DE19953275A1 - Emulsifiers - Google Patents

Abstract

The invention relates to emulsions for use in agriculture, comprising (a) oil-soluble pesticides and (b) esterquats. The preparation is characterized by a particularly long storage stability and can be easily diluted with water.

Description

Field of the Invention

The invention is in the field of agrochemicals and relates to special emulsions Pesticides and selected emulsifiers.

State of the art

In order to protect valuable crops from pests, there are many in the landscape Emulsions of oil-soluble pesticides are used. However, these preparations are not sufficiently stocked stable and in particular do not allow the preparation of dilutions or the addition of anything water soluble pesticides without breaking the emulsion. Another problem be is that the activity of the emulsions is not always satisfactory.

Accordingly, the complex object of the present invention has been to create new plants protective agents with solid as well as liquid, water-soluble as well as oil-soluble pesticides are available places that are characterized by higher storage stability and activity (adjuvant effect) NEN and in particular can be easily diluted with water as well as the stable Allow incorporation of additional water-soluble pesticides.

Description of the invention

The invention relates to emulsions containing
(a) pesticides and
(b) Esterquats.

Surprisingly, it has been found that emulsions containing pesticides along with cationic ones Contain emulsifiers of the ester quat type and optionally nonionic co-emulsifiers, the fulfilling complex requirements in an excellent way. The invention closes the knowledge a that particularly advantageous emulsions of the composition mentioned are present if these have been prepared by the phase inversion temperature method ("PIT emulsions). The accessories Rittungen are characterized by a compared to conventional emulsions of the prior art improved storage stability and higher activity. You can also easily with water dilute and also allow the subsequent incorporation of water-soluble pesticides.

Pesticides

The pesticides which are suitable as component (a) are preferably oil-soluble substances. Fungicides, herbicides, insecticides or mixtures thereof can be used reach. Typical examples of suitable fungicides are azoxystrobin, benalaxyl, carbendazim, Chlorothalonil, cupfer, cymoxanil, cyproconazole, diphenoconazole, dinocap, epoxiconazole, fluazinam, Flusilazole, flutriafol, Folpel, fosetyl aluminum, kresoxim methyl, hexaconazole, mancozeb, metalaxyl, Metconazole, myclobutanil, ofurace, phentin hydroxide, prochloraz, pyremethanil, soufre, tebucanazole, and tetraconazole and mixtures thereof. As herbicides, alachlor, acloniphene, acetochlor, Amidosulfuron, aminotriazole, atrazine, bentazone, biphenox, bromoxyl octanoate, bromoxynil, cletho dim, Chlodinafop-Propargyl, Chloridazon, Chlorsulfuron, Chlortoluron, Clomazon, Cycloxydim, Desme dipham, dicamba, dicyclofop-methyl, diurea, difluphenicanil, dimithenamide, ethofumesate, flua zifop, fluazifop-p-butyl, fluorochloridone, fluroxypyr, glufosinate, glyphosate, haloxyfop-R, ioxynil octa noate, isoproturon, isoxaben, metamitron, metazachlor, metolachlor, metsulfuron-methyl, nicosulfuron, Nofflurazon, Oryzalin, Oxadiazon, Oxyfluorphen, Paraquat, Pendimethalin, Phenmedipham, Phenoxy prop-p-ethyl, propaquizafop, prosulfocarb, quizalofop, sulcotrione, sulphosate, terbutylazine, triasulfu ron, trichlorpyr, triflualin and triflusulforon-methyl can be used individually or in a mixture. As Finally, insecticides come biphenthrin, carbofuran, carbosulfan, chlorpyriphos-methyl, chlorpyri phos-ethyl, β-cyfluthrin, λ-cyhalothrin, cyhexatin, cypermethrin, dicofol, endosulfan, τ-fluvalinate, α- Methrin, δ-methrin, phenbutatin, pyrimicarb, terbuphos and tebuphenpyrad and their mixtures in Consideration. Other suitable pesticides can be found, for example, in the Phytosanitaire 1998, 34 index. Edition (ed .: Association de Coordination Technique Agricole, Paris). Preferred two glufosinates or glyphosphates are used.  

Esterquats

Under the name of esterquats, which form component (b) as emulsifiers, in general understood my quaternized fatty acid triethanolamine ester salts. These are known Substances obtained by the relevant methods of preparative organic chemistry can. In this context, reference is made to the international patent application WO 91/01295 (Henkel) referenced, after which one triethanolamine in the presence of hypophosphorous acid with fatty acids partially esterified, air passed through and then quaternized with dimethyl sulfate or ethylene oxide. Out German patent DE 43 08 794 C1 (Henkel) is also a process for the production of solid Esterquats known in which the quaternization of triethanolamine esters in the presence of ge suitable dispersants, preferably fatty alcohols. There are overviews on this topic for example by R. Puchta et al. in Tens.Surf.Det., 30, 186 (1993), M. Brock in Tens.Surf.Det. 30, 394 (1993) R. Lagerman et al. in J. Am. Oil.Chem.Soc., 71, 97 (1994) and I. Shapiro in Cosm.Toil. 109, 77 (1994) appeared.

The quaternized fatty acid triethanolamine ester salts follow the formula (I)

in which R ¹ CO stands for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the sense of the inven tion are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures how they occur, for example, in the pressure splitting of natural fats and oils. Technical C _12/18 coconut _fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids and elaidic acid-rich C _16/18 fatty acid cuts are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm fatty acid (iodine number 0 to 40 ). From an application point of view, quaternized fatty acid thanolamine ester salts of the formula (I) have proven to be particularly advantageous in which RICO for an acyl radical having 16 to 18 carbon atoms, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for a methyl group, m, n and p is 0 and X is methyl sulfate. Corresponding products are on the market under the Dehyquart® AU brand (Co gnis Deutschland GmbH).

In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as esterquats.

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (III) should be mentioned as a further group of suitable ester quats,

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

Also suitable as ester quats are substances in which the ester bond has been replaced by an amide bond and which preferably follow the formula (IV) based on diethylenetriamine,

in which R ¹ CO represents an acyl radical having 6 to 22 carbon atoms, R ^{2 represents} hydrogen or R ¹ CO, R ⁶ and R ⁷ independently of one another represent alkyl radicals having 1 to 4 carbon atoms and X represents halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.

Finally, suitable esterquats are also substances which are obtainable on the basis of ethoxylated castor oil or its hardening products and preferably follow the formula (V)

in which R ⁸ CO represents a hydroxyacyl radical with 16 to 22 carbon atoms ethoxylated with 1 to 50 mol of ethylene oxide, R ⁹ and R ¹⁰ independently of one another for hydrogen or R ⁸ CO, R ¹ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H group, m, n and p in total for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the for examples mentioned for (I) also for the esterquats of the formulas (II) to (V). For the production of the esters Quats of the formulas (I) to (V) can contain both fatty acids and the corresponding triglycerides be assumed. Such a process, representative of the corresponding status of Technology should be mentioned is featured in European patent EP 0750606 B1 (Cognis) beat. It is also possible to counter the condensation of the alkanolamines with the fatty acids were defined amounts of dicarboxylic acids, such as. B. oxalic acid, malonic acid, succinic acid, malein acid, fumaric acid, glutaric acid, adipic acid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or dodecanedioic acid. This leads to a partially oligomeric Structure of the esterquats, which is particularly soluble when using adipic acid on the clear of the products can have an advantageous effect. Corresponding products under the Dehyquart® D brand 6003 (Cognis Deutschland GmbH) are available in the Handei and are for example in the Europäischei described patent EP 0770594 B1 (Cognis). Usually the esterquats get into Form 50 to 90 wt .-% alcoholic solutions on the market, which if necessary with What can be diluted.

Nonionic co-emulsifiers

In a preferred embodiment of the invention, in addition to the cationic emulsifiers, the emulsions can furthermore contain nonionic co-emulsifiers (component c) as optional components. For example, nonionic surfactants from at least one of the following groups can be used:

• 1. Addition products of 2 to 120 moles of ethylene oxide and / or 0 to 75 moles of propylene oxide linear fatty alcohols with 8 to 22 C atoms, on fatty acids with 8 to 22 C atoms, on alkyl phae noles with 8 to 15 carbon atoms in the alkyl group and fatty amines with 6 to 22 carbon atoms;
• 2. C _12/18 fatty acid _mono- , di and triesters of adducts of 1 to 120 moles of ethylene oxide with glycerol or technical oligoglycerols;
• 3. Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated Fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products;
• 4. Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxy analogs;
• 5. Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;
• 6. Polyol and especially polyglycerol esters such as. B. polyglycerol polyricinoleate or polyglyce rinpoly-12-hydroxystearate. Mixtures of compounds of several are also suitable of these substance classes;
• 7. Addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil; (8) Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerin, polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. Methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
• 8. trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;
• 9. wool wax alcohols;
• 10. polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• 11. Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 11 65 574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methylglucose and polyo len, preferably glycerin,
• 12. Polyalkylene glycols as well
• 13. Glycerol carbonate.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters as well as sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are homologous mixtures whose average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C _12/18 fatty acid _monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 20 24 051 as refatting agents for cosmetic preparations. C _8/18 alkyl mono- and oligoglycosides, their preparation and their use as surface-active substances are, for example, from US 3,839,318, US 3,707,535, US 3,547,828, DE-OS 19 43 689, DE-OS 20 36 472 and DE-A1 30 01 064 and EP-A1 0077167 known. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue applies that both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol, as well as oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Solvents

Especially when pesticides are to be incorporated into the emulsions, which are solids at room temperature, it is advisable to use non-polar solvents. As a further fa cultivative component (d) come, for example, mineral oils, alkyl aromatics and hydrocarbons such as z. B. are sold under the name Solvesso® by the Exxon company, Fettäu reniedrigalkylester, such as. B. the C ₁ -C ₄ -, ie the methyl, ethyl, propyl and / or butyl ester of Ca pronic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid; Myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Vegetable triglycerides such as coconut oil, palm oil, palm kernel oil, sunflower oil, olive oil and the like are also suitable.

Emulsions

In a preferred embodiment, the emulsions according to the invention contain

• a) 1 to 60, preferably 5 to 55% by weight of pesticides,
• b) 0.5 to 45, preferably 5 to 30% by weight of ester quats,
• c) 0 to 10, preferably 1 to 3% by weight of nonionic co-emulsifiers and
• d) 0 to 40, preferably 5 to 30% by weight of solvent,

with the proviso that the quantities indicated with water and possibly other usual Add auxiliaries and additives to 100% by weight. The water content of the emulsions is through On average 10 to 90 and in particular 30 to 60 wt .-%, the droplet size at 0.01 to 1, preferably as 0.1 to 0.5 microns.  

The invention further relates to a method for producing pesticide emulsions, in which the oil-soluble pesticides together with the esterquats (as well as the non- ionic emulsifiers and the solvents) and 40 to 60 wt .-% - based on the final formulation - Water homogenized until heated to the phase inversion temperature, the remaining amount of water added, the emulsion can cool and then optionally with a further amount of water on the Diluted application concentration and / or additional water-soluble pesticides are added.

A final object of the invention is ultimately directed to the use of the ester quats as Emulsifiers for the preparation of pesticide formulations in which they are present in amounts of 0.5 to 45 preferably 5 to 30 wt .-% - based on the agent - may be included.

Examples

Plant protection emulsions were used using liquid or solid at room temperature Pesticides examined. The emulsions 1 to 4 according to the invention and the comparison emulsion V1 were prepared by the PIT process, the comparison emulsion V2 by conventional hot method. The emulsions were then stored at 20 ° C. for 1 week or at 40 ° C. for 4 weeks and examined for their stability; (++) means stable, (+) slight turbidity and (-) phase centers nung. Furthermore, the emulsions were after the preparation at 20 ° C with water except for one Active substance content of 1 wt .-% diluted and the stability assessed in the same way. The result se are summarized in Table 1.

Table 1

Stability of pesticide formulations

Claims (16)

1. Containing emulsions
(a) pesticides and
(b) Esterquats. 2. Emulsions according to claim 1, characterized in that they are oil-soluble as component (a) and / or contain water-soluble pesticides. 3. Emulsions according to claims 1 and / or 2, characterized in that they as a compo nente (a) contain fungicides, herbicides, insecticides or mixtures thereof. 4. Emulsions according to at least one of claims 1 to 3, characterized in that they contain esterquats of the formula (I) as component (b),
in which R ¹ CO stands for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate. 5. Emulsions according to at least one of claims 1 to 4, characterized in that they contain esterquats of the formula (II) as component (b),
in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate. 6. Emulsions according to at least one of claims 1 to 5, characterized in that they contain esterquats of the formula (III) as component (b),
in which R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in sum for 0 or Numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate. 7. Emulsions according to at least one of claims 1 to 6, characterized in that they contain esterquats of the formula (IV) as component (b),
in which R ¹ CO is an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁶ and R ^{7 are,} independently of one another, alkyl radicals having 1 to 4 carbon atoms and X is halide, alkyl sulfate or alkyl phosphate. 8. Emulsions according to at least one of claims 1 to 7, characterized in that they contain esterquats of the formula (V) as component (b),
in which R ⁸ CO is a hydroxyacyl radical with 16 to 22 carbon atoms ethoxylated with 1 to 50 mol of ethylene oxide, R ⁹ and R ¹⁰ independently of one another for hydrogen or R ⁸ CO, R ¹ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H group, m, n and p in total stand for 0 or numbers from 1 to 12, q stands for numbers from 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate. 9. Emulsions according to at least one of claims 1 to 8, characterized in that they further contain non-ionic co-emulsifiers as optional component (c). 10. Emulsions according to claim 9, characterized in that they contain, as component (c), non-ionic emulsifiers which are selected from the group formed by system products from 2 to 120 mol of ethylene oxide and / or 0 to 75 mol of propylene oxide linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group; C _12/18 fatty acid _mono- , di-, triesters of adducts of 1 to 120 moles of ethylene oxide with glycerol; Glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products; Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; Polyol esters; Addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil; Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols; Alkyl glucosides; Trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates; Wool alcohol; Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives; Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols; Polyalkylene glycols and glycerine carbonate. 11. Emulsions according to at least one of claims 1 to 10, characterized in that they further contain as optional component (d) solvents. 12. Emulsions according to claim 11, characterized in that they are mineral oil as component (d), Contain alkyl aromatics, fatty acid lower alkyl esters and / or vegetable triglycerides. 13. Emulsions according to at least one of claims 1 to 12, characterized in that they

• a) 1 to 60% by weight of pesticides,
• b) 0.5 to 40% by weight of esterquats,
• c) 0 to 10 wt .-% nonionic co-emulsifiers and
• d) 0 to 40 wt .-% solvent

with the proviso that the quantities with water and, if appropriate, further conventional auxiliaries and additives are 100% by weight. 14. Emulsions according to at least one of claims 1 to 13, characterized in that they Have droplet sizes in the range of 0.01 to 1 µm (PIT emulsions). 15. Process for the preparation of pesticide emulsions, in which the oil-soluble pesticides are combined men with the ester quats and 40 to 60 wt .-% - based on the final formulation - water ho mogenized until heated to the phase inversion temperature, added the remaining amount of water, allows the emulsion to cool and then optionally with a further amount of water on the Diluted application concentration and / or additional water-soluble pesticides are added. 16. Use of esterquats as emulsifiers for the preparation of pesticide formulations.