DD236446A5 - FLOWABLE HERBICIDES COMPOSITIONS - Google Patents

Abstract

The invention relates to flowable herbicidal compositions containing as active component at least one herbicidally active urea derivative. The aim of the invention is to provide those compositions which are stable to transport and storage even when the content of active substance is more than 500 g / l. According to the invention, the novel flowable herbicidal compositions contain 35-66% by weight of one or more urea derivatives of the formula I in which, for example, R1 is benzothiazol-2-yl, 5-trifluoromethyl-1,3,4-thiadiazol-2-yl and the like. R2 is hydrogen or methyl, R3 is methyl; R4 is methyl, methoxy, hydrogen; 1-10% by weight of at least one mono- or di (phenol polyglycol ether) phosphoric acid ester or a salt thereof; 0.1-5% by weight of at least one polyglycol ether; 0-3% by weight of an auxiliary dispersant; 0-10% by weight of an antifreeze and 20-55% by weight of water.

Description

Characteristic of the known technical solutions

It is known that herbicidally active urea derivatives can be used alone or in combination with other herbicidal active compounds, e.g. Triazine derivatives to formulate as aqueous suspension concentrates. It has been possible to produce transportable and storage-stable suspension concentrates which contain a maximum of 500 g / l of active substance using special anionic surfactant combinations. The preparation of stable aqueous suspensions with higher active ingredient contents, which are desirable from an economic and application point of view, was not possible with the hitherto known surfactant combinations.

Object of the invention

The aim of the invention is the provision of transportable and storable herbicidal compositions which have a higher active ingredient content.

Explanation of the essence of the invention

The present invention is therefore based on the object to provide flowable herbicidal compositions in the form of aqueous suspensions, which are transport and storage stable even with a content of active ingredient of more than 500g / l.

According to the invention, a flowable herbicidal suspension concentrate is proposed, which is characterized in that

35-66% by weight

one or more urea derivatives of the formula I.

in which R is benzothiazol-2-yl, 5-trifluoromethyl-1,3,4-thiadiazol-2-yl or a Phenyirest of the formula

in which R _{5 is} hydrogen, chlorine, bromine or C ₁ -C ₄ -alkyl, R _{6 is} hydrogen, chlorine, trifluoromethyl or Ci-Ci-alkylaminocarbonyloxy, wherein R ₅ and R ₆ can not simultaneously be hydrogen, R ₂ Is hydrogen or, when R _{1 is} benzothiazol-2-yl or 5-trifluoromethyl-1,3,4-thiadiazol-2-yl, is methyl, R _{3 is} methyl and R _{4 is} methyl, methoxy or, when R _{1 is} benzothiazole-2 is -yl or 5-trifluoromethyl-1,3,4-thiadiazol-2-yl, is hydrogen, or a mixture of one or more urea derivatives of the formula I and another water-insoluble solid herbicidal active substance,

1-10 wt .-% of at least one mono- or di- (phenolpolyglykoläther) phosphoric acid ester or a salt thereof of the formula II

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/ λ O) ^(ΙΙ)

in which R is a radical of the formula

(R) 9 m

R _{8 has} the same meaning as R ₇ or is hydrogen and M is a proton, a sodium, potassium, diethylammonium, triethylammonium, diethanolammonium or triethanolammonium cation, where R _{9 is} hydrogen, C ₃ -C ₁₀ -Alkyl or styryl, m is an integer from 1-4 and η is an integer from 4-40, 0.1-5 wt .-% of at least one polyglycol ether of the formula III

Rn ( PTT -Pu ^ n TT fTTT ^

wherein R _{10 is} C ₁₂ -C ₁₈ alkyl, C ₁ 2 -C ₂₂ alkanoyl, C ₁₂ -C ₂₂ alkenoyl, C ₁ 2 -C ₂ 2-alkadienonyl, C ₁₂ -C ₂₂ alkatrienonyl or by C ₃ -C ₁₀ -Aikyl, C ₅ -C ₈ -CyClOalkyl or styryl 1-3-substituted phenyl and ρ is an integer from 1-6,

0-3Gew .-% of an auxiliary dispersant 0-10 wt .-% of an antifreeze and 20-55 wt .-% water.

The herbicidal compositions according to the invention are suspension concentrates which contain as active component 35-66% by weight of one or more urea derivatives of the formula I or a mixture of one or more urea derivatives of the formula I with a further sparingly water-soluble solid herbicide. The suspension concentrates according to the invention preferably contain

45-60% by weight of one or more urea derivatives of the formula I or of a mixture of one or more urea derivatives

¹ . derivatives of the formula I with a further sparingly soluble in water solid herbicide, 2-5 wt .-% of at least one mono- or di- (phenolpolyglykoläther) phosphoric acid ester or a salt thereof

of the formula II, 0.1-2% by weight of at least one polyglycol ether of the formula III

0-3 wt .-% of an auxiliary dispersant 0-10Gew .-% of an antifreeze and 23-40 wt .-% water.

Preferred among the ureas of the formula I are those in which R _{1 is} 3-chloro-4-methylphenyl, 3-trifluoromethylphenyl-4-isopropylphenyl, 3,4-dichlorophenyl, S-tert-butylaminocarbonyloxyphenyl, 4-bromo-3-chlorophenyl or 4-bromophenyl, R _{2 is} hydrogen, R _{3 is} methyl and R _{4 is} methyl or methoxy. Further suitable ureas of the formula I are preferably those in which R _{1 is} benzothiazol-2-yl or δ-trifluoromethyl- _1- methyl-thiadiazolyl, R ₂ and R _{3 are} methyl and R _{4 is} hydrogen. Particular preferred representatives of ureas of the formula I are: N- (3-chloro-4-methylphenyl) -N ', N'-dimethylurea (chlorotoluron) N- (3-trifluoromethylphenyl) -N', N'-di methyl urea (fluorormuron) N- (4-isopropyl-1-phenyl) -N ', N'-dimethylurea (isoproturon) N- (3,4-dichlorophenyl) -N', N'-dimethylurea (Diuron )

N- (3-tert-butylaminocarbonyloxyphenyl) -N ', N'-dimethylurea (carbutylate) N-fSi-dichlorophenyl-N'-methoxy-N'-methyl-halo (linuron) N- (4-bromo-3 -chlorophenyl) -N'-methoxy-N'-methylurea (chlorobromuron) N- (4-bromophenyl) -N'-methoxy-N'-methyl-urea (metobromuron) N- (5-trifluoromethyl-1,2,4-thiadiazole -2-yl) -N, N'-dimethylurea (thiazafluron) N- (benzthiazol-2-yl) -N, N'-dimethylurea (methabenzthiazuron)

Preferred urea derivatives of the formula I are chlortoluron, metobromuron, fluometuron and isoproturon. As further herbicidal active substances, which together with one or more urea derivatives of the formula I can form the active component of the herbicidal suspension concentrates according to the invention are basically any solid, sparingly soluble in water herbicidal active substances into consideration, provided that their combination with a derivative of urea of formula I from any one Reason, for example broadening of the spectrum of action or synergism, is desirable. Such further herbicidal active substances which together with one or more urea derivatives of the formula I can form the active component of the suspension concentrates according to the invention can be selected, for example, from the following classes of herbicidal active substances:

Oiphenylätherderivate,

Phenoxyphenoxyalkancarbonsäurederivate,

Nitroanilines,

haloacetanilides,

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O-aryl oxime,

triazines,

benzamide derivatives,

sulfonylureas,

halogenated pyridyloxyalkanoic acid,

Imidazolinylbenzoesäurederivate,

Imidazolinylnikotinsäurederivate,

N-substituted halopyrrolidones,

Hydroxybenzonitriles and

Benzthiadiazinonderivate.

In particular, compounds of the type described in US Pat. No. 365,265, especially methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (bifenox), and also compounds of the type described in DE-OS 2831262, in particular 2-chloro, are used as diphenyl ether derivatives 6-nitro-3-phenoxyaniline (aclonifen), as well as compounds of the type described in US Pat. No. 4,322,375, in particular 2- (2-chloro-4-trifluoromethyl-phenoxy) -5-nitrophenyl-phosphonic acid dimethyl ester, and compounds of the type Patent Application 69055, in particular 2- [4- (3-trifluoromethylphenoxy) phenyl] -3-ethoxycarbonyl-4-oxo-5-ethyl-5,6-dihydropyran. Compounds of the type described in DE-OS 2 223894, in particular a- [4- (2,4-dichlorophenoxy) -phenoxy] -propionic acid methyl ester (llloxane), are particularly suitable as phenoxyphenoxyalkanecarboxylic acid derivatives. Particular examples of nitronailines are compounds of the type described in US Pat. No. 4,199,669, preferably N- (1-ethylpropyl) -2,6-dinitro-3,4-xylidine (pendimethalin). Preferred haloacetanilides are compounds of the type described in DE-OS 2305495, in particular N- (1-methyl-2-methoxyethyl) -N-chloroacetyl-2,6-dimethylaniline. Preferred O-aryloximes are the compounds of the type described in US Pat. No. 3,733,359, in particular 3,5-dibromo-4-hydroxybenzaldehyde-O-2,4-dinitrophenyloxime (bromofenoxime). As triazines, preference may be given to compounds of the type described in British Pat. No. 814,948, in particular 2-ethylamino-4-tert-butylamino-6-methylthio-1,3,5-triazine (terbutryn), 2,4-bis-isopropylamino 6-methylthro-1,3,5-triazine (prometry) and 2,4-bis-isopropylamino-6-ethylthio-1,3,5-triazine (dipropetryn). Suitable benzamide derivatives are compounds of the type described in EP Patent Application 49071, in particular N- [3- (1-ethyl-1-methylpropyl-5-isoxazolyl) -2,6-dimethoxybenzamide (benzamizole).] Suitable sulfonylureas are the compounds of the in EP Patent Application 44808, in particular N- [2- (2-chloroethoxy) phenylsulfonyl] -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea and also the compounds of the type described in US Pat. No. 4,127,405, in particular N- (2-chlorophenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea ( Chlorosulfuron) and the compounds of the type described in U.S. Patent No. 4,383,113, especially N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea As halogenated pyridyloxyalkanecarboxylic acid derivatives, the compounds of the type described in US Pat. No. 4,110,104, in particular 2- (4-amino-3,5-dichloro-6-fluoropyrid-2-yloxy) -acetic acid (DOWCO433), are suitable As imidazole inylbenzoic acid derivatives are, in particular, the compounds of the type described in US Pat. No. 4,188,487, in particular 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -4-methylbenzoic acid methyl ester and 2- (4-isopropyl 4-methyl-5-oxo-2-imidazolin-2-yl) 5-methylbenzoic acid methyl ester or a mixture of these two compounds, into consideration. As Imidazolinylnikotinsäurederivate especially the compounds described in EP patent application 41 623, in particular 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid can be used. Suitable N-substituted halopyrrolidinones are the compounds described in DE-OS 2612731, in particular 1- (3-trifluoromethylphenyl) -2-chloro-4-chloromethyl-2-pyrrolidone. Preferred hydroxybenzonitriles are the compounds described in US Pat. No. 3,397,054, in particular 3,5-dibromo-4-hydroxybenzonitrile (bromoxynil) and 3,5-diiodo-4-hydroxybenzonitrile (loxynil). As Benzthiadiazinonderivate preferably compounds of the type described in DE-OS 1 542836, in particular 3-isopropyl (1 H) benzo-2,1,3-thiadiazin-2-one-2,2-dioxide (bentazone) can be used , _...._-

Preferred herbicidal active substances which together with one or more urea derivatives of the formula I can form the active component of the suspension concentrates according to the invention are 5- (2,4-dichlorophenoxy) -2-nitrobenzoic acid methyl ester

N- (1-methyl-2-methoxyethyl) -N-chloroacetyl-2,6-dimethylaniline

2-ethylamino-4-tert-butylarnino-6-rnethoxylthio-1,3,5-triazine

2,4-bis-isopropylamino-6-methylthio-1,3,5-triazine

2,4-bis-isopropylamino-6-ethylthio-1,3,5-triazine

N- [2- (2-chloroethoxy) phenylsulfonyl] -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea N- (2-chlorophenylsulfonyl-N'- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea N- (2-Methoxycarbonylphenylsulfonyl) -N '- (4-rriethoxy-6-methyl-1,3,5-triazine -2-yl) -urea.

The herbicidal compositions according to the invention may contain one or more mono- or di- (phenolpolyglycol ether) -phosphoric acid esters or salts thereof of the formula II.

The mono- and di- (phenolpolyglycol ether) -phosphoric acid esters of the formula II are preferably used as salt, in particular as triethanolammonium salt, it being possible to use the pure mono- or disalts or mixtures of mono- and disalts. The bound to the phenyl radical of the radical R7 Rg as C3-Ci _o alkyl means straight primarily alkyl radicals such as n-propyl, η-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n Nonyl or n-decyl, but also includes the branched isomers of these radicals, such as tert. Butyl, dimethylpentyl, dimethylhexyl, dimethyloctyl and diethylpropyl. Preferred meanings of the radical R ₉ are n-nonyl and styryl. The preferred meaning for m is 1-3 and the preferred meaning for

nist6-26. _ -

Examples of substituted phenyl groups which may be present in the radical R ₇ are 4-n-nonylphenyl, 2,4,6-tri-n-butylphenyl, 2,4,6-tristyrylphenyl, 2,4-di-n-nonylphenyl , 2,4,6-tri-n-pentylphenyl, 2,4-distyrylphenyl, 4-styrylphenyl, 2,3,4,6-tetrastyrylphenyl, 4-n-decylphenyl, 4-n-heptylphenyl, 4-n Pentylphenyl-2,4-di-n-hexylphenyl, 2,4-di-n-octylphenyl, 4-n-octylphenyl, 4-n-hexylphenyl, 2,4-di-n-pentylphenyl and 2,4,6 Tri-n-pentylphenyl called. Preferred phenyl groups biw for R ₇ . R ₇ and R ₈ may be 4-n-nonylphenyl and trisubstituted phenyl groups, especially 2,4,6-tristyrylphenyl. In the mono- and di- (phenolpolyglycol ether) -phosphoric acid esters or salts thereof of the formula II, n is when R ₇ or R ₇ and R _{3 are} 4-n-nonylphenyl, preferably 6-9 and, if R ₇ or R ₇ and R _{8 represent} 2,4,6-triphenylstyryl, preferably '6-26.

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Typical representatives of mono- and di- (phenolpolyglycol ether) -phosphoric esters of the formula II which can be used according to the invention are mono- and di- (tristyrylphenolhexadecaglycol ether) phosphoric acid esters, mono- and di- (tristyrylphenol octadecaglycol ether) phosphoric acid esters, mono- and di (tristyrylphenol nonadecadecyl ether mono- and di-tristyrylphenoleicosaglycol ether phosphoric acid esters, mono- and di- (tristyrylphenol dicosoglycol ether) phosphoric acid esters, mono- and di- (nonylphenol hexaglycol ether) phosphoric acid esters, mono- and di- (nonylphenol octahlycol ether) phosphoric acid esters and mono- and di The commercially available phenol polyglycol ether phosphoric acid esters of the formula II are generally present as mixtures of the corresponding mono- and diesters or as salts of mixtures of mono- and diesters, and also with regard to the substitution in the phenyl radical the commercially available products Gemisc with different degrees of substitution (m = 1-4). Such mixtures can be advantageously used for the preparation of the herbicidal compositions of the invention.

Suitable, commercially available mono- and di- (phenolpolyglykoläther) -phosphorsäureesterderivate of formula I are, for example

HOE S 3475 triethanolamine salt of a mixture of mono- and di (2,4,6-tristyrylphenol polyglycol ether) ester phosphate, the polyglycol ether part consisting on average of 20 ethylene glycol units (n = 20);

Soprophor F1 triethanolamine salt of a mixture of mono- and di (2,4,6-tristyrylphenol polyglycol ether) ester phosphate in which the polyglycol ether portion contains 16-20 ethylene glycol units (n = 16-20);

Soitem8FL / N triethanolamine salt of a mixture of mono- and di (2,4,6-tristyrylphenol polyglycol ether) ester phosphate in which the polyglycol ether portion contains on average 18 ethylene glycol units Cn = 18);

Celanol PS-17 potassium salt of a mixture of mono- and di- (nonylphenoipolyglycol ether) ester phosphate with an average of 6 ethylene glycol units (n = 6);

Celanol PS-19 potassium salts of a mixture of mono and DHnonyl phenol polyglycol ether ester phosphate with on average 9 ethylene glycol units (n = 9);

The polyglycol ethers of the formula III preferably contain 1-3 glycol ether units (p = 1-3).

The radical Ri ₀ includes as C ₁₂ -C ₁₈ alkyl primarily straight-chain alkyl radicals such as n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl, but also their isomers with branched chains such as trimethylnonyl, tetramethylnonyl, dimethylundecyl and dipropylhexyl. As the cycloalkyl group of 5-8 carbon atoms, R ₁₀ includes cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Alkanoyl, alkenoyl, alkadienoyl and Alkatrienoylresten with 12-22 carbon atoms are the acyl radicals of the corresponding 1-, 2- or 3-fold unsaturated carboxylic acids to understand. The saturated carboxylic acids from which the alkanoyl radicals derive are lauric acid, myristic acid, palmitic acid or stearic acid. Unsaturated carboxylic acids, from which the alkenyl radicals falling under the definition of Ri ₀ are derived, are lauroleinic acid, myristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, ricinoleic acid and erucic acid. Examples of di- or tri-unsaturated carboxylic acids, of which the alkadienoyl and alkatrienoyl radicals which fall under the meaning of R ₁₀ , are linoleic acid, linolenic acid, ricinic acid and α-estestinic acid.

As a monosubstituted to trisubstituted phenyl radical, R _{10 is,} for example, 4-n-nonylphenyl, 2,4,6-tri-n-butylphenyl, 2,4,6-tristyrylphenyl, 2,4-di-n-nonylphenyl, 2,4 , 6-tri-n-pentylphenyl, 2,4-distyrylphenyl, 4-styrylphenyl, 4-n-decylphenyl, 4-n-heptylphenyl, 4-n-pentylphenyl, 2,4-di-n-hexylphenyl, 2,4 Di-n-octylphenyl, 4-n-octylphenyl, 4-n-hexylphenyl, 2,4-di-n-pentylphenyl, 2,4,6-tri-n-pentylphenyl, 4-cyclohexylphenyl, 4-cyclopentylphenyl and 2 , 4-Dicyclohexylphenyl.

Commercially available polyglycol ethers of the formula III are, for example

Arkopal N 030 4-nonylphenol polyglycol ether with on average 3-ethylene glycol units (p = 3); Arkopal N 040 4-nonylphenol polyglycol ether with an average of 4-ethylene glycol units (p = 4); Disponil NP 3 4-nonylphenol polyglycol ether containing on average 3-ethylene glycol units (p = 3); AntaroxCO210 4-nonylphenol polyglycol ether with 1-2 ethylene glycol units (p = 1-2); Brij 92 oleyl polyglycol ether with an average of 2 ethylene glycol units (p = 2); Genapol 0-020 oleyl polyglycol ether with an average of 2 ethylene glycol units (p = 2).

Suitable auxiliary dispersants which may be present in the herbicidal compositions according to the invention are both substances which favorably influence the degree of viscosity and substances which additionally stabilize the suspension. For example, water-swellable thickeners or synthetic or semisynthetic macromolecules can be added as auxiliary dispersants in water or in water. Suitable auxiliary dispersants which can be added to the herbicidal compositions according to the invention are polysaccharides, in particular polysaccharides of the xantham, alginate, guar or cellulose type, or synthetic macromolecules, such as polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols, polyacrylates, in particular with triethanolamine or alkali-neutralized mixed polymers of acrylic acid and acrylic acid esters, or swellable, structurally-forming silicates, such as pyrogenic or precipitated silicas, bentonites, montmorillonites, hectonites, attapulgites or organic derivatives of aluminum silicates.

As antirust agents which can be added to the herbicidal compositions according to the invention for maintaining the flowability at low temperatures and for preventing the freezing of water, other additives, such as ethylene glycol, propylene glycol, glycerol, di-, tri- and tetraethylene glycol and urea are suitable.

The herbicidal compositions according to the invention, in addition to the aforementioned ingredients nor conventional additives such as anti-foaming agents, such as. As silicone oil, and preservatives, such as. For example, formaldehyde. The herbicidal compositions of the invention are flowable and are characterized by good transport and storage stability. The combination according to the invention of special anionic and nonionic surfactants makes it possible to prepare herbicidal suspension concentrates which, per unit volume, may contain substantially more active substance than previously known suspension concentrates.

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embodiment

The invention is explained in more detail below with reference to some examples. The herbicidal compositions according to the invention can be prepared as follows:

In a stirred tank, the available amount of water is introduced and the surfactants of the formula II and III and optionally an auxiliary dispersant of the aforementioned type of synthetic polymers, an antifreeze and an antifoaming agent are stirred until the mixture is homogeneous. Then the herbicidal active ingredient or the mixture of herbicidal active ingredients is added and first homogenized for 10-30 minutes and then finely ground. For fine grinding, for example, a glass bead mill can be used.

The suspension concentrate obtained in this way can be further added to influence the viscosity by adding a further auxiliary dispersant of polysaccharide type (thickener) and, if desired, a preservative. For this purpose, it is advisable so that the polysaccharide stirred in a separate stirred tank in the necessary for the preparation of a 2.5% gel amount of water and with the intended amount of preservative, eg. B. 37% aqueous formaldehyde solution. The mixture is stirred for 10 minutes and then allowed to swell for at least 2 hours. The mixture thus obtained may be added to the finely ground suspension concentrate prepared as described above in the amount required in each case, taking into account the amount of water introduced thereby in the calculation of the total available amount of water.

The flowable herbicidal compositions thus obtained have the following quality characteristics depending on the type and concentration of the active ingredients used:

Viscosity (20 ⁰ C): 600-1 200m. Pa.s (measured in a Brookfield LV viscometer, measuring system III) pH: 6.5-8.5

Density (20 ⁰ C): 1.08 to 1.3.

In the following examples, some typical herbicidal compositions are given to illustrate the present invention. The preparation of these herbicidal compositions can be carried out by the method indicated above.

Example 1: Suspension concentrate of chlorotoluron

58.90% by weight of chlorotoluron techn. (99%)

3.10% by weight of triethanolamine salt of a mixture of mono- and di (2,4,6-tristyrylphenol polyglycol ether) ester phosphate with 16-20 ethylene glycol units

0.75% by weight of nonylphenol triglycol ether 6.25% by weight of ethylene glycol 0.40% by weight of silicone oil

0.12 wt% Xantham type polysaccharide 0.40 wt% polyacrylic acid

0,12Gew .-% formaldehyde 29.96 wt .-% water content of active substance per liter: 700g Density (20 ⁰ C): 1.19 to 1.21 g / cm ³

Example 2: Suspension concentrate of chlorotoluron

66.15 wt .-% Chlortoluron techn. (99%)

3.10% by weight of triethanolamine salt of a mixture of mono- and di (2,4,6-tristyrylphenol polyglycol ether) ester phosphate with 16-20 ethylene glycol units

0.80% by weight of nonylphenol triglycol ether 6.25% by weight of ethylene glycol 0.40% by weight of silicone oil

0.04 wt% Xantham type polysaccharide

0.04% by weight of formaldehyde 23.22% by weight of water Content of active substance per liter: 800 g Density (20 ° C.): 1.21-1.23 g / cm ³

Example 3: Suspension Concentrate of Chlortoluron and Benzamizole

57.70% by weight of chlorotoluron techn. (99%) 2.40% by weight of benzamizole tec'hn. (91.7% pure)

3.00 wt .-% triethanolamine salt of a mixture of mono- and di- (2,4,6-tristyrylphenolpolyglykoläther) ester phosphate with 16-20 ethylene glycol units

0.80% by weight of nonylphenol triglycol ether 6.00% by weight of ethylene glycol 0.50% by weight of silicone oil

0.12% by weight Xantham type polysaccharide

0.12% by weight of formaldehyde 29.36% by weight of water Content of active substance per liter: 700 g density (20 ° C.): 1.18-1.20 g / cm ³

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Example 4: Suspension Concentrate of Chlortoluron and Bifenox

43.50% by weight of chlorotoluron techn. (99%) 17.3% by weight Bifenox techn. (99.8% pure)

3.10% by weight of triethanolamine salt of a mixture of mono- and di (2,4,6-tristyrylphenol polyglycol ether) ester phosphate with 16-20 ethylene glycol units

0.80% by weight of nonylphenol triglycol ether 5.00% by weight of ethylene glycol 0.50% by weight of silicone oil

0.40 wt% polyacrylic acid 0.15 wt% Xantham type polysaccharide

0,15Gew .-% formaldehyde 29,10Gew .-% water content of active substance per liter: 700g Density (20 ⁰ C): 1,15-1,17g / cm ³

Example 5: Suspension Concentrate of Chlortoluron and Terbutryn

18.40% by weight of chlorotoluron techn. (99%) 36.50% by weight Terbutryn techn. (99.6% pure)

2.50% by weight of potassium salt of a mixture of mono- and di (nonylphenol polyglycol ether) ester phosphate with 6 to 9 ethylene glycol units

1.10% by weight of mixture of nonylphenol monoether and diglycol ether 2.70% by weight of ethylene glycol 0.50% by weight of silicone oil

0.12% by weight Xantham type polysaccharide

Ö, 12Gew .-% formaldehyde 38.06 wt .-% water content of active substance per liter: 600g density (2O ⁰ C): 1.08-1.10 g / cm ³

Examples: Suspension concentrate of chlorotoluron and dipropetryn

32.50% by weight of chlorotoluron techn. (99%) 21.80% by weight of dipropetryn techn. (98%)

2.80% by weight of potassium salt of a mixture of mono- and di- (nonylphenol polyglycol ether) ester phosphate with 6-9 ethylene glycol units

0.70% by weight of nonylphenol mono- and nonyldiglycol ether mixture 5.60% by weight of ethylene glycol 0.40% by weight of silicone oil

0.12% by weight Xantham type polysaccharide

0,12Gew .-% formaldehyde 35,96 wt .-% water content of active substance per liter: 600g Density (20 ⁰ C): 1,11-1,13g / cm ³

Example 7: Chlorotoluron suspension concentrate and N- [2- (2-chloroethoxy) phenylsulfonyl] -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea

58.35 wt .-% Chlortoluron techn. (99% pure) 6.10% by weight of N- [2- (2-chloroethoxy) phenylsulfonyl] -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea techn. (96%)

3.10% by weight of triethanolamine salt of a mixture of mono- and di (2,4,6-tristyrylphenol polyglycol ether) ester phosphate with 16-20 ethylene glycol units

0.75% by weight of nonylphenol triglycol ether 6.25% by weight of ethylene glycol 0.40% by weight of silicone oil

0.40 wt% Mixture of polyacrylic acid and polyacrylic acid ester 0.12 wt% Xantham type polysaccharide

0.12% by weight of formaldehyde 24.41% by weight of water Active substance content per liter: 700 g density (20 ° C.): 1.19-1.21 g / cm ³

Examples: suspension concentrate of fluometuron

59.90% by weight of fluometuron techn. (97.3%) 3.10Gew .-% triethanolamine salt of a mixture of mono- and di- (2,4,6-tristyrylphenolpolyglykoläther) ester phosphate with

16-20 ethylene glycol units 0.80% by weight nonylphenol triglycol ether 5.00% by weight ethylene glycol 0.50% by weight silicone oil

0.40% by weight triethanolamine neutralized mixture of polyacrylic acid and polyacrylic acid ester 0.15% by weight Xantham type polysaccharide

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0.15% by weight of formaldehyde 30.00% by weight of water Content of active substance per liter: 700 g density (20 ° C.): 1.19-1.21 g / cm ³

Example 9: Suspension Concentrate of Fluometuron and Nti-methyl-1-methoxyethyl J-N-chloroacetyl-Z 1 -diniethylaniline

42.55% by weight of fluometuron techn. (97.3%) 10% BGew-yoN-d-methyl-methoxyethyl-N-chloroacetyl-e-dimethylanilineOS.r / oig)

3.10% by weight of triethanolamine salt of a mixture of mono- and di (2,4,6-tristyrylphenol polyglycol ether) ester phosphate with 16-20 ethylene glycol units

0.80% by weight of oleyl polyglycol ether with 2-4 ethylene glycol units 5.00% by weight of ethylene glycol 0.50% by weight of silicone oil 0.10% by weight of a mixture of polyacrylic acid and polyacrylate ester neutralized with triethanolamine

0.10 wt .-% formaldehyde 37,30 wt .-% water content of active substance per liter: 600g density (2O ⁰ C): 1,15-1,17g / cm ³

Example 10: Suspension Concentrate of Metobromuron

53.00% by weight of metobromuron techn. (98.65% pure)

3.50 wt .-% triethanolamine salt of a mixture of mono- and di- (2,4,6-tristyrylphenolpolyglykoläther) ester phosphate with 16-20 ethylene glycol units

0.50 wt% nonylphenol triglycol ether 9.00 wt% ethylene glycol 0.30 wt% silicone oil 0.15 wt% Xantham type polysaccharide

0.15% by weight of formaldehyde

33,40 wt .-% water content of active substance per liter: 670g Density (20 ⁰ C): 1,28-1,30g / cm ³

Example 11: Suspension Concentrate of Isoproturon

54.80% by weight isoproturon techn. (99%)

2.40 wt .-% triethanolamine salt of a mixture of mono- and di- (2,4,6-tristyrylphenolpolyglykoläther) ester phosphate with 16-20 ethylene glycol units

0.60% by weight of oleyl diglycol ether 4.00% by weight of ethylene glycol 0.50% by weight of silicone oil 0.10% by weight of xantham type polysaccharide 0.10% by weight of formaldehyde 37.50% by weight of water Content of active substance per liter: 600g density (20 ° C): 1,08-1,10g / cm ³ .

Claims (15)

Invention claim: (D in which R _{1 is} benzothiazol-2-yl, 5-trifluoromethyl-1,3,4-thiadiazol-2-yl or a phenyl radical of the formula 1-10Gew .-% means, in which R ₅ is hydrogen, chlorine, bromine, or C ₁ -C ₄ -alkyl, R ₆ is hydrogen, chlorine, trifluoromethyl or Ci-C ₄ alkylaminocarbonyloxy, where R ₅ and R ₆ can not simultaneously represent hydrogen, R _{2 is} hydrogen or when R _{1 is} benzothiazol-2-yl or 5-trifluoromethyl-1,3,4-thiadiazol-2-yl is methyl, R _{3 is} methyl and R _{4 is} methyl, methoxy or, when Ri Benzthiazol-2-yl or 5-trifluoromethyl-1,3,4-thiadiazol-2-yl, is hydrogen, or a mixture of one or more urea derivatives of the formula I and a further, sparingly soluble in water solid herbicides active substance, at least one mono- or di- (phenolpolyglykoläther) phosphoric acid ester or a salt thereof of the formula II R ₇ -O (II) ^R 8- in which R _{7 is} a radical of the formula 0.1-5% by weight 0-3% by weight 0-10Gew .-% 20-55% by weight , R ₈ has the same meaning as R ₇ orfor hydrogen and My proton, sodium, potassium, Diäthylamrnonium-.Triäthylammonium-, Diäthylammonium- or Triäthanolammoniumkation, wherein R ₉ is hydrogen, C3-C _O alkyl or Styryl, m stands for an integer of 1-4 and only an integer of 4-40,
at least one polyglycol ether of the formula III ₀ -0 (-CH ₂ -CH ₂ -Oi H (III) WOrInR ₁₀ C ₁₂ -C ₁₈ -AlkYl, Ci2-C22 alkanoyl, C _l 2-C22 alkenoyl, C ₁ 2 -C ₂ 2-alkadienonyl, C ₁ 2 -C ₂ 2-Alkatrienonyl or by C ₃ -C ₁₀ Alkyl, Cs-Cs-cycloalkyl or styryl 1-3x substituted phenyl and ρ is an integer of 1-6 means an auxiliary dispersant of an antifreeze and water. 2. Flowable composition according to item 1, characterized by a content of 45-60% by weight of one or more urea derivatives of the formula I or of a mixture of one or more urea derivatives of the formula I with a further water-insoluble solid herbicide, 2-5% by weight of at least one mono- or di- (phenolpolyglycol ether) -phosphoric acid ester or a salt thereof of the formula II, -2- 755 64 0.1-2 wt .-% of at least one polyglycol ether of the formula III 0-3 wt .-% of an auxiliary dispersant 0-10% by weight of an antifreeze and 23-40 wt.% Water. 3. Flowable herbicidal composition according to items 1 and 2, characterized in that it contains a urea of the formula I in which Ri is S-chloro-methylphenyl, 3-trifluoromethylphenyl, 4-isopropylphenyl, 3,4-dichlorophenyl, 3-tert Butylaminocarbonyloxyphenyl ^ -bromo-S-fluorophenyl or 4-bromophenyl, R _{2 is} hydrogen, R _{3 is} methyl and R _{4 is} methyl or methoxy. 4. Flowable herbicidal composition according to items 1 and 2, characterized in that it contains a urea of the formula I in which R _{1 is} benzothiazol-2-yl or 5-trifluoro-1,2,4-thiadiazoi-2-yl, R ₂ and R _{3 is} methyl and R _{4 is} hydrogen. 5. Flowable herbicidal composition according to items 1 and 2, characterized in that it contains as a herbicidally active urea derivative of the formula I chlortoluron, fluometuron, isoproturon, diuron, carbutylate, linuron, chlorobromuron, metobromuron, thiazafluron or methabenzthiazuron. 6. Flowable herbicidal composition according to items 1 and 2, characterized in that it contains as the urea derivative of the formula I chlortoluron, metobromuron, fluometuron or isoproturon. 7. Flowable herbicidal composition according to item 1, characterized in that in addition to a urea derivative of the formula I, another solid, sparingly soluble in water herbicidal active ingredient from the class of Diphenylätherderivate, Phenoxyphenoxyalkancarbonsäurederivate, nitroanilines, Halogenacetaniline, O-Aryloxime, triazines, Benzamidderivate, Sulfanoylhamstoffe halogenated ^ pyridyloxyalkanecarboxylic acid, imidazolinylbenzoic acid derivatives, imidazolinyl nicotinic acid derivatives, N-substituted halopyrrolidinones, hydroxybenzonitriles and benzothiadiazinone derivatives. ... - - ~ "" '. 8. A flowable herbicidal composition according to items 1 and 7, characterized in that, in addition to a herbicidally active urea derivative of the formula I, a further solid, sparingly soluble in water herbicidal active substance from the group 5- (2,4-dichlorophenoxy) -2-nitrobenzoesäuremethylester, 2-Chloro-6-nitro-3-phenoxyaniline, 2- (2-chloro-4-trifluoromethyl-phenoxy) -5-nitrophenyl-phosphonic acid dimethyl ester, 2- [4- (3-trifluoromethylphenoxy) -phenyl] -3- ethoxycarbonyl-4-oxo-5-ethyl-5,6-dihydropyran, a- [4- (2,4-dichlorophenoxy) -phenoxy] -propionic acid methyl ester, N- (1-ethyl-propyl) -2,6-dinitro-3, 4-xylidine, N-1-methyl-1-methoxyethyl-N-chloroacetyl, 4-dimethylaniline, 3,5-dibromo-4-hydroxybenzaldehyde, 0-2,4-dinitrophenyloxime, 2-ethylamino-4-tert-butylamino 6-methylthio-1,3,5-triazine, 2,4-bis-isopropylamino-6-methylthio-1,3,5-triazine, -2,4-bis-isopropylaminol-6-ethylthio-1,3,5-triazine , N- [3- (1-Ethyl-1-methylpropyl-5-isoxazolyl] -2,6-dimethoxybenzamide, N- [2- (2-chloroethoxy) -phenylsulfonyl] -N '- (4-m ethoxy-6-methyl-1,3,5-triazin-2-yl) urea, N- (2-chlorophenyl-sulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazine-2 -yl) -urea, N- (2-methoxycarbonylphenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea, 2- (4-amino-3, Methyl 5-dichloro-6-fluoropyrid-2-yloxy (-acetic acid, 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -4-methylbenzoate, 2- (4-isopropyl- Methyl 4-methyl-5-oxo-2-imidazolin-2-yl) -5-methylbenzoate, 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid, 1- ( 3-trifluoromethylphenyl) -2-chloro-4-chloromethyl-2-pyrrolidone, 3,5-dibromo-4-hydroxybenzonitrile, 3,5-diiodo-4-hydroxybenzonitrile or 3-isopropyl- (1H) -benzo-2, 1,3-thiadiazin-2-one-2,2-dioxide. 9. Flowable herbicidal composition according to items 1 and 7, characterized in that, in addition to a urea derivative derformel I, another solid, sparingly soluble in water active substance from the group 5- (2,4-dichlorophenoxy) -2-nitrobenzoesäuremethylester, N- (1-methyl-2-methoxyethyl) -N-chloroacetyl-2,6-dimethyiliniline, 2-ethylamino-tert-butylamino-e-methoylthio-1'-triazine ^^ -bis-isopropylamino e-methylthio-IS3-triazine, 2,4-bis-isopropylamino-6-ethylthio-1,3,5-triazine, N- [2- (2-chloroethoxy) -phenylsulfonyl] -N '- (4-methoxy-6 -methyl-1,3,5-triazin-2-yl) urea, N- (2-chlorophenyl-sulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazine-2-yl) yl) urea, N- (2-methoxy-carbonylphenylsulfonyl) -N '- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea. 10. A flowable herbicidal composition according to item 1, characterized in that it contains as mono- and di- (phenolpolyglykoläther) phosphoric acid ester of formula II a triethanolamine salt of a mixture of a mono- and di- (phenolpolyglykoläther) phosphoric acid ester of the formula II. 11. Flowable herbicidal composition according to items 1 and 10, characterized in that one uses mono- and di- (phenolpolyglykoläther) phosphoric acid ester of the formula II, in which R ₉ n-nonyl and styryl, m 1-3 and η 6-26 means. 12. Flowable herbicidal composition according to items 1 and 2, characterized in that they are mono- and di- (phenolpolyglykoläther) -phosphorsäureester of formula II mono- and di- (tristyrylphenol-hexadecaglykoläther) phosphoric acid ester, mono- and di-Ctristyrylphenoloctadecaglykolätherl- phosphoric acid esters, mono- and di (tristyrylphenol nonadecaglycol ether) phosphoric acid esters, mono- and di- (tristyrylphenoleicosaglycol ether) -phosphoric acid esters, mono- and di-tristyrylphenol cocoaglycol ether-phosphoric acid esters, mono- and di- (nonylphenolhexaglycol ether) phosphoric acid esters, mono- and di-inonylphenolactaglycol ethers phosphoric acid ester and mono- and di- (nonylphenol nonaglycol ether) phosphoric acid ester. 13. A flowable herbicidal composition according to items 1 and 10, characterized in that it is the triethanolamine salt of a mixture of mono- and di- (2,4,6-tristyrylphenolpolyglycol ethers) as mono- and di (phenolpolyglycol ether) phosphoric ester derivative of the formula II. ester phosphate having an average of 20 ethylene glycol units in the polyglycol ether portion, the triethanolamine salt of a mixture of mono- and di (2,4,6-tristyrylphenol polyglycol ether) ester phosphate with 16-20 ethylene glycol units in the polyglycol ether portion, the triethanolamine salt of a mixture of mono- and di (2, 4,6-tristyrylphenol polyglycol ether) ester phosphate having an average of 18 ethylene glycol units in the polyglycol ether portion, the potassium salt of a mixture of mono- and di- (nonylphenol polyglycol ether) residual phosphate having an average of 6 ethylene glycol units in the polyglycol ether portion, the potassium salt of a mixture of mono- and di- (nonylphenol polyglycol ethers); ester phosphate with an average of 8 Aethylenglykoleinheiten in Polyglykolätherteil or the potassium salt of a mixture of mono- and di- (nonylphenolpolyglykoläther) ester phosphate with an average of 9 ethylene glycol units in Polyglykolätherteil contains. 14. Flowable herbicidal composition according to item 1, characterized in that it contains a polyglycol ether of the formula III, which has 1-3 ethylene glycol units contains. -3- 755 64 15. Flowable herbicidal composition according to items 1 and 10, characterized in that it contains as Polyglykoläther of formula III nonylphenol monoglycol ether, Nonylphenoldiglykoläther, Nonylphenoltriglykoläther or mixtures of such Nonylphenolglykoläther or Oleyldiglykoläther. Field of application of the invention The present invention relates to flowable herbicidal compositions in the form of aqueous suspensions which consist of at least one solid disperse phase and a continuous aqueous phase and which contain as active component at least one herbicidally active urea derivative. The herbicidal compositions according to the invention are active substance concentrates which are intended for the transport and storage of herbicidal compositions. These active substance concentrates are brought to a suitable concentration for the respective application before use by dilution with water.