CN114711244B - Composite dispersing agent and application thereof in preparation of water dispersible granule - Google Patents

Composite dispersing agent and application thereof in preparation of water dispersible granule Download PDF

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Publication number
CN114711244B
CN114711244B CN202110003177.7A CN202110003177A CN114711244B CN 114711244 B CN114711244 B CN 114711244B CN 202110003177 A CN202110003177 A CN 202110003177A CN 114711244 B CN114711244 B CN 114711244B
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water dispersible
dispersible granule
dispersing agent
flazasulfuron
composite dispersing
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CN114711244A (en
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王泳强
林琪
包如胜
蒋冰
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Shunyi Co ltd
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Shunyi Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to a composite dispersing agent and application thereof in preparation of water dispersible granules, in particular to flazasulfuron water dispersible granules. The invention is compounded with active ingredients by adding a composite dispersing agent, wherein the composite dispersing agent specifically comprises alkyl naphthalene sulfonate formaldehyde condensate and sulfosuccinic monoester in a specific ratio of 1:1-2. The pesticide water dispersible granule prepared by the invention has better suspension property, dispersibility and stability. Rapidly disintegrates after being added with water, has finer grain diameter, proper viscosity, good fluidity, difficult water separation and sedimentation and good storage stability, has strong stability at-4 ℃ and 54 ℃, the suspension rate is more than 95 percent, no caking exists, and the viscosity is basically kept unchanged. Moreover, the test result proves that the flazasulfuron water dispersible granule has the prevention and treatment efficacy of 98% on nutgrass galingale rhizome and crabgrass, the prevention and treatment level is obviously improved, and the flazasulfuron water dispersible granule has good industrial application value.

Description

Composite dispersing agent and application thereof in preparation of water dispersible granule
Technical Field
The invention relates to the field of pesticide preparations, in particular to a composite dispersing agent and application thereof in preparation of water dispersible granules, and particularly relates to flazasulfuron water dispersible granules.
Background
Flazasulfuron (Flazasulfuron) is a sulfonylurea herbicide that mainly inhibits the reaction of acetolactate synthase, a precursor for the production of side chain amino acids, leucine, isoleucine and valine. Can effectively prevent and remove most of lawn weeds, is suitable for warm-season lawns (zoysia and bermuda grass), and has high safety to lawn weeds. The product has broad weed control spectrum, and can effectively prevent and remove most grass family, sedge family and broadleaf weeds in 3-4 leaf period, and has especially outstanding control effects on barnyard grass, green bristlegrass, garrulous sedge, green amaranth, bluegrass, shepherd's purse, baocai, chickweed and nest.
The water dispersible granule is also called as a dry suspending agent or granular wettable powder, has the particle size of 200-5000 um, and can be rapidly disintegrated when being placed in water to form a high-suspension dispersion system. The water dispersible granule has the following advantages: (1) no dust exists, and the safety to operators is ensured; (2) pesticides which are stable in physicochemical properties, in particular exhibit instability to water; (3) the fluidity is good, the packaging is easy, and the metering is easy; (4) high content of effective components and good dispersibility in water. At present, the water dispersible granule becomes a hot spot for developing new dosage forms, has extremely rapid development, and becomes one of main pesticide dosage forms in the market in China.
The suspension and dispersion rate of the water dispersible granule directly influence the quality of the drug effect, and the main factors influencing the suspension and dispersion rate are more, but the main factors are: the first is the particle size of the particles and the second is the viscosity. In addition, the composition of the adjuvants in the formulation can also have an effect on the suspension rate.
If the pesticide active ingredient is incompatible with the auxiliary ingredient, the problems of incapability of forming due to overlarge particle viscosity or easiness in crushing due to overlarge viscosity, uneven particle size and the like can be generated, so that the suspension rate is reduced, and the absorption of the pesticide to the leaf surface is affected. This is particularly important for stem and leaf treated pesticides, and is derived from factors such as chemically unstable medium (such as impurities brought in raw pesticide) or addition of various auxiliary agents and additives, or when a dispersing agent is selected to be unsuitable, these all cause crosslinking of an adsorption layer, gel and charge to be neutralized or bridging and lap joint of the dispersing agent around particles, so that a protective layer of stable particles is damaged or changed, and further suspension and dispersion performance of the water dispersible granule is affected.
Different from other preparations, the investigation standard of the water dispersible granule also comprises the disintegration property of the water dispersible granule in water. If the formulation of the preparation is imperfect, the strength of the water dispersible granule particles is too high, the disintegration is not facilitated, the strength is too low, the particles are not strong enough and are easy to crush, and the problem that the particles cannot be completely disintegrated to the original particle size is likely to exist in the disintegration process. To a certain extent, the disintegration performance also affects the suspension property and the dispersibility of the water dispersible granule.
Meanwhile, the production process of the water dispersible granule is also required to be completely selected according to the physicochemical properties of the processed pesticide, so that the optimal processing process route is determined.
The existing pesticide water dispersible granule has the following problems:
1. poor physical and chemical properties, especially poor suspension and dispersion, uneven particle size after disintegrating in water, and no suspension, dispersion and disintegration properties meet the requirements.
2. Has lower prevention and treatment effect.
Therefore, the urgent need exists for providing the pesticide water dispersible granule with excellent physical and chemical properties and high prevention effect. The composite dispersing agent is the research focus in recent years, CN1957698A discloses an kresoxim-methyl water dispersible granule, and the embodiment specifically discloses that an alkyl naphthalene sulfonate formaldehyde condensate and dioctyl sodium sulfosuccinate are adopted as the dispersing agent to prepare the kresoxim-methyl water dispersible granule; surprisingly, the applicant found that when a specific proportion of a complex dispersant comprising an alkyl naphthalene sulfonate formaldehyde condensate and disodium sulfosuccinate ethoxylated alcohol monoester is used for preparing the pesticide water dispersible granule, the dispersant has good compatibility with the pesticide active ingredient, particularly flazasulfuron, and the water dispersible granule with excellent physicochemical properties, particularly suspension property and dispersibility can be prepared.
Disclosure of Invention
The invention aims to provide a pesticide composite dispersing agent, and the second purpose is to apply the composite dispersing agent to the preparation of pesticide water dispersible granules, so that the suspension rate, the dispersibility and the prevention and control efficacy of the pesticide water dispersible granules can be effectively improved, and the purposes are realized by the following technical scheme:
a composite dispersing agent consists of alkyl naphthalene sulfonate formaldehyde condensate and sulfosuccinic monoester in the weight ratio of 1:1-2.
A water dispersible granule comprising: 1-75% of pesticide active ingredient, 1-10% of composite dispersing agent, 1-10% of wetting agent and the balance of carrier, wherein the composite dispersing agent is a composition of alkyl naphthalene sulfonate formaldehyde condensate and sulfosuccinic acid monoester with the weight ratio of 1:1-2.
A flazasulfuron water dispersible granule comprising: 10-50% of flazasulfuron, 1-10% of composite dispersant, 1-10% of wetting agent and the balance of carrier, wherein the percentages are weight percentages; the composite dispersing agent is a composition of alkyl naphthalene sulfonate formaldehyde condensate and sulfosuccinic monoester in a weight ratio of 1:1-2.
Preferably, the water dispersible granule comprises the following components in parts by weight: 25% of flazasulfuron, 10% of composite dispersant, 1-10% of wetting agent and the balance of carrier;
preferably, the composite dispersing agent is a composition of alkyl naphthalene sulfonate formaldehyde condensate and sulfosuccinic monoester in a weight ratio of 1:1;
the alkyl naphthalene sulfonate formaldehyde condensate is NNO, NO or MF; preferably NNO;
the sulfosuccinic monoester is disodium sulfosuccinic ethoxylated alcohol monoester;
the wetting agent is one or more of methyl taurate, sodium dodecyl sulfate, fatty acid ester sulfate, laurate, alkylphenol ethoxylate, benzene sulfonate, naphthalene sulfonate and fatty alcohol polyoxyethylene ether;
the carrier is one or more of talcum powder, white carbon black, calcined kaolin, organic bentonite, light calcium carbonate, diatomite, magnesium aluminum silicate, corn starch, sodium sulfate, methyl cellulose and modified corn starch.
The composite dispersing agent provided by the invention is suitable for preparing pesticide water dispersible granules, and particularly has good compatibility with pesticide flazasulfuron. The composite dispersing agent, the wetting agent and the filler are added to serve as auxiliary agents, the auxiliary agents act synergistically, the defect of slow wetting of particles in water is overcome by combining the wetting agent and the filler, the defect of easy agglomeration of suspended particles is overcome by adding the composite dispersing agent, and the particles have the advantages of quick dispersion in water, good atomization, high suspension rate, uniform particle size and the like, so that the water dispersible granule with quick disintegration speed, good suspension dispersibility and uniform particle size is obtained, the stability is greatly improved, and the pesticide water dispersible granule, especially the prevention and treatment effect of the flazasulfuron water dispersible granule, is also improved by selecting the types of the auxiliary agents.
The pesticide water dispersible granule provided by the invention is matched with an active ingredient by adding the composite dispersing agent, is specifically composed of the alkyl naphthalene sulfonate formaldehyde condensate and the sulfosuccinic monoester in a specific proportion, and is combined with proper auxiliary materials for use, so that the pesticide water dispersible granule prepared by the invention has better suspension property, dispersibility and stability. The pesticide water dispersible granule prepared by the invention is rapidly disintegrated after being put into water, has finer grain diameter, proper viscosity, good fluidity, difficult water separation and sedimentation, good storage stability, strong stability at-4 ℃ and 54 ℃, suspension rate of more than 95 percent, no caking and basically unchanged viscosity. Meanwhile, the test result proves that the flazasulfuron water dispersible granule has the prevention and treatment efficacy of 98% on nutgrass galingale rhizome and crabgrass, the prevention and treatment level is obviously improved, and the flazasulfuron water dispersible granule has good industrial application value.
Detailed Description
Example 1 25% flazasulfuron Water dispersible granule
According to the requirements of the formula, the raw materials, the composite dispersing agent, the filler and the like are mixed and crushed, then water is added for kneading, and the mixture is added into a granulator for granulation, and then the water dispersible granule product is prepared after drying and screening.
Example 2 25% flazasulfuron Water dispersible granule
According to the requirements of the formula, the raw materials, the composite dispersing agent, the filler and the like are mixed and crushed, then water is added for kneading, and the mixture is added into a granulator for granulation, and then the water dispersible granule product is prepared after drying and screening.
Example 3 25% flazasulfuron Water dispersible granule
According to the requirements of the formula, the raw materials, the composite dispersing agent, the filler and the like are mixed and crushed, then water is added for kneading, and the mixture is added into a granulator for granulation, and then the water dispersible granule product is prepared after drying and screening.
Example 4 70% Imidacloprid Water dispersible granule
According to the requirements of the formula, the raw materials, the composite dispersing agent, the filler and the like are mixed and crushed, then water is added for kneading, and the mixture is added into a granulator for granulation, and then the water dispersible granule product is prepared after drying and screening.
Example 5 5% emamectin benzoate Water dispersible granule
According to the requirements of the formula, the raw materials, the composite dispersing agent, the filler and the like are mixed and crushed, then water is added for kneading, and the mixture is added into a granulator for granulation, and then the water dispersible granule product is prepared after drying and screening.
Example 6 75% clomazone Water dispersible granule
According to the requirements of the formula, the raw materials, the composite dispersing agent, the filler and the like are mixed and crushed, then water is added for kneading, and the mixture is added into a granulator for granulation, and then the water dispersible granule product is prepared after drying and screening.
The following test is a composite dispersant screening and testing test.
Test example 1 screening of dispersants
Test variety
Variety of dispersant: alkyl naphthalene sulfonate formaldehyde condensate (NNO), carboxymethyl cellulose (CMC), sodium lignin sulfonate (REAX 910), sulfosuccinate (disodium sulfosuccinate ethoxylated alcohol monoester).
Experimental method
According to different performances and actions of the tested dispersants, 25 compound formulas and 4 single formulas are properly combined and screened by adopting a repeated test method. The pesticide flazasulfuron is selected as an active ingredient.
Weighing the following components in percentage by mass: the flazasulfuron content is 25% (test example); the total amount of the composite dispersant is 10 percent (the different compositions and the amounts are shown in Table 1); methyl taurate 8%; the rest is complemented by diatomite.
The preparation method of the pesticide water dispersible granule comprises the following steps: adding the pesticide active ingredients, the compound dispersing agent and the grinding, mixing and crushing into powder, adding water for kneading, adding into a granulator for granulating, drying and screening to obtain the pesticide.
2 test results the test results are shown in Table 1.
Table 1 influence of different dispersant combinations and ratios on Water dispersible granule Performance
As can be seen from table 1, the composite dispersants obtained by combining the dispersant alkylnaphthalene sulfonate formaldehyde condensate (NNO), carboxymethyl cellulose (CMC), sodium lignin sulfonate (REAX 910), and sulfosuccinic acid monoester (disodium sulfosuccinate ethoxylated alcohol monoester) in different types and using the same combination type in different amounts have significant differences in the indexes such as suspension property, dispersibility, and stability. The suspension property and the dispersibility are key indexes for reflecting the performance of the preparation, and the low-temperature and heat storage stability is another important index for reflecting the good and bad performance of the water dispersible granule.
According to the test data in table 1, it can be seen that the composite dispersant obtained by mixing the alkyl naphthalene sulfonate formaldehyde condensate (NNO) and the sulfosuccinic acid monoester (disodium sulfosuccinate ethoxylated alcohol monoester) according to the mass ratio of 1:1-2 has a remarkable synergistic effect, so that the dispersibility and suspension property of the water dispersible granule can be remarkably improved, and the low-temperature and heat storage stability of the water dispersible granule can be effectively improved; that is, when the alkyl naphthalene sulfonate formaldehyde condensate (NNO) and the sulfosuccinic monoester (disodium sulfosuccinate ethoxylated alcohol monoester) are combined in a mass ratio of 1:1-2, the synergistic effect of the two is very remarkable compared to the other combinations; particularly, when the alkyl naphthalene sulfonate formaldehyde condensate (NNO) and the sulfosuccinic acid monoester (sulfosuccinic acid ethoxylated alcohol monoester disodium) are mixed according to the mass ratio of 1:1, compared with other combinations, the prepared pesticide water dispersible granule is obviously superior to other combinations in terms of dispersibility, suspension property, stability and other performances, can comprehensively and obviously improve various performances of the pesticide water dispersible granule, and is very suitable for serving as a composite dispersing agent of the pesticide water dispersible granule, in particular flazasulfuron water dispersible granule.
Test example 2 physical and chemical properties were measured.
Based on the example 1, corresponding water dispersible granules were prepared with the amounts of the components shown in table 2, wherein the total amount of the composite dispersing agent is 10%, the composition of the composite dispersing agent or the active ingredient is only changed, and the dispersion rate and the suspension rate are tested at normal temperature.
TABLE 2 physical and chemical Property test
The test results of the groups 1-10 and 11-14 are compared, and it can be seen that the alkyl naphthalene sulfonate formaldehyde condensate and the disodium sulfosuccinate ethoxylated alcohol monoester are used as the composite dispersing agent for preparing the pesticide water dispersible granule, and are superior to the alkyl naphthalene sulfonate formaldehyde condensate and the sodium dioctyl sulfosuccinate. Test results of 1-10 groups prove that the composite dispersant alkyl naphthalene sulfonate formaldehyde condensate, the disodium sulfosuccinate ethoxylated alcohol monoester and the pesticide active ingredient, especially flazasulfuron, have remarkable synergistic effect. Moreover, according to the comparative tests 1-2, 11-12 and 9-10 and 13-14, it can be seen that the different composite dispersing agent compositions have a larger influence on the performance of the pesticide flazasulfuron water dispersible granule, and a smaller influence on the performance of the kresoxim-methyl water dispersible granule, so that the application range of the different composite dispersing agents is proved to be different, and the optimal conditions are required to be searched. Meanwhile, referring to CN1957698A, the alkyl naphthalene sulfonate formaldehyde condensate and dioctyl sodium sulfosuccinate are prepared into the water dispersible granule (test group 9) taking kresoxim-methyl as an active ingredient in a ratio of 2:1, and the dispersion performance and the suspension performance of the water dispersible granule are far lower than those of the test groups 1-2.
In conclusion, the conclusion is that the invention takes the alkyl naphthalene sulfonate formaldehyde condensate and the disodium sulfosuccinate ethoxylated alcohol monoester of a specific proportion as the composite dispersing agent, so that the dispersibility and suspension property of the pesticide water dispersible granule, in particular the flazasulfuron water dispersible granule, are greatly improved.
Test example 3 field efficacy test of 25% flazasulfuron Water dispersible granule for controlling Menira lawn weeds
1 test materials and test methods
1.1 test agents: 25% flazasulfuron water dispersible granule (invention), 25% flazasulfuron water dispersible granule is sold in the market.
1.2 test targets: warm season turf grass manila, main weed: nutgrass galingale rhizome and crab grass.
1.3 methods of administration: in the period of 2.5-5 leaves of nutgrass flatsedge or crabgrass, the Chinese medicinal materials are diluted with water according to the dosage of the medicament required by the test, and the water consumption per mu is 30 ml/mu.
1.4 investigation method: the turf grass was investigated for the presence of phytotoxicity 7 days after the drug, and the phytotoxicity symptoms (distortion, albino yellowing, etc.) were recorded in detail, and photographed. Fresh weight control was investigated 21 days after the drug, 5 spots were investigated per treatment, and 1m2 weeds were weighed and recorded per spot.
1.5, calculation of control effect: control (%) = [ (fresh weight of weed in clear water control group-fresh weight of weed in treatment group)/fresh weight of weed in clear water group ] ×100
2 test results: the results of the field efficacy investigation are shown in tables 2 and 3.
Table 3 results questionnaire for field efficacy test of controlled nutgrass galingale rhizome
Test agent Dosage of preparation (g/mu) Content of active ingredient (g/mu) Control effect (%)
Example 1 8 2 90.37b
Example 2 12 3 95.25ab
Example 3 16 4 98.42a
Commercial medicament 8 2 81.21d
Commercial medicament 12 3 85.49c
Commercial medicament 16 4 90.26b
Clear water control / / /
TABLE 4 results questionnaire for field efficacy test of control of crabs
Test agent Dosage of preparation (g/mu) Content of active ingredient (g/mu) Control effect (%)
Example 1 8 2 85.14c
Example 2 12 3 91.20b
Example 3 16 4 97.83a
Commercial medicament 8 2 80.01d
Commercial medicament 12 3 83.17cd
Commercial medicament 16 4 88.24bc
Clear water control / / /
By examining the test results and combining tables 3 and 4, the following conclusions can be drawn: each treatment after 7 days of the drug is safe to the manila lawn, has no drug injury, and has the symptoms of slight yellowing after the nutgrass galingale and barnyard grass start to be poisoned. Fresh weight control effect investigation 21 days after medicine shows that: with the increase of the dosage of the 25% flazasulfuron water dispersible granule, the control effect on the weed nutgrass flatsedge and crabgrass is improved, and the control effect of the 25% flazasulfuron water dispersible granule on the weed nutgrass flatsedge and crabgrass in turf grass is obviously better than that of the 25% flazasulfuron water dispersible granule sold in the market with the same dosage.
While the present invention has been described with respect to one embodiment of the invention and its use in preparing water dispersible granules, those skilled in the art may, by reference to the present invention, suitably modify the links of the raw materials, process conditions, etc. to achieve other corresponding objects, and all similar alternatives and modifications will be apparent to those skilled in the art without departing from the scope of the invention.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather to enable any modification, equivalent replacement, improvement or the like to be made within the spirit and principles of the invention.

Claims (7)

1. A water dispersible granule, comprising: 1-75% of pesticide active ingredient, 1-10% of composite dispersing agent, 1-10% of wetting agent and the balance of carrier, wherein the percentages are weight percentages;
the composite dispersing agent is a composition of alkyl naphthalene sulfonate formaldehyde condensate and sulfosuccinic monoester in a weight ratio of 1:1-2;
the pesticide active ingredient is one of imidacloprid, emamectin benzoate, flazasulfuron and clomazone;
the alkyl naphthalene sulfonate formaldehyde condensate is NNO, NO or MF.
2. The water dispersible granule according to claim 1, wherein the water dispersible granule comprises the following components and the amounts thereof: 10-50% of flazasulfuron, 1-10% of composite dispersing agent, 1-10% of wetting agent and the balance of carrier.
3. The water dispersible granule according to claim 2, wherein the water dispersible granule comprises the following components and the amounts thereof: 25% of flazasulfuron, 10% of composite dispersing agent, 1-10% of wetting agent and the balance of carrier.
4. The water dispersible granule according to claim 1, wherein the composite dispersant is a combination of an alkyl naphthalene sulfonate formaldehyde condensate and a sulfosuccinic monoester in a weight ratio of 1:1.
5. The water dispersible granule according to claim 1, wherein the sulfosuccinic monoester is disodium sulfosuccinic ethoxylated alcohol monoester.
6. The water dispersible granule according to claim 1, wherein the wetting agent is one or more of methyltaurine, sodium dodecyl sulfate, fatty acid ester sulfate, laurate, alkylphenol ethoxylate, benzenesulfonate, naphthalenesulfonate, fatty alcohol polyoxyethylene ether.
7. The water dispersible granule according to claim 1, wherein the carrier is one or more of talc, white carbon, calcined kaolin, organobentonite, light calcium carbonate, diatomaceous earth, magnesium aluminum silicate, corn starch, sodium sulfate, methylcellulose and modified corn starch.
CN202110003177.7A 2021-01-04 2021-01-04 Composite dispersing agent and application thereof in preparation of water dispersible granule Active CN114711244B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1269135A (en) * 1999-03-03 2000-10-11 日本拜耳农药株式会社 Farm chemicals preparation for application on water
CN1957698A (en) * 2006-11-24 2007-05-09 华南理工大学 Water dispersion granules agent of Kresoxim and preparation method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2563261C (en) * 2004-04-14 2013-04-09 Fmc Corporation Dispersible pesticidal compositions
CA3066512A1 (en) * 2017-07-06 2019-01-10 Rhodia Operations Pesticide compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1269135A (en) * 1999-03-03 2000-10-11 日本拜耳农药株式会社 Farm chemicals preparation for application on water
CN1957698A (en) * 2006-11-24 2007-05-09 华南理工大学 Water dispersion granules agent of Kresoxim and preparation method

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