CN109757502A - Herbicidal combinations, herbicidal formulations and preparation method thereof - Google Patents

Abstract

The present invention provides a kind of Herbicidal combinations comprising: 2,4-D dimethylamine salts, diuron and terbutryn, the mass ratio of 2, the 4-D dimethylamine salt, diuron and terbutryn are 1:(1~6): (1~6).Present invention also provides a kind of herbicidal formulations, are made of above-mentioned Herbicidal combinations and auxiliary material pesticide-acceptable, and present invention also provides the preparation methods of herbicidal formulations.Herbicidal combinations provided by the present application make its synergistic effect, effectively expand degrass spectrum, improve herbicidal effect, slow down the generation of drug resistance by compounding 2,4-D dimethylamine salt, diuron and terbutryn；Further, due to using specific dispersing agent in herbicidal formulations, and make herbicidal formulations that there is preferable stability.

Description

Herbicidal combinations, herbicidal formulations and preparation method thereof

Technical field

The present invention relates to technical field of pesticide more particularly to Herbicidal combinations, herbicidal formulations and preparation method thereof.

Background technique

2,4-D be systemic herbicide, can be entered in plant from root, stem, leaf, and degradation slowly, therefore can accumulate certain dense Degree destroys nucleic acid and protein metabolism, promotes or inhibit certain organ growths, make miscellaneous so that plant hormone in vivo be interfered to balance The distortion of grass blade leaf, stem foot is thicker, swells and splits.

Diuron (Diuron, C₉H₁₀Cl₂N₂It O) is interior suction steriland herbicide, herbicide range is very wide, to 1 year most of Life, perennial weeds are all effective, generally make soil treatment, are absorbed into aerial part by weeds root system, inhibit photosynthesis, first There is " scarce chlorine " symptom, it is last malnutritive and withered.Diuron mainly prevents and kill off upland weeds, such as herba digitariae grass, herba setariae viridis, drought Barnyard grass, emarginate amaranth herb or seed, chenopodium album linn etc. can also prevent and kill off rice field bog pondweed, four leaf duckweed, fescue etc..

Terbutryn (Terbutryn, C₁₀H₁₉N₅S), inner-adsorption conduction-type herbicide, before can be used for bud, weeding after bud, in soil Lasting period 3-10 weeks；It is mainly used for winter wheat, barley, sorghum, sunflower, potato, pea, soybean, fields of peanut and other crops, Prevent and kill off herba stellariae mediae, amur foxtail, herba digitariae, the herba setariae viridis etc. that perennial naked barley grass, rye grass and autumn sprout.

2,4-D, diuron and terbutryn are sugarcane field Common Herbicides, but as a large amount of of each single dose make for a long time With part weeds generate obvious resistance, this just needs to solve the problems, such as that control efficiency is poor by compounding.Secondly, multivariate product Poor compatibility when bucket is mixed the problems such as easily flocculation after bucket is mixed, easily blocks spray head and the problem of phytotoxicity, drug effect difference occurs.

Summary of the invention

Present invention solves the technical problem that being to provide a kind of Herbicidal combinations and herbicidal formulations, weeding provided by the present application Composition has preferable herbicidal effect, and further, herbicidal formulations stability is good.

In view of this, this application provides a kind of Herbicidal combinations, comprising: 2,4-D dimethylamine salts, diuron and Te Ding Only, the mass ratio of 2, the 4-D dimethylamine salt, diuron and terbutryn is 1:(1~6): (1~6).

Preferably, the mass ratio of 2, the 4-D dimethylamine salt, diuron and terbutryn is 1:(1~3): (1~3).

Preferably, the mass ratio of 2, the 4-D dimethylamine salt, diuron and terbutryn is 1:1.5:1.8.

Present invention also provides application of the Herbicidal combinations in management of weeds.

Present invention also provides a kind of herbicidal formulations, comprising: can connect in Herbicidal combinations described in above scheme and pesticide The auxiliary material received.

Preferably, the auxiliary material includes dispersing agent, wetting agent, defoaming agent, thickening stabilizing agent and antifreeze.

Preferably, the wetting agent be one of alkylbenzene sulfonate and alkyl sulfate that mass ratio is 3:5 with The mixture of lignosulfonates；The dispersing agent is the dodecyl polyoxyethylene ether phosphate and poly- carboxylic that mass ratio is 2:3 The mixture of hydrochlorate；The defoaming agent be selected from organosiloxane, the fatty acid ester compounded object of higher alcohols, organosilicon ketone and C8~ One of fatty alcohol of C10；The antifreeze is selected from one of glycerine, ethylene glycol and diethylene glycol (DEG) or a variety of；The increasing Thick stabilizer is selected from one of carboxymethyl cellulose, xanthan gum, Sodium Polyacrylate and aluminium-magnesium silicate.

Oleamide, the dosage form of the herbicidal formulations is suspending agent.

Preferably, the content of the Herbicidal combinations is 100~600g/L.

Present invention also provides a kind of preparation methods of herbicidal formulations, comprising the following steps:

Ball milling after diuron, terbutryn, auxiliary material and water are mixed, adds 2,4-D dimethylamine salt, obtains herbicidal formulations.

Preferably, the time of the ball milling is 2~3h, and the partial size of the mixture after ball milling is less than 5 μm.

This application provides a kind of Herbicidal combinations comprising: 2,4-D dimethylamine salts, diuron and terbutryn, described 2, The mass ratio of 4-D dimethylamine salt, diuron and terbutryn is 1:(1~6): (1~6).The application is by by 2,4-D dimethylamine Salt, diuron are compounded with terbutryn, and the Herbicidal combinations made can expand degrass spectrum, are improved weeding ratio, are slowed down anti- Pharmacological property generates.Further, the weeding water that herbicidal formulations provided by the present application are made due to the specific dispersing agent of use is outstanding Floating agent stability is good.

Specific embodiment

For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention Limitation.

For the problem of 2,4-D, diuron and terbutryn single dose weeding control efficiency difference, the embodiment of the invention discloses one Kind Herbicidal combinations comprising: it include: 2,4-D dimethylamine salt, diuron and terbutryn, 2, the 4-D dimethylamine salt, enemy's grass Grand and terbutryn mass ratio is 1:(1~6): (1~6).

In certain specific embodiments, the mass ratio of 2, the 4-D dimethylamine salt, diuron and terbutryn is 1:(1 ~3): (1~3)；In certain specific embodiments, the mass ratio of 2, the 4-D dimethylamine salt, diuron and terbutryn is 1:1.5:1.8.

The application makes three act synergistically, finally by being compounded 2,4-D dimethylamine salt, diuron and terbutryn The Herbicidal combinations enable expand degrass spectrum, improve herbicidal effect, slow down drug resistance generation.

Further, the application present invention also provides the Herbicidal combinations in management of weeds.

Present invention also provides a kind of herbicidal formulations comprising is subjected in Herbicidal combinations described in above scheme and pesticide Auxiliary material.

According to the present invention, the auxiliary material is the common auxiliary material of those skilled in the art, and more specifically, the auxiliary material, which is selected from, to be divided Powder, wetting agent, defoaming agent, thickening stabilizing agent and antifreeze.Wherein, the wetting agent is selected from alkylbenzene sulfonate, alkylbenzene One of sulfate, alkylnaphthalene sulfonate condensation polymer, alkylphenol-polyethenoxy base ether and lignosulfonates are a variety of, are having In body embodiment, the wetting agent be one of the alkylbenzene sulfonate that mass ratio is 3:5 and alkyl sulfate with it is wooden The mixture of plain sulfonate.The dispersing agent is selected from double naphthalenesulfonate formaldehyde condensation compounds, alkylamide polyoxyethylene ether, polycarboxylic acids Salt, polyoxyethylene polyoxypropylene base ether block copolymers, dodecyl polyoxyethylene ether phosphate and alkyl phenol polyoxyethylene ether One or more of formaldehyde condensation products sulfate；In a particular embodiment, the dispersing agent is ten that mass ratio is 2:3 The mixture of dialkyl group polyoxyethylene ether phosphate and polycarboxylate.

The defoaming agent be selected from organosiloxane, the fatty acid ester compounded object of higher alcohols, organosilicon ketone and C8~C10 rouge One of fat alcohol, in a particular embodiment, the defoaming agent are selected from organosilicon ketone compound；The antifreeze is selected from the third three One of alcohol, ethylene glycol and diethylene glycol (DEG) are a variety of, and in a particular embodiment, the antifreeze is selected from ethylene glycol；The thickening Stabilizer is selected from one of carboxymethyl cellulose, xanthan gum, Sodium Polyacrylate and aluminium-magnesium silicate.Herein described herbicidal formulations Dosage form be it is well known to those skilled in the art, this application is not particularly limited；In a particular embodiment, the weeding The dosage form of preparation is aqueous suspension agent, and stability is good, is not in precipitation, susceptible to plugging problem；The composition pesticide is in institute The content stated in herbicidal formulations is 100~600g/L, and in a particular embodiment, the composition pesticide is in the herbicidal formulations Content be 300~500g/L.

The present invention also provides the preparation methods of the herbicidal formulations, comprising the following steps:

Ball milling after diuron, terbutryn, auxiliary material and water are mixed, adds 2,4-D dimethylamine salt, obtains herbicidal formulations.

During preparing herbicidal formulations, the application first mixes diuron, terbutryn, auxiliary material and water, in order to make Above-mentioned raw materials are uniformly mixed, and the mixed mode is high speed shear mixing；The diuron, terbutryn, auxiliary material it is above-mentioned into It has gone detailed description, has no longer been repeated herein.Ball milling is then carried out after blending, and the ball milling is that those skilled in the art are ripe The technical approach known is not particularly limited this application.The time of the ball milling is 2~3h.Mixture after ball milling Partial size is 5 μm hereinafter, with the stability of the herbicidal formulations of guarantee preparation.

2,4-D dimethylamine salt is then added after milling to be mixed again to get herbicidal formulations are arrived.2,4-D diformazan is added afterwards Sand milling efficiency can be improved in amine salt, reduces the probability that livering is sanded.The herbicidal formulations being prepared at this time are suspending agent, with good Good stability.

In this application, the diuron, terbutryn and 2,4-D dimethylamine salt respectively represent diuron original drug, terbutryn Raw medicine and 2,4-D dimethylamine salt raw pesticide.

Preparation method about herbicidal formulations further includes two kinds: 1) 2,4-D dimethylamine salt is dissolved in water, adds other groups Point, it is sanded；2) all components are added, and are sanded；Preparation method provided by the present application compared to above two method, grinding is fast, Production capacity is high, the preparation of the aqueous suspension agent suitable for high-content, and quality is stablized.

For a further understanding of the present invention, herbicidal formulations provided by the invention are carried out specifically below with reference to embodiment Bright, protection scope of the present invention is not limited by the following examples.

Embodiment 1

By dodecyl polyoxyethylene ether phosphate 20g/L, polycarboxylate 30g/L, alkylbenzene sulfonate or sulfate 3g/ L, lignosulfonates 5g/L, ethylene glycol 50g/L, silicone compound 5g/L, aluminium-magnesium silicate 1.5g/L, xanthan gum 1g/L and Water is uniformly mixed by high speed shear, is added diuron original drug 140g/L, terbutryn 165g/L, is sanded in sand mill 1~2 hour, make diameter of particle all at 5 μm hereinafter, 95g/L 2 is then added, 4-D dimethylamine salt (acid meter) raw medicine high speed is cut Mixing is cut, weeding suspending agent product is made.

Embodiment 2

By dodecyl polyoxyethylene ether phosphate 40g/L, polycarboxylate 10g/L, alkylbenzene sulfonate or sulfate 3g/ L, lignosulfonates 5g/L, ethylene glycol 50g/L, silicone compound 5g/L, aluminium-magnesium silicate 1.5g/L, xanthan gum 1g/L and Water is uniformly mixed by high speed shear, is added diuron original drug 140g/L, terbutryn 165g/L, is sanded in sand mill 1~2 hour, make diameter of particle all at 5 μm hereinafter, 95g/L 2 is then added, 4-D dimethylamine salt (acid meter) raw medicine, then high speed Shearing mixes, and weeding suspending agent product is made.

Embodiment 3

By dodecyl polyoxyethylene ether phosphate 60g/L, alkylbenzene sulfonate or sulfate 3g/L, lignosulfonates 5g/L, ethylene glycol 50g/L, silicone compound 5g/L, aluminium-magnesium silicate 1.5g/L, xanthan gum 1g/L and water pass through high speed shear It is uniformly mixed, adds diuron original drug 140g/L, terbutryn 165g/L, be sanded 1~2 hour, make micro- in sand mill All at 5 μm hereinafter, 95g/L 2 is then added, 4-D dimethylamine salt (acid meter) raw medicine, then high speed shear mix grain partial size, are made Weeding suspending agent product.

Embodiment 4

By alkylamide polyoxyethylene ether 30g/L, polyoxyethylene polyoxypropylene base ether block copolymers 20g/L, lignin Sulfonate 3g/L, glycerine 50g/L, organosiloxane 4g/L, carboxymethyl cellulose 5g/L, xanthan gum 1g/L and water are through excessively high Fast shear-mixed is uniform, adds diuron original drug 33.3g/L, terbutryn 33.3g/L, and it is small that 1~2 is sanded in sand mill When, make diameter of particle all at 5 μm hereinafter, 33.3g/L 2 is then added, 4-D dimethylamine salt (acid meter) raw medicine, then high speed shear It mixes, weeding suspending agent product is made.

Embodiment 5

By dodecyl polyoxyethylene ether phosphate 60g/L, alkylbenzene sulfonate or sulfate 3g/L, alkyl phenol polyoxy second Alkene ether 8g/L, diethylene glycol (DEG) 60g/L, higher alcohols fatty acid ester compounded object 4.5g/L, aluminium-magnesium silicate 1.5g/L, Sodium Polyacrylate 10g/L and water are uniformly mixed by high speed shear, diuron original drug 100g/L, terbutryn 150g/L are added, in sand It is sanded 1~2 hour in grinding machine, makes diameter of particle all at 5 μm hereinafter, 50g/L 2 is then added, 4-D dimethylamine salt (acid meter) Raw medicine, then high speed shear mix, and weeding suspending agent product is made.

Embodiment 6

By polycarboxylate 30g/L, polyoxyethylene polyoxypropylene base ether block copolymers 30g/L, lignosulfonates 8g/L, Diethylene glycol (DEG) 60g/L, C8~C10 fatty alcohol 6g/L, xanthan gum 2g/L and water are uniformly mixed by high speed shear, add enemy The grand raw medicine 214.2g/L of grass, terbutryn 214.2g/L, are sanded 1~2 hour in sand mill, make diameter of particle all in 5 μ Hereinafter, 71.6g/L 2 is then added, 4-D dimethylamine salt (acid meter) raw medicine, then high speed shear mix m, and weeding suspending agent is made and produces Product.

Embodiment 7

By polyoxyethylene polyoxypropylene base ether block copolymers 25g/L, dodecyl polyoxyethylene ether phosphate 45g/L, Alkylbenzene sulfonate or sulfate 3g/L, alkylphenol-polyethenoxy base ether 4g/L, lignosulfonates 2g/L, ethylene glycol 50g/L, The fatty acid ester compounded object 4g/L of higher alcohols, aluminium-magnesium silicate 1.5g/L, carboxymethyl cellulose 8g/L and water are mixed by high speed shear It closes uniformly, adds diuron original drug 277g/L, terbutryn 277g/L, be sanded 1~2 hour in sand mill, make particle All at 5 μm hereinafter, 46g/L 2 is then added, 4-D dimethylamine salt (acid meter) raw medicine, then high speed shear mix partial size, are made and remove Careless suspending agent product.

Embodiment 8

By double naphthalenesulfonate formaldehyde condensation compound 65g/L, APES formaldehyde condensation products sulfat 10g/L, alkane Base benzene sulfonate or sulfate 3g/L, alkyl sulfate 3g/L, alkylnaphthalene sulfonate condensation polymer 3.5g/L, glycerine 60g/L, Organosiloxane 4.5g/L, aluminium-magnesium silicate 10g/L and water are uniformly mixed by high speed shear, add diuron original drug 270g/L, terbutryn 90g/L are sanded 1~2 hour in sand mill, make diameter of particle all at 5 μm hereinafter, then adding Enter 90g/L2,4-D dimethylamine salt (acid meter) raw medicine, then high speed shear to mix, weeding suspending agent product is made.

Comparative example 1

By double naphthalenesulfonate formaldehyde condensation compound 45g/L, APES formaldehyde condensation products sulfat 30g/L, alkane Base benzene sulfonate or sulfate 1g/L, alkyl sulfate 4g/L, alkylnaphthalene sulfonate condensation polymer 3.5g/L, ethylene glycol 60g/L, Organosiloxane 3.5g/L, aluminium-magnesium silicate 10g/L and water are uniformly mixed by high speed shear, add diuron original drug 160g/L, terbutryn 160g/L are sanded 1~2 hour in sand mill, make diameter of particle all at 5 μm hereinafter, then adding Enter 20g/L 2,4-D dimethylamine salt (acid meter) raw medicine, then high speed shear to mix, weeding suspending agent product is made.

Comparative example 2

By dodecyl polyoxyethylene ether phosphate 60g/L, alkylbenzene sulfonate or sulfate 5g/L, alkyl phenol polyoxy second Alkene ether 2g/L, diethylene glycol (DEG) 60g/L, higher alcohols fatty acid ester compounded object 4.5g/L, aluminium-magnesium silicate 2.5g/L, Sodium Polyacrylate 10g/L and water are uniformly mixed by high speed shear, diuron original drug 110g/L, terbutryn 110g/L are added, in sand It is sanded 1~2 hour in grinding machine, makes diameter of particle all at 5 μm hereinafter, 220g/L2 is then added, 4-D dimethylamine salt (acid meter) Raw medicine, then high speed shear mix, and weeding suspending agent product is made.

Comparative example 3

By alkylamide polyoxyethylene ether 40g/L, polyoxyethylene polyoxypropylene base ether block copolymers 25g/L, lignin Sulfonate 3.8g/L, glycerine 50g/L, organosiloxane 5g/L, xanthan gum 1.5g/L and water are equal by high speed shear mixing It is even, diuron original drug 240g/L is added, is sanded 1~2 hour in sand mill, makes diameter of particle all at 5 μm hereinafter, then 40g/L 2,4-D dimethylamine salt (acid meter) raw medicine, then high speed shear is added to mix, weeding suspending agent product is made.

Comparative example 4

By dodecyl polyoxyethylene ether phosphate 40g/L, polyoxyethylene polyoxypropylene base ether block copolymers 25g/L, Alkylbenzene sulfonate or sulfate 4g/L, alkylphenol-polyethenoxy base ether 3g/L, glycerine 60g/L, high-carbon alcohol fatty acid ester are multiple Object 4.5g/L is closed, aluminium-magnesium silicate 1.8g/L, Sodium Polyacrylate 10g/L and water are uniformly mixed by high speed shear, add spy The net raw medicine 210g/L of fourth is sanded 1~2 hour in sand mill, makes diameter of particle all at 5 μm hereinafter, 70g/L is then added 2,4-D dimethylamine salts (acid meter) raw medicine, then high speed shear mix, and weeding suspending agent product is made.

Comparative example 5

By polycarboxylate 40g/L, polyoxyethylene polyoxypropylene base ether block copolymers 35g/L, lignosulfonates 3g/L, Lignosulfonates 4g/L, diethylene glycol (DEG) 60g/L, C8~C10 fatty alcohol 6g/L, xanthan gum 2g/L and water pass through high speed shear It is uniformly mixed, adds diuron original drug 140g/L, terbutryn 140g/L, be sanded 1~2 hour, make micro- in sand mill Grain partial size is all at 5 μm hereinafter, be made weeding suspending agent product.

The stability data table of the herbicidal formulations of 1 embodiment of table preparation

Known by table 1, in embodiment 2-8, heat storage after quality be deteriorated, and use preferred promoter embodiment 1 heat storage before and After heat storage, quality is good, and preferred promoter plays key effect in product quality.

9 sugarcane field control of weeds field control effectiveness test of embodiment

1) test medicine

Embodiment 1-8 and comparison medicament (comparative example 1-5).

2) experimental condition and application method

This experiment is arranged in the progress of Changtai County, Zhangzhou City, Fujian Province, and sugarcane field soil fertility is medium, pH value 7.2.Test When, 15 days after cane planting, the weeds 3-5 leaf phase is oriented spraying medicament.Instrument used is -16 type back carried hand of workers and peasants Sprayer.Entire test process sprays 1 time altogether, and 750kg/ hectares of water consumption.Weather is good during test, and the application same day is fine, day 27.3 DEG C of temperature on average, relative humidity 60%, the front and back application 48h is without rainfall.

Sugarcane field main weeds are as follows: herba digitariae, herba eleusines indicae, Myriogyne minuta, Mazus japonicus, Ageratum conyzoides, purslane etc., each weeding control effect Relatively uniformly.

3) investigation method

30d investigates weeds remaining strain number, fresh weight after medicine, and calculates strain number preventive effect and fresh weight preventive effect；It is indefinite after medicine simultaneously Phase observes sugarcane production situation, and whether there is or not the generations of phytotoxicity for observation.

Calculation formula is as follows:

The check plot is clear water check plot, does not spray medicament.

4) experimental result

During experiment, invention formulation has no adverse effects to target crop in test scope of medication, and control efficiency is shown in The following table 2.

2 2,4-D of table, diuron, terbutryn compound preparation are to the control efficiency of sugarcane field weed

As can be seen from Table 2, the generation that sugarcane field weed can be effectively prevented after 2,4-D, diuron, terbutryn compounding, prevents It controls effect and is superior to comparison medicament；Preferred promoter and the embodiment preventive effect of optimum ratio will be substantially better than other embodiments, and right Sugarcane field Weed-control effect is up to 85% or more, wherein preventive effect is 95% or more with the preventive effect highest of embodiment 1.

The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.

The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one The widest scope of cause.

Claims (11)

1. a kind of Herbicidal combinations, comprising: 2,4-D dimethylamine salts, diuron and terbutryn, 2, the 4-D dimethylamine salt, enemy's grass Grand and terbutryn mass ratio is 1:(1~6): (1~6).

2. Herbicidal combinations according to claim 1, which is characterized in that 2, the 4-D dimethylamine salt, diuron and Te Ding Net mass ratio is 1:(1~3): (1~3).

3. Herbicidal combinations according to claim 1, which is characterized in that 2, the 4-D dimethylamine salt, diuron and Te Ding Net mass ratio is 1:1.5:1.8.

4. application of the described in any item Herbicidal combinations of claims 1 to 3 in management of weeds.

5. a kind of herbicidal formulations characterized by comprising in the described in any item Herbicidal combinations of claims 1 to 3 and pesticide Acceptable auxiliary material.

6. herbicidal formulations according to claim 5, which is characterized in that the auxiliary material includes dispersing agent, wetting agent, defoaming Agent, thickening stabilizing agent and antifreeze.

7. herbicidal formulations according to claim 6, which is characterized in that the wetting agent is the alkylbenzene that mass ratio is 3:5 The mixture of one of sulfonate and alkyl sulfate and lignosulfonates；The dispersing agent is that mass ratio is 2:3's The mixture of dodecyl polyoxyethylene ether phosphate and polycarboxylate；The defoaming agent is selected from organosiloxane, high-carbon alcohol ester One of fat acid esters compound, organosilicon ketone and fatty alcohol of C8~C10；The antifreeze is selected from glycerine, ethylene glycol With one of diethylene glycol (DEG) or a variety of；The thickening stabilizing agent is selected from carboxymethyl cellulose, xanthan gum, Sodium Polyacrylate and silicic acid One of magnalium.

8. herbicidal formulations according to claim 5, which is characterized in that the dosage form of the herbicidal formulations is suspending agent.

9. herbicidal formulations according to claim 8, which is characterized in that the content of the Herbicidal combinations is 100~600g/ L。

10. a kind of preparation method of herbicidal formulations, comprising the following steps:

Ball milling after diuron, terbutryn, auxiliary material and water are mixed, adds 2,4-D dimethylamine salt, obtains herbicidal formulations.

11. herbicidal formulations according to claim 10, which is characterized in that the time of the ball milling is 2~3h, after ball milling The partial size of mixture is less than 5 μm.