹ 10 " 46 10 0.2XlO ¹¹ 00983 (O 28 κ » 56

cm 091
838
344 visible Particles in the * total surface 0.11
0.50
0.99 Tabel 2. number 8xlO ¹³ volume 90.7 Oberf: 35 laugh 40 Surface of the _?
Pesticide in m per cm
middle per 100
liter
spray f ο,
ο,
3, 9.3 2
m 63, cc. 2
m fo 3 ?, 74 126.38 <+4
W.
cn
cn 039
, 105 Size distribution 0.14
0.63 '
1,? 6 - 0.07
0.09 emulsion 6xlO ¹³ 41.727 99 ^ 85 24, QL 98 84 rj>
CO co ο,
ο, volume 42, 2.96 ^ 83.15 δ 0.515 0.06
0.08 invisible 27.856 83, 99 ο
33
δ , 052
, 335
, 669 respectively 0.05
0.15
0.22 , OxIO ¹³ 98.1 , 73 , 58 Z
> 0
0
0 0.20
1.80
7.30 1.9 84 2.93 164.42 I. 0.07
0.25
0.37 54.944 L63 99 OJ
-J
I. 0.140
0.375 CO
O
CD 839; to 0.10
0.60
1.20

(+) Density = 1.13

Bpi- • · * v / v surface active
middle v / v Tabel Gram
Dinocap Total number of
Particles / ^U * * Number m '
. 1 game
No. 90 Art 10 20.3 2XlO ¹¹ 0.5
1
2
4th 65
35 1,3XlO ¹¹
0.7XlO ¹¹ W-. 1567138. 11 90 Nonyl
phenol
glycol
(9.5 Grup
pen) 10 ■ 40.6 5XlO ¹¹ 0.5
1
2
4th 65
13th
22nd 3,25xl0 ⁿ
0.65XlO ¹¹
i, 10xl0 ^U 12th 80 Il 20th i 3 19.75 2.5x10 ^T1 0.5
1
2
4th 100 2-, 5XlO ¹¹
V 13 ■ composition . It ' I.
co
I. Dinocap 009839/21 shape Dosage / 100 1 # - *
IV
S.
^: §.
δ
>
Γ " Tech
niche
9 5 % ("*") cm
at
middle Il 21 Il 42 23 * '

Tabel

Particles in the emulsion

visible

invisible

Surface of the pesticide in m *

Size distribution

volume

cm·

respectively

total

surface

Number volume surface

per cm "
middle

Per

liter

spray

0, OGR
O,? 93

CD OO € *> CD

0.169
O,? 72
3,675

0.3?

1.38

0.40

0.65
8.80

0.10 0. ??

0.16 0,? 5

31.5x10

13th

20.639 93.3

61.50

99.49

?, 94

1.7

0.26 0.20 1.38

9.85

0.22 0.18

1.20

579XlO ¹ ?

90.15

112.89

98.40

2.73

61.82

114.73

0.130

0.6

0.20

0.30

34.9x10

13th

99.4

68.1

99.70

2.97

0.6 68.35

(+) Density = 1.13

O CD OO CaJ

at
game
No. composition v / v surface active
middle v / v Dosage / 100 1 Gram
Dinocap ■ - 0.5
1
2
4th * number ■ 1
(
<
i
i 14th Dinocap 80 Art 20th cm
at
middle 39.5 0.5
1
.2
4th 100 1,5XlO ¹¹ 15th shape 70 Il 30th 46 21 Total number of
Particles 0.5
1
2
4th 75
25th 3XlO ¹¹
ixlO ¹¹ 16 11 70 It 30th 28 42 1,5XlO ¹¹ 84
16 1.26XlO ¹¹
0.24x10 ^L1 Il Il 56 4XlO ¹¹ Tabel Il 1,5XlO ¹¹ s 3

Table 3

O 35

visible ■ 3 cm respectively total surface * ■ "invisible number volume * surface 99.93
99.33 Surface of the _?
Pesticide in m per 100
liter
spray Size distribution 0.078 0.17 0.17 m ² 0.09 70.2XlO ¹³ cc. 99.83 2
m 99.50 per cm
middle 136.97 volume 0.156
0.419
P. 0.55
1.55 2.1 0.12 0.29
0.38 41.9 x 10 ¹³ 45.922 97.9 -36.85 ? _P 97 82.28 i
O _? O66
0.101 0.12
0.18 0.3 0.24
0.31 0.05
0.45 39.5 x 10 ¹³ 27.425 99 s 7 81 ₉ 73 2.93 167.24 0.10
0.76 55.833 165.36
C. 2 _f 98 Particles in the emulsion

tn CO

(+) Density = 1.13

Table 4

Bapiel

No-

17th

18th

composition

Dinocap

shape

Technically

V / V

90

80

surface-active σ middle

Art

Oleocctyl al cohol-

ather nile 5 ivlo'l. Ae I hy Ί. on oxide

ν / ν

10

20th

Dosierunp / lOO 1

cm

of means

23

Grams of dinocap

Total number of
Particles

? 0.3

19.75

1.25XlO

¹¹

0.5

0.5

2 4th

37 33 3?

80 20

number

], 48XlO 1.24x10

^13th

T

- co

IxIO

¹¹

0.25X10

¹¹

19th

70 '

30th

38

21

2XlO

¹¹

05.

50 50

ixlO

¹¹

.BOO

Table 4

Particles in the emulsion visible cm * respectively total surface 0.24
0.78
3.20 invisible number volume 76.8 surface 95.78 Surface of the «
Pesticide in m per 100
liter
spray Size distribution 0.0769
0.5? 0
4,280 0.36
?, 47
20.37 23.2 0.12
0.12 24.6 x 10 ¹³ cc. 99.3 m ² 99.76 per cm
middle 50.16 volume - S.
0.052
0.105 0.25
0.45 0.7 0.1?
0.39
3.6] 0.10
0.38 , 34.9 x 10 ¹³ 16.1? 3 98.3 48.04 99.52 2.38 68.23 0.052
0.419 0.20
1.50 1.7 0.08
0.08 42, IxIO ¹³ 22.843 68.07 2.96 82.43 0.08
0.31 27,529 82.04 2.94

■ Add ; · • M. v / v * 70 'ti Γ' pt » ^r Al Π Γ ¹ * v / v Tabel - • 28 Gram Total number of
Particles - ■ 0.25 x 10 ^X / U * - number - * Pinocap Binocap 0.5 100 - cn 1 0 25XlO ¹¹ OO Teepee shape 70 > 4 0.25x10 "" " - - - co r.pi el 21 2 - OO \ ^: r. Db e ι · Π ?! oh cm.kti ν er; b - Il Dooierun ^ lOO 1 4th - Art cm _ 20th io der:, ν Τ at
T. 'Mittel 0.5 65 _ 70 bori '/. οΊ- 30th 1,5XlO ¹¹ i 17th 0.975XlO ¹¹
11 -ul nhoti- ' 21 · 2 18th 0.255x10 viurc ?8th ■ 4 0.27 OxIO ¹¹ Il - Il 0.5 100 21 25th 1 0.25x10 Cetyl 2 palmitin
oleyl 5 21 j amine 28 4th ethylene
oxide '15 KoI. - 22nd Il Dodecyl Denenzene sulphone acid

Table 4

visible cm f ° respectively total surface % invisible number volume 99.96 surface 99.9 "/ Surface of the _?
Pesticids in m per 100
liter
spray Size distribution 0.013 0.04 . 0.04 m ² 0.03 42.8 x 10 ¹³ . cc. 96.2 m ² ' 99.38 per cm
middle 83.42 volume 0.051
0.107
; 0.092 0.20
0.38
t 3.22. 3.8 0.02 0.10
0.10
0.42 4I ₉ 2XlO ¹³ 27.987 99.96 83, 4C 99.98 2.97 80.78 0.013 0.04 0.08
0.08
0.34 0.02 42.8XlO ¹¹ 26,940 80.28 83.42 0.02 27.987 83.4C 2.97 = 1.13 (+) Density = Particles in the emulsion

Selection of the upper

surfactant

. To formulate a suitable pesticidal agent of the present invention using any type of one liquid pesticides or a liquid, for example eutectic, mixture of 2 or more pesticides at room temperature the following work steps are expediently observed, which also from the information in Tables 1 to. 4 can be seen.

The first step is to get one

Selects inexpensive surfactant that is soluble in the liquid pesticide active ingredient being formulated. Liecc Surfactants such as vinyl phenol are dissolved in various concentrations in the pesticide-active component and the solution obtained is then emulsified in the water, and (see the tables) it is tested whether the smock produced meets the requirements.

Surfactants that are various

Have HLB numbers, show the surfactants of the nonionic type in general different numbers. of ethylene oxide groups per molecule. If you're using a surfactant If no advantageous results are obtained by means of a certain HLB number, then it is advisable to try one with a different HLB number.

These working methods are described in the tables using the formulation of "Dinocap". And you can see that the emulsifier based on vinylphenol, the 5 and 6 ■ The molecule has ethylene oxide groups, is not emulsified particularly well. A good emulsification starts when there are seven groups Ethylene oxide bound., Are and in this case, as can be seen from Example 5, a ratio of surface-active. Middle . to Dinocap can be chosen in the range from 1 to S.

However, if at this ratio the dosage

is increased from 20 g ^ Dinocap ^ to 40 g dinocap per 100 liters, then the number of invisible particles falls from 25 vol. # to 14 vol. $ and in this case the ratio of to lower surfactants to Dinocap to 1 in 4,

BAD OflKHNAL

so that good results can be achieved. By this reduction then the number of invisible particles increases (see Example 7) immediately to 87. i "and if one then increasing the dosage (see Example 8) occurs no reduction in the proportion of invisible particles, even a slight increase Sonderen, namely to 90.7 #.

In Examples S and 10 (see Table 2)

were obtained with 30 # surfactants nearly 100 ^c j "to invisible particles and dare h increase in the dosage of 28 to 56 cm cnr dinocap dinocap falls, the number of invisible particles only very slightly, n'imlich of 99.5 $ to 98, 1 #.

In Example 11 (see Table 3) another surface-active agent has now been selected which has 9.5 ethylene oxide groups per molecule and in this example 10 f> surface-active agent, i.e. with an I-f oil ratio of surface-active agent to dinocap of 1 in 9 received the invisible particles in an amount of 98.3 ° .

As the dosage increases, the number decreases

of the invisible particles to 90.15 i » (see Example 12). However, it increases with increasing the content of the surfactant coats to 20 1> already returned to nearly 100 # to invisible particles (see Examples 13 and lO. A further increase of the content of the surfactant coats on 3Q Vol.jS leads as seen from Examples 15 and 16 sees better results.

Instead of using surface-active agents based on alkylaryl-alkylene oxide, there are also alkyl polyether alcohols be used, and there was, for example, the oleocetyl alcohol ether, which has 5 moles of ethylene oxide groups per Molecule used. Such surfactant gowns are also inexpensive. You can see from example 17 that for the Case that 5 ethylene oxide groups per molecule are present at

10 1 » surface-active agent 76.8? $ Of invisible particles are formed and at 20 ° ß> this surface-active agent (see Example 18) this number rises to 99.3 ahv'-

From example 19 you can see that an increase

BAD ORSGINAL 0 0 98 3 9/5 O 4

The surfactant to 3O vol. # 41β no longer increases the number of invisible particles formed.

In Example 20, the influence of an addition

from 5 $> dodecylbenzenesulphonic acid to the oleocetyl alcohol polyglycol ether, which gives practically $ 100> of invisible particles.

In Example 21, the use of ethyl

palfflitinoley.lamin with 15 moles of ^ condensed ethylene oxide 30 # surfactant formed only $ 96.2. Invisible particles. -

Example 22 again illustrates the beneficial effect of adding dodecylbenzenesulfonic acid, because the number of invisible particles increases again to practically 100 #.

Using this approximation method

A pesticidal agent according to the invention can be prepared from any liquid pesticide, preferably less than 50%, in particular less than 30 $> surface-active agent, based on the solution of pesticid-active component and surface-active agent being present. Less than $ 50> surfactant should therefore be present so that the critical mycella concentrations are exceeded. An even finer emulsification or a solution of the active component in water should, as already explained earlier, be avoided, both to prevent the gown from running off and to prevent phytotoxic effects of the surface-active agent on the plants .

The commercially available wettable powders containing dinocap have $ 25 of the active component. she are made with surfactants and carrier materials. The carrier is generally not porous, the pH value of products varies. Product C is neutral, product D is strongly acidic and product E is alkaline.

The particle size of the wettable powder will be

principally determined by the particle size of the carrier material. Dinocap covers the particles of the carrier in the form of a thin film.

~ ^4e " BAD ORfGiNAL

009839 / 2U4

For state-of-the-art products

the dinocap adsorbs on the surface of the support, but not in a monomoleleular layer, but unevenly distributed, whereby uncovered surface alternates with surface covered by several layers of dinocap molecules. That is why this is gesarate Dinocap does not work immediately after use. The wettable powders have the following particle size distribution:

Maximum particle- Maximum conglomerate size size

Product C 110 micron 150

Product D 60 "-

Product E 4O "2OO

Products C and E also form conglomerates, which do not appear in the spray liquid with normal stirring disintegrate.

For these reasons, the pesticid is effective

The surface area of these powders is significantly lower than that of the invention manufactured powders.

Due to the neutrality of product C and the

Alkalinity of Product E is its shelf life in the presence of moisture in abundance. The acidic product D is more stable.

The wettable powders according to the present invention produced for comparison with the previously known products can be obtained by using the active solution (see product A as described above) adsorbed on a suitable carrier, e.g. synthetic silicates, cellulose products or the like.

In this adsorption, the product designated as product A 'is obtained. When this dispersed in water then this product A 'forms an emulsion of the liquid Pesticides in water and the particle size of the colloidal particles of this emulsion is in the range according to the invention.

Maximum particle size

Product A ¹ ....., ... 10

, 49 - _BAD OBiGmAt 00983 9/2144

In practical application, when a spray liquid * 100 g of a 25 #igen wettable powder (intermediate-level dosage) is added, then the following important points must be considered:

1. How much active ingredient (Dinocap) gets into the spray liquid.

2. What amount of active ingredient is retained on the carrier.

3. How easily the active ingredient is released from the carrier.

4. In what form does Dinocap get into the

Spray liquid! as an emulsion or hydrolysis product, i.e., v / ie Dinocap is stable under the given conditions.

5. What is the mean particle size in the Emulsion.

Corresponding provisions were made as follows:

The wettable powder is dispersed in the spray liquid with stirring, followed by filtration. The filtrate is examined for the number and size of the particles dispersed therein as described above. The residue filtered off is v / ird dried and weighed and indicates the amount of the pesticide in emulsified form or in solution in the aqueous phase is. To determine the amount remaining on the support, the substrate can be mixed with methylene chloride or pyridine or the like extracted.

Examples 2λ - 26 (Table 5)

Table 5 shows

1 »The percentage of sedimentation when using 4 g / l after 10 minutes.

2. The pH of the spray liquid.

3. The amount of free dinocap that is easily emulsifiable.

4. The amount of hydrolyzed dinocap that goes into the solution.

5. The amount of fixed dinocap extracted from the substrate using organic solvents .

- 50 -

00 9835/2144 _BAD ORIGINAL

ψ-m b 1

DINOCAP as wettable powder, comparison

Example product
No.

23

Dispersion

FH

Sedimentation

DINOCAP (active material)

free extraction

fixed dispersed hydrolyzed

16.5

4.3

46%

O I. cc 24 * C. 70.2 6.8 74 ° / « semi-colloi- O VJI
H dal and colloi OO I. 25th D. 15.0 5.4 74.5? ' dal co , 26 E. 73.0 8.8 58 '/ co traces K) 25.5 # traces

$ 26

$ 42

easy

difficult * CO 00 easy

difficult

The following can be seen from the results given in Table 5:

1. The product according to the invention and the product D are easily extracted, Vas on a favorable selection

of substrate, surfactant and concentration · · iet and thus the active ingredient easily reaches the point of use. This is not the case for products C and E. A slight release of the adsorbed material is very important during use.

2. The products A 'and D are acidic and this

leads to their durability, i.e. there is no hydrolyzed dinocap in the spray liquid.

3. The products C and E have almost neutral -or alkaline pH and this is why the proportion

of hydrolyzed product is quite high.

4. The products C and E have strong
Sedimentation, ie a low susceptibility to suspension.

. 5 · The best product is product A ', because it contains the greatest amount of dispersed in colloidal form Dinocap and semi-colloidal material, with no hydrolyzed fractions. In addition, the portion that adheres to the substrate, easy to extract. This is why the active ingredient is available to combat the pest in question.

Dusts are usually made from a base material made with talc, caolin, calcium carbonate, or similar materials with a suitable bulk weight and · corresponding Particle size is diluted. A sieve no. 3 ^ 0 the Tyler series (sieve openings about 45 / u). Dusts are e.g. prepared by placing the active product on a suitable adsorbent carrier such as a synthetic silicate, diatomaceous earth, Kaolin, attapulgite or the like. Sprayed on, or by simply mixing the two components with one another.

According to the present invention, wettable

Powder or dusts can be produced by spraying the active solution (l _t 45 f ") (see product A above) onto a substrate, e.g.

009839 / 2H4 BAD OKOINM.

Product A consisting of cid and surface-active agent is mixed with sulfur powder and then diluted with talc 84.55 1 °. ■ In this way one can, for example, a powder of 1.45 ° f Product A, 14 produce i »sulfur and 84.55" i "Talk. The amount of liquid concentrate can be up to 10 fi . Sulfur alone can be used as the carrier or diluent , or any materials known per se for this purpose can be used as the carrier.

The manufacturing process described above; driving has the following advantages:

Easy and rapid production of the dust. The lipophilic surface of the sulfur particles holds the liquid Dinocan weakly and no conglomerates are formed. The adsorption is very low.

There will be an even distribution of the

active material : When the diluent, namely the talc, is added, ^the excess dinocap easily passes from the surface of the sulfur particles to the talc particles.

Maximum coverage

The presence of surfactant

in the emulsifiable active solution reduces the surface tension of the drops of water on the leaves, for example dew drops or raindrops. This ^l% .sser serves to distribute on the treated plant surface the active material. In fact, certain wetting of the plant surfaces occurs every day, so that the active ingredient distribution of. Getting better day by day. The particles of the dinocaps are released in colloidal form.

liability

The surfactant that is dissolved in the dinocap suC. slightly water with gel formation, which the adhesion between the particles of the treatment thaw. and the. Sheet surface improved. The particles of the emulsion adhere firmly to the surface.

Fungicidal activity

The sulfur also acts as a fungicide and because of its acidic surface it also acts as a stabilizer

for the dinocap. . JPf *

The following conclusions can be drawn from the results of Examples 23 to 26 (see Table 5):

a) The emulsion concentrate according to the state of the art (product B) results, in the presence of solvent, Spray liquids in which more than 90% of the active ingredient is not in in colloidal form.

b) With the wettable powders or dusts known to date, practically no colloidal particles are formed.

"c) According to the present invention, one obtains

Spray liquids in which the active ingredient (Dinocap) is in Porm Particles of colloidal size are present. Even in the production of wettable powders and dusts will be colloidal or semicloidal at the place of use (under the influence of dew or rain) Achieved particle size of the active ingredient.

In the following examples, the influence of the particle size on the pesticidal effect is investigated.

Examples 27 to Έ5

The tests were carried out with the same 5 products which, as described above, were formulated differently and which lead to different particle sizes in the spray liquid. As above, these products are again marked with A, B, C and D.

The product A is a product according to the invention, i.e. it contains no solvent and so much surfactant that the required amount of colloidal Particles of the specified size is achieved. The remaining products B to E are commercial products.

Product B is a liquid concentrate of $ 48> Dinocap.

Products C, D and E are wettable powders

with 25 $ Dinocap and the particle sizes present in them have already been stated above.

The concentrations of active material in

the spray liquid used corresponds to the amounts usually used in the event of severe infestation.

- 54 QG9839 / 2144 BAD OfHGINAL

1b 6 7 1 38

The results obtained are shown in Table 6

reproduced.

- 55 -009839/2144

η ί / 6 ε e β ο ο

isp. Class Art

Table 6

Pesticidal effect: Ponnulation and particle size Oidiura attack before product A product B product C product D

the hand spray gram £ gram # gram J6 gram ^lun «dinocap cf. dinocap cf. dinocap cf. dinocap

* Part P ^{er l0} ° * P ^er 1 °° 1 perlOO 1 _per lOO 1

CO OO

Products

Gram

Dinocap V per 100 ι

27 33 Apples Rome
Beauty Super-
star 83 Buds 1 26th 5 86 31 70 25th 66 31 72 31 5 he, 34 Peach Franco Tendral 92 leaves 1 22 100 24 76 25th 80 24 83 24 7th ? 3 35 Roses Il 71 leaves 1 45 5 81 48 75 50 69 48 71 48 6th 30th Melons MacabGο 79 leaves 1 22 100 24 91 25th 89 24 90 24 7th 31
α ti 79 leaves 1 45 5 100 48 94 50 90 48 92 48 Ί δ 32.
Q Robes 64 leaves away. 22 100 24 91 25th 84 24 87 24 6th JO
a b) b. c) w. 5 Cucumber 67 leaves 22 100 24 76 25th 71 24 72 224 5 Cucumber 67 leaves 30th 5 100 31 81 31 75 31 78 31 6th Cucumber ⁶ T leaves 37, 100 39 87 37.5 84 39 88 39 .Blossom . Plant tongue .Re- fung d. Grapes 1 1 1

A solution was prepared which contained 74 wt. 7 °

Malathion (technical, 95 #) and 26% by weight Ethylan MC or Tensio-. fix J.A. contained. When using this solution in a consentration of 100 g of active ingredient per 100 liters of spray liquid, the malathion was completely dispersed in the form of colloidal particles.

If the amount of surface-active gown is reduced to 20% by weight, only a small proportion of the active ingredient is in Particles of colloidal size are transferred while more than 40 $ des Product settle.

The example demonstrates that preliminary tests must be carried out on a case-by-case basis to determine the concentration ranges are.

Example T7

Using nonylphenol polyethylene glycol with 14 ethylene oxide units, at concentrations of surfactant of 20 fo and more, emulsion concentrates of Chlordane are obtained which give spray liquids which contain the active ingredient in the form of droplets of colloidal size.

Example ^ 8

From 35 wt. $ Dimethoate, 44 wt. ^ Malathion and

21% by weight of Ethylan MC surfactant become liquid Concentrates "are obtained which, at a concentration of 25 g of malathion per 100 liters of spray liquid, contain the entire active ingredient contained in colloidal distribution.

A pesticidal effect was observed against green lice uni Cemiostoma scitella on apple trees with this liquid concentrate according to the invention, which contains 20 g of dimethoate and 25 g of malathion per 100 liters of spray liquid, which corresponded to the effect of 40 g of bimethoate and 75 g of malathion in the conventional formulation (Killing of $ 90> of the insects).

Example3ft .

Diaelhoatj ChlQrfsnson. and. Malathion as well as

BAD RIGINS

surface-active agent ethylan "C τ / urden in the categories of 12, 16, 45 and 20 wt. # Processed into an emulsion concentrate.

A spray liquid was made

from 165 g per 100 liters of water; a semi-colloidal one was obtained Emulsion.

With this composition it becomes en synergistic: Effect on the red spider mite, green aphid and Cemiostoma scitella achieved on apple trees.

Example 40

180 kg technical dinocap (degree of purity approx.

$ 95 >) was placed in a 250 liter stainless steel container equipped with a heater and stirrer. Bann was slowly heated to 40 ° C., and 25 kg of nonylphenol polyethylene glycol with 9 to 11 ethylene oxide units per molecule were slowly added with stirring. The addition was finished after 15 minutes.

The resulting mixture can be used directly for example as follows:

20 to 40 ml of the mixture are under good

Stir poured into a container containing 100 l v / ater; this is a colloidal dispersion of the above pesticide mixture obtained which are applied to plants infected with oidium can.

To implement the present invention, you can

also mixtures of non-phytotoxic, non-ionic and anionic or cationic surfactants, provided that the liquid pesticide itself becomes emulsifiable and, when added to '«" water, provides a colloidal dispersion.

The present invention is further illustrated by the following examples:

BAD OBiGiNAL - 58 -

839/2144

Table 7

at-

^ game

Type of formulation

Pl. Concentrate

Active material

Dinocap t

surface act. middle

TConyl-benzene-polyethylene-glycol (E.0.7-10.3]

thinner

Ratio number]

v'l.

4'5.

to

CXJ CO

46.

! ■ 7.

Ma lath ion Γ [A

, Ethylene M.C.

Chlorclnno

! polyethylon - ':; l.yool

'fufchhnrna powder

V. 41)

Ma lath ion ΓΙ concentrate (v / ie Prod. 42)

30..

Chlordane liquid concentrate (like Prod-, 42)

dust

Dinocnp Cl. Concentrate (v / io Prod. 41)

Diatomaceous earth

Knölin

! - sulfur

70 ak'o.Mnt

Xa) OO

70

η ti

70

ti Il

20 1: 200 ^: 73 'to 1:10

- 59 -

■ ■ * did rush 7 (continued) Active material 10 surface act
middle ί 1 thinner 40
50 - Prohibitions
nis-
number - Type of formulation MaIathion fl.conc.
. (like Prod. 42) 10 kaolin
Talk 80 1: 100
until
1: 4 dust Chlordane (such as Prod.
43) ■ 40
GO
40
60 Attapulgites
Talk O Il Oi. η ο CTO fl. Kort ssen tr.
(νLg Prod. 41)
Ha In Mi ion ΓΙ. Kon / ,.
(ν / io Pi * or 42) 60
40 I.
I. cn
CD "-ο
'α
cc
α
C *. ^; Λ1.Π ::::;, concentrate Bimc'ühoate
Malathion
(like Prod. 42). «■ j
CO
OO
f
t a
r
2 ti Malathion f1.conζ.
(like Prod. 42)
Chlordane liquid conc.
(like Prod. 43) i
i
i ί
i Il 3ei-
3piol
¹ Ir, ^ «... ! • 9.
■■ ·).

\ 3

Table 7 (continued)

game j

Type of lOrmulieruüg Active material

surface act, middle

thinner

Ratio *.

nis _T zanl

53.

«B 34.
to

j £ 55.

56.

57,

powder

dust

Dinocap fl Kalathion liquid conc, (like Proa. 50) 40

Diiaethoate + Malathion liquid concentrate, (like Ρϊ-οά. 51)

Malathion f1 Conc. + Chlorda-QG f 1st conc. (v / ie Prod 52)

Ώιώοcap fl.conc. + Mala thioTi f 1st conc . (like Prod. 50)

Pimethoate + Malathion f1, conc. (Prod. 51) 70

40

10

15th

Synthetic Silicates

60

1: 9 to 4: 1

kaolin
"Dia to m ο en- ·
Earth

20 40

Kaolin I j 60

Pyrophyllite J-1 30

kaolin
Talk

20 65.

1: 9 to 4: 1

1: 100}

up to I 1: 4

Table 7 (port setting)

example No.

formulation Active material

surface act, medium

thinner

Ratios

58

dust

Malathion liquid conc. + Chlordane liquid conc. (like Prod. 52).

59

60

liquid conc
kicked

Diine thoa te + ■ Malathion fl. Konss.

(like Prod. 51) +

Chlorine cone

netTsares
'Powder

dust

DiTiicthoato +

Mala thion "f 1. Kon r ,. ■; ■

Chlorfcnoon

(like Prod. 59)

Dimethoate + Malathion fl.Konz, Ghlorfenson (like Prod, 59)

20th

Talk

95

1: 100 to 1: 4

ι- .Ό

Earth
103 oil in

Synthetic 2D

Silicates

Talk 60

100: 1 to 3: 1 from _ » Prod. 51 au chlorine-cn fencon. CD

1:10 bio <VcrdüTincrs

dec

1: 100 to 1: 3 j of thinner, j

Claims (1)

Claims 1. Liquid pesticides, characterized in that it contains a liquid pesticide and an anionic and / or cationic and / or nonionic surfactant dissolved therein, the surfactant being soluble in the liquid pesticide at least to such an extent that the solution of the surface active agent in the pesticide when mixed with lOO liters of water in an amount corresponding to the maximum dosage of Pesticids, forms an emulsion of the liquid pesticicen agent in water in which at least 28 1> of the volume of the added liquid pesticide «Kittels are in the form of colloidal particles which have a maximum particle size νση 1 yu. 2. Pesticides Γ-'ittel according to claim 1, characterized in that when the maximum application dose of the agent is mixed with 100 liters of water, at least 87 ^r A of the total volume of the added liquid pesticider. Kittel in the form of violets, which have a maximum particle size of 1M. 3. Means according to claim 2, characterized in that 20 to 56 ml of the same when introduced into 100 liters of water form an emulsion in which at least 87 '/ »of the total volume of the pesticide added in the form of parts of a maximum particle size of 1 ^ u present. 4. Pesticides ".itte! According to one of the patent claims 1 to 3, characterized in that the liquid pesticide- active component is a " mixture of at least two different pesticides. ι 5. Gown according to claim 4, characterized in that the mixture of at least two Fosticiöen contains components that are solid at Zinnnertenrperatur, but at this temperature in the mixed state as a liquid are present. ><· .- ■; ■ 6. Pesticides r-'ittei after one; the patrr.tan- 98 * 317 2144 ORIGINAL. ': ■■ "■' ν eprüche 1 to 5 characterized "in that it is located on a solid? support material adsorbed. 7. Pesticidal gown according to claim 6, characterized in that the solid carrier material is sulfur. 8. Pesticidal smock according to one of claims 1 to 7, characterized in that the pesticidally active component contains a fungicide, an insecticide, a nematocide, an acaricide, a sterilizing agent, an agent preventing vermin or a herbicide. 9. Pesticides smock according to claim 8, characterized in that the pesticidally active component is ethyl 4 »4 '-dichlorobenzilate, l ^ -dibromo-ß-chloropropane ^^ - dinitro-o- (2-octyl) phenyl crotonate, nonyl dinitrophenyl butyrate or a Mixture of the isomers of 1,3 dichloropropane un .; 1.2 contains dichloropropane. 10. Pesticides coat according to claim 8, characterized in that the pesticide-active component OjO-diethyl-S-ip-chlorophenylthiomGthylJ-phosphorodithioate, 0,0- diethyl-O- (or S ) -2- (ethylthio) ethyl-pho sphorthioat , 0,0-Diethyl-0- {2-isopropyl-6-methyl-4-pyrimidinyl) -phosphorothioate [0,0,0 ', 0' - tetraethyl S, S '-methylene bisphosphorodithioate, 0,0-dimethyl SI, 2-dicarbethoxyethyl-phosphorodithioate, 0,0-dimethyl-S - [- 2- (ethylsulfinyl) -ethyl] -phosphorothioate or 0,0-dimethyl-0 (2,2-dichlorovinyl) phosphate . Contains. 11. Pesticides agent according to one of claims 1 to 10, characterized in that the surface-active agent in a maximum amount of 50 vol. $, Preferably in a maximum amount of 30 vol. #, Based on the solution of surface-active agent in the Pesticid is present. 12. Pesticidal smock according to one of claims 1 to 11 | characterized in that the surfactant is a mixture of a nonionic with a cationic or a nonionic with an anionic surfactant . 13. Pesticides smock according to one of the claims 1-12, characterized in that the liquid pesticide-active component a "ischur.g from at least two different 009839/2144 - 6i - BATH ORIGINAL different pesticides, this mixture being a synergistic one Has effect. 14. Method of making the liquid Pesticide according to one of claims 1 to 13, characterized in that an anionic, cationic or nonionic surface-active agent is dissolved in a liquid pesticide in such an amount that the solution, if it is in an amount corresponding to the maximum dosage, preferably corresponding to an amount of 20 to 56 ml, of the liquid pesticide poured into 100 liters of water, an emulsion formed, of which at least 28 vol. $ of the added liquid pesticide, preferably at least 87 vol. ^ ₁ . are emulsified in the form of particles with a maximum particle size of 1 ax. «Jose Antonio Serrallach-Julia: BATH ORIGINAL 009839 / 2U4 Dr.TM-mr ■ - 65 -