JPH02295907A - Liquid concentrated composite based on n- phosphonomethylglycine - Google Patents

Abstract

PURPOSE: To obtain the subject herbicidal composition excellent in rapid dispersibility and high in concentration, comprising N-phosphonomethylglycine and/or one derivative of N-phosphonomethylglycine having fixed intrinsic water solubility, and a specific surfactant in an (aqueous) organic solvent. CONSTITUTION: This composition comprises an (aqueous) organic solvent dispersion containing (a) N-phosphonomethylglycine and/or one derivative of N- phosphonomethyl glycine having >5g/L, preferably >9g/L intrinsic water solubility (N-phosphonomethyl glycine and/or its derivative exists in the ratio of at least glyphosate equivalent and at least a part of the N-phosphonomethylglycine or its derivative is in an insoluble state in a considered medium) and (b) a surfactant of the formula (R is an 8-22C alkyl, etc.; A is an alkylene; (n) and (n') are 2-40 in terms of n+n'; R<1> is H, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel concentrated compositions based on compounds containing N-phosphonomethylglycine or N-phosphonomethylglycyl groups.

N-phosphonomethylglycine (sometimes referred to as glyphosate) and its analogous compounds, and their herbicidal properties and compositions containing them, are described in particular in U.S. Pat.
No. 799,758. Although a number of water-soluble and water-insoluble derivatives of glyphosate are known, in practice it is generally preferred to use water-soluble derivatives, N-
This is why phosphonomethylglycine salts, especially inpropylammonium salts, are commonly developed or commercially available.

More recently, European Patent Application No. 290416
, N-phosphonomethylglycine in the acid form, but in any case the N-phosphonomethylglycine and/or
The development of N-phosphonomethylglycine salt-based concentrates containing N-phosphonomethylglycine or derivatives thereof in soluble or solubilized form has been undertaken. These concentrates are solutions characterized by the presence of an activator, which is a special type of alkoxylated amine. The alkoxylated amine must have no more than 12 alkoxy groups per molecule and must have surfactant properties such that N
- The herbicidal activity of phosbomethylglycine derivatives must be promoted. 1oo~6001 at least outdoors
For the production of concentrates applied in the form of dilute spray mixtures at a rate of N
- Can be used in smaller amounts than known surfactants in known compositions containing phosphonomethylglycine.

Compositions containing a substantially water-insoluble tetraaluminum salt of N-phosphonomethylglycine and a special type of surfactant have also been proposed (U.S. Pat. No. 4,528,029).
No. 3). Such insolubility of the active substance results in that when the concentrate is diluted with water to obtain the final spray mixture for spraying, this spray mixture is not in complete solution form and cannot be used satisfactorily. It is disadvantageous to obtain the effect. However, the person skilled in the art did not attempt to apply the composition of the patent to more soluble active substances. This is because experience has shown that it is very difficult to produce concentrated suspensions from partially soluble active substances, since concentrated suspensions tend to coagulate.

One of the reasons for these difficulties and solidification is the strong tendency for crystal growth in the continuous (aqueous) layer of the suspension. This growth can progress to extremes until coagulation occurs.

One of the objects of the present invention is to provide a composition based on N-phosphonomethylglycine or its derivatives and having a much higher concentration of active substance than similar compositions known in the prior art. .

Another object of the invention is to incorporate adjuvants such as inorganic ammonium salts into a concentrate based on N-phosphonomethylglycine or its derivatives and at a much higher concentration than in similar compositions known in the prior art. Another object of the present invention is to provide a composition that may further include:

Another object of the invention is to provide a concentrate based on N-phosphonomethylglycine or its derivatives which produces a dilute spray mixture with good herbicidal activity.

Another object of the invention is to use one or more surfactants based on N-phosphonomethylglycine or derivatives thereof and having an active effect, i.e. having the effect of promoting the biological activity of the active substance, in particular its herbicidal activity. Another object of the present invention is to provide a concentrated composition further comprising an agent.

Another object of the invention is to provide fA condensation compositions based on N-phosphonomethylglycine or derivatives thereof and having favorable properties, such as good and rapid dispersibility in water.

Another object of the invention is to provide a concentrated composition based on N-phosphonomethylglycine or its derivatives and having favorable properties, such as good flowability at low temperatures.

Another object of the invention is to provide a concentrated composition based on N-phosphonomethylglycine or its derivatives and having favorable properties, such as a low foaming rate and the use of antifoam agents. .

Yet another object of the invention is to provide concentrated compositions (also referred to as condensates) based on N-phosphonomethylglycine and in particular a slightly water-soluble single N-phosphonomethylglycine. .

Another object of the invention is to provide compositions based on N-phosphonomethylglycine having the advantages mentioned above and further comprising one or more other herbicides.

It has been found that these objects can be achieved in whole or in part by the compositions of the invention. Unless otherwise specified, ratios in the text are weight/volume ratios (%).

Furthermore, the corresponding amount of product if all the N-phosphonomethylglycine derivatives were in the normal N-phosphonomethylglycine form is referred to as glyphosate equivalent.

These compositions contain: a) N-phosphonomethylglycine and/or 5g/
exceed l. Preferably a derivative of N-phosphonomethylglycine having an inherent solubility in water of greater than 9 g/f [the N-phosphonomethylglycine and/or its derivatives are present in the composition in a proportion of at least 100 g glyphosate equivalents] However, at least a portion of this N-phosphonomethylglycine or its derivatives is in an insoluble form in the considered medium (especially if the amount of N-phosphonomethylglycine and/or its derivatives exceeds the solubility limit in the medium). b) have activator properties and have the formula: where R is a straight or branched alkyl or alkenyl hydrocarbon chain having 8 to 22 carbon atoms;
is an alkylene group, preferably ethylene or propylene, n and n'' are integers such that n + n' is 2 to 40, preferably 16 to 30, more preferably 20 to 25, and R1 is a hydrogen atom Or formyl.

Acetyl, 10 pionyl (i.e. C1, -CH2-C0)
A liquid composition consisting of an organic solvent (concentrated) suspension, or in some cases an aqueous organic solvent (concentrated) suspension, containing a surfactant represented by an acyl group such as benzoyl or an acyl group such as benzoyl. be.

The derivative of N-phosphonomethylglycine is -CO-CI(
, -N-C)1. - means a compound containing the group P.0, preferably a salt, ester or amide. These terms are to be understood in a broad sense to include, for example, sulfonamides.

Of course, instead of this single surfactant, R, n and n
Mixtures of surfactants can be used, where o has on average active agent properties corresponding to the definitions given above.

The herbicidal active substance used according to the invention is therefore N-phosphonomethylglycine and/or a derivative of N-phosphonomethylglycine having an inherent solubility in water of more than 5 g/l, preferably more than 9 g/l. Derivatives that can be used include a number of known derivatives of N-phosphonomethylglycine,
In particular, the salts obtained individually or as a mixture. The most suitable derivatives are sodium salts, potassium salts or inorganic or organic ammonium salts, especially isopropylammonium salts, and sulfonium salts; N-methyl-N-(methylsulfonyl)-N@,N'-(phosphonomethyl)-glycylamine. can be mentioned. Aluminum salts are not included in this invention. Of course, these products must be used in compliance with the ratios and solubility conditions specified elsewhere.

Advantageously, the invention further relates to a concentrated composition of the above-mentioned type having one of the characteristics and/or other characteristics described below.

a) The amount of N-phosphonomethylglycine or its derivative exceeds the solubility limit in the medium considered, preferably 1
20-250g/l, more preferably 160-220g
/L2. The proportion of undissolved derivatives of N-phosphonomethylglycine exceeds 30%, preferably exceeds 75%.

b) The insoluble N-phosphonomethylglycine or its derivatives are in the form of solid particles with a diameter of less than 30 microns, preferably from 1 to 20 microns.

C) The concentrated composition contains ammonium (NH) in a proportion of 100 to 500 g/l, preferably 200 to 350 g/l.
) salts such as nitrates, phosphates, sulfamates (su!phan++1te), thiocyanates or preferably sulfates.

d) Concentrated compositions contain these dilute spray mixtures from 100 to 6
It is diluted by the farmer in a water-containing container so that it can be applied at a rate of 0.001/ha. The active substance itself is 0.125~
Applied at a rate of 1.5 kg/ha.

e) The glyphosate equivalent/surfactant (active agent) weight ratio is between 0.5 and 6, preferably between 0.6 and 2. This relatively large amount of surfactant may have biologically active/herbicidal properties.The compositions of the present invention may also contain any type of other ingredients, especially wetting, dispersing or emulsifying properties, as described below. It is contemplated that a wide variety of surfactants may further be included. These surfactants can then be used in doses that are much lower than the active agent dose.

f) The solvent is preferably an organic solvent that is miscible with water and may contain up to 50%, preferably less than 30% water. In this solvent, N-phosphonomethylglycine is unevenly dissolved, that is, the dissolved amount is less than SQ, 71, preferably 40 g.
It is less than 71.

The concentrated suspensions of the invention are produced in such a way as to obtain a stable fluid product that does not settle (milling).

The concentrated suspensions of the invention usually contain 10-75% active substance (herbicide), 0.5-40% surfactant with active agent properties and 10-50% ammonium salt (adjuvant). and,
0.1 to 10% of conventional surfactants, i.e. surfactants with dispersing and/or wetting and/or emulsifying properties;
0% of suitable additives (antifoams, corrosion inhibitors, protective colloids, thickeners, sequestering agents, thixotropic or pseudoplastic agents, stabilizers, penetrants and adhesives); The carriers include organic liquids in which the active substances are slightly soluble or insoluble. Solid organic substances or inorganic salts may be dissolved or suspended in the carrier to prevent settling or to prevent gelling. More generally, the compounds used according to the invention can be used together with all solid or liquid additives that correspond to conventional manufacturing techniques.

Besides N-phosphonomethylglycine and/or its derivatives, the compositions used according to the invention may contain other known active substances having herbicidal or plant growth regulating properties.

Herbicidal substances that can be mixed with glyphosate derivatives in the compositions of the invention include acifluorfen, aclon
ifen, bifenox, diflufenica
n, asulam, triazines (especially 5iniaz
ine and atrazine), diuron and ox
herbicides of the ad 1azon, hormonal or phenoxy type, especially 2.4-D, 2.4-DB, MCPP, hydroxybenzonitriles (especially bromoxylin
and 1oxynil), imidazoleynones (especially 1
Mention may be made of the following: azaquin and imazapur) and sulfonylureas (in particular chlorsulfuron and metsulfuron). The above-mentioned names are standardized names for herbicides.

These herbicides are most often used in proportions of 1 to 400 parts by weight per 100 parts of glyphosate or glyphosate equivalents. By using the term glyphosate equivalent, all glyphosate derivatives are
These moieties are reduced as if in the form of phosphonomethylglycine.

More precisely, when herbicidal active substances other than glyphosate are used in admixture with glyphosate, the following weight ratios (wr) generally apply:

(The weight ratio is (glyphosate or glyphosate equivalent)/(
other herbicides), glyphosate) +acirluo+(en:
4/1010O3≦9/100 glyphosate) +
diuron or oxadiazon: 2
≦sr≦4 glyphosate + aclonifen:
t/3≦@r≦10/3 glyphosate + bifenox: 1/3≦
wr≦1 glyphosate + dif Iufenican
: 2Swr≦20 glyphosate+as
ulam: 1/4≦wr≦1 glyphosate + phenoxy: 2/3≦-r≦4 glyphosate + hydroxybenzonitrile: 1! sr≦10 glyphosate + triazine = 173≦sr≦1 glyphosate + imidazolinone = 1≦sr≦4 glyphosate sulfonylurea: 100/6≦wr
≦100 The concentrated suspension of the present invention contains an organic solvent (sometimes referred to as carrier) based on what has been described above. The solvent is a natural or synthetic organic or inorganic substance, with which the active substance is used in order to facilitate its application to plants or soil. This solvent is therefore generally inert and acceptable for agriculture, especially plant care. The solvents of the invention are therefore organic liquids, such as esters, especially methyl glycol acetate; ketones, especially cyclohexanone and influorone; petroleum fractions; aromatic hydrocarbons,
In particular, they can be xylene or paraffinic hydrocarbons; aliphatic or aromatic chlorinated hydrocarbons, chlorobenzenes, glycols, especially low molecular weight oligo- or polyglycolic liquids or esterifiable vegetable oils.

Based on what has been described above, the concentrated compositions of the present invention may contain one or more surfactants in addition to the surfactants having the active agent properties described above. The surfactants used can be ionic or nonionic emulsifiers, dispersants or wetting agents, or mixtures of such surfactants. For example,
Salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic acids or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols, fatty acids or fatty amines, substituted phenols (especially alkylphenols or arylphenols), sulfo-amber salts of acid esters, taurine derivatives (especially alkyl taurates),
Mention may be made of phosphoric esters of alcohols or of polycondensates of ethylene oxide and phenol, esters of fatty acids and polyols, and derivatives of said compounds containing sulfate, sulfonate and phosphate functional groups. .

The invention is illustrated in the following non-limiting examples, in particular the concentrated suspensions of the invention, the use of said suspensions and the method of making said suspensions.

Example I N-phosphonomethylglycine (acid) 2
00g 7N ammonium sulfate (auxiliary agent)
200g//Surfactant (active agent) as defined below: 200g/fDispersant/wetting agent: Polycondensate of ethylene oxide and tris(phenylethyl)phenol phosphate 20F1/1 Ammonium dodecylbenzenesulfonate 10g71 Organopolymer Siloxane oil (antifoaming agent) 2g/(1 bentonite (thixotropic agent) 2g
7ti polyvinyl alcohol (protective colloid)
8g#' Solvent: Propylene glycol 300g7
#! water
250 g/l The surfactant used in this example was a product having the formula: % Formula % [3].

This mixture is ball milled to obtain a concentrated microsuspension in which 73% of N-phosphonomethylglycine is suspended in the form of particles with dimensions of 5 to 20 microns.

A portion of this concentrated suspension was centrifuged and after analysis of the liquid phase 27 g/l of N-phosphonomethylglycine was detected in this liquid phase.

This concentrated composition can be stored a) at 50°C for 1 month, and b) after 1 month is divided into 8 periods of the same period (already at 35°C).
The physicochemical properties were retained even after storage for four periods alternately at 10°C and -10°C.

The iM condensation composition as prepared in this example is then diluted in water by using 11 parts concentrate to 100 parts water. In this way a homogeneous dilute spray mixture is obtained virtually instantly, which can be used for weeds (Portulac
a oleraeeae, Centauria cya
Nus.

5inapis arvensis, Panicum
trichoides and eight butilon theo
phrasti) at a rate of 250 l/ha. Using a dose of 50,067 ha of active substance, the weeds are destroyed with destruction rates of 95%, 100%, 98%, 100% and 100%, respectively.

Example 2 N-phosphonomethylglycine (acid) 2
00g#! Ammonium sulfate (adjuvant)
200g/l Surfactant (active agent) used in Example 1: 200g, #Dispersant/wetting agent: Polycondensate of ethylene oxide and tris(phenylethyl)phenol phosphate 20g/f Ammonium dodecylbenzenesulfonate 10g / β organopolysiloxane oil (antifoaming agent) 2g/l! Polyvinyl alcohol (protective colloid) 8g
/l bentonite (thixotropic agent)
2g/l Solvent: Polyethylene glycol (molecular weight = 400) 5
52 g/l This mixture, when milled as in Example 1, had a stability similar to that of the concentrated composition of Example 1.

Example 3 N-phosphonomethylglycine (acid) 1
25g/10xadiazon
125g/l' Surfactant used in Example 1: 125g/1(NH4)2S0
4 125g, #! Dispersant/wetting agent: Polycondensate of ethylene oxide and tris(phenylethyl)phenol phosphate 20 g/l'ammonium dodecylbenzenesulfonate 10 g/l polycondensate of ethylene oxide and dodecanol (20EO)
50g/l organopolysiloxane oil 2g/N bentonite (thixotropic agent) 2g/fl polyvinyl alcohol (protective colloid>8g/l Solvent: polyethylene glycol (molecular weight = 400) 4
10 g/l This mixture, when milled as in Example 1, had a stability similar to that of the concentrated composition of Example 1.

Example 4 N-phosphonomethylglycine CM>1
25g/l^clonifen
250g/l Surfactant used in Example 1: 125g/1 (NH-
>2S04
125g#! Dispersant/wetting agent: Polycondensate of ethylene oxide and tris(phenylethyl)phenol phosphate 30g71 Propylene glycol Z70g/11120
175g/
4 This mixture, when milled as in Example 1, had stability similar to the concentrated composition of Example 1.

Example 5 N-phosphonomethylglycine (acid) 2
00g/1IC Chlorsulfuron
2g/l Surfactant used in Example 1: 200g/1(NH4)25
0-200g#! Dispersant/wetting agent: Polycondensate of ethylene oxide and tris(phenylethyl)phenol phosphate 14 g/β4:1 ethylene oxide/dodecanol polycondensate 14 g#'
6:1 ethylene oxide/decanol polycondensate 40g#!
Attapulgite (thixotropic agent) 8
g, a sufficient amount of solvent for #11: petroleum distillate containing aromatic hydrocarbons, C9-C1+ compounds. This mixture, when ground as in Example 1, yields a concentrate composition similar to that of Example 1. It had stability.

This concentrated composition is diluted so that 750 g/ha of active substance and 3001/ha of a dilute spray mixture are applied to the weed-covered land. The following destruction rates were observed for the treated weeds: 99.7% (Cer+tauria
cyanus), 97.5% (chrysanthem
um), 80% (Galium aparine), 8
5% (Sinapis alba), 92.5% (Si
napis arvensis), 92.5% (Ste.
llaria media), 93.5% (ΔHrot
iste, nuip), 96.5% (^Iopehur
myosuroides), 98.5% (^ve
na fatua), 97.6% (Loliu+++m
ultiflorum), 97.6% (Phalari
s canariensis) and 82.5% (Poa
annua).

Claims (10)

[Claims] (1)a) N-phosphonomethylglycine and/or 5g
A derivative of N-phosphonomethylglycine (
This N-phosphonomethylglycine and/or its derivative is present in the composition in a proportion of glyphosate equivalents of at least 100 g/l, and at least a portion of this N-phosphonomethylglycine or its derivative is insoluble in the medium considered. b) has activator properties and has a formula: ▲Mathematical formula, chemical formula, table, etc.▼ (wherein R is a straight-chain or branched alkyl having 8 to 22 carbon atoms or is an alkenyl hydrocarbon chain, A
is an alkylene group, preferably ethylene or propylene, n and n' are integers such that n+n' is 2 to 40, and R^1 is a hydrogen atom or formyl, acetyl,
a surfactant represented by propionyl (i.e., an acyl group such as CH_3-CH_2-CO) or benzoyl), or in some cases, an aqueous organic solvent suspension. A concentrated composition comprising N-phosphonomethylglycine and/or a derivative thereof, characterized in that it is a composition. 2. The composition according to claim 1, wherein (2) A is an ethylene or propylene group and/or n+n' is 16-30, preferably 20-25. (3) A claim characterized in that the derivatives of N-phosphonomethylglycine are selected from the group consisting of sodium salts, potassium salts or inorganic or organic ammonium salts, in particular isopropylammonium salts and sulfonium salts, obtained individually or as a mixture. Item 2. The composition according to item 1 or 2. (4) The amount of N-phosphonomethylglycine or its derivatives is above the solubility limit in the medium considered, preferably from 120 to 250 g/l.
The composition according to any one of 3 to 3. (5) Claim 4, characterized in that the amount of N-phosphonomethylglycine or its derivative is 90 to 220 g/l.
The composition described in . (6) The composition according to claim 4 or 5, characterized in that the proportion of undissolved derivatives of N-phosphonomethylglycine exceeds 30%, preferably exceeds 75%. (7) Any of claims 1 to 6, characterized in that the insoluble N-phosphonomethylglycine or its derivative is in the form of solid particles having a diameter of less than 30 microns, preferably from 1 to 20 microns. Composition according to item 1. (8) The composition contains adjuvants such as ammonium salts, especially nitrates, phosphates, sulfamates,
Composition according to any one of claims 1 to 7, characterized in that it can be a thiocyanate or a sulfate. 9. Composition according to claim 8, characterized in that the composition contains adjuvants in a proportion of 50 to 500 g/l, preferably of 100 to 350 g/l. (10) The composition is diluted with water so as to be applied at a rate of 100-600 l/ha, and the active substance itself is 0.125 l/ha.
Composition according to any one of claims 1 to 9, characterized in that it is applied at a rate of ~1.5 kg/ha.