CN112136826A - Cross-linked chitosan suspension seed coating agent and preparation method thereof - Google Patents
Cross-linked chitosan suspension seed coating agent and preparation method thereof Download PDFInfo
- Publication number
- CN112136826A CN112136826A CN202010978458.XA CN202010978458A CN112136826A CN 112136826 A CN112136826 A CN 112136826A CN 202010978458 A CN202010978458 A CN 202010978458A CN 112136826 A CN112136826 A CN 112136826A
- Authority
- CN
- China
- Prior art keywords
- agent
- cross
- chitosan
- seed coating
- coating agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01C—PLANTING; SOWING; FERTILISING
- A01C1/00—Apparatus, or methods of use thereof, for testing or treating seed, roots, or the like, prior to sowing or planting
- A01C1/06—Coating or dressing seed
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N25/00—Biocides, 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
- A01N25/02—Biocides, 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
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
- A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N45/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N47/00—Biocides, 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
- A01N47/08—Biocides, 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
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
- A01N47/14—Di-thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N47/00—Biocides, 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
- A01N47/08—Biocides, 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
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N47/00—Biocides, 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
- A01N47/08—Biocides, 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
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/26—Oxidation products of dithiocarbamic acid derivatives, e.g. thiuram sulfides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Soil Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a crosslinked chitosan suspended seed coating agent and a preparation method thereof, wherein the crosslinked chitosan suspended seed coating agent comprises the following components in parts by mass: 0.5-3% of film forming agent, wherein the film forming agent is chitosan with different crosslinking degrees; 2-20% of pesticide, 2-15% of bactericide, 0.5-5% of trace elements, 0.5-5% of growth regulator, 0.1-2% of thickening agent, 0.5-3% of wetting agent, 0.1-2% of dispersing agent, 0.1-2% of defoaming agent, 0.1-5% of antifreezing agent, 0.1-2% of preservative, 0-2% of pigment, 0-40% of filler and the balance of aqueous solution containing sodium acetate, wherein the content of sodium acetate is 1.5-4.0%. The invention adopts the cross-linking agent to modify the solubility and the film-forming property of the chitosan, and explores the proper formula of the film-forming agent and other substances, so as to obtain the cross-linked chitosan suspended seed coating agent which is easy to biodegrade.
Description
Technical Field
The invention belongs to the technical field of seed coating agents, and particularly relates to a crosslinked chitosan suspension seed coating agent and a preparation method thereof.
Background
In the modern agricultural production process, a large amount of chemical fertilizers and pesticides are often needed, so that the production cost is increased, and social and ecological problems such as environmental pollution and the like are caused. In addition, the excessive frequent use of the same chemical agents can cause the pests to generate drug resistance, so that the harm is increasingly serious, and particularly the pests are more easily harmed in the seedling stage; meanwhile, the pesticide can cause different degrees of harm to beneficial insects, birds and mammals in the environment. As a high and new technology for increasing yield and harvest in agriculture, the seed coating technology can effectively kill pathogenic bacteria carried on the surface of seeds, prevent and treat crop diseases and insect pests, improve the immunity and resistance of crops, promote growth and development, and effectively reduce the problems of high cost, poor effect, serious pollution and the like caused by application of chemical pesticides. Therefore, compared with the later-stage wide pesticide spraying, the seed coating agent has the obvious advantages that the seed coating agent directly wraps the active ingredients on the surfaces of the seeds for the growth and development of the seeds, so that the application cost is reduced, the harm of pathogenic bacteria and harmful insects to the seeds can be reduced by utilizing the introduced active ingredients, and even the pathogenic bacteria and the harmful insects are eliminated, the seed value is greatly increased, the pesticide using amount is reduced, and the influence of the pesticide on the environment is obviously reduced. The seed coating agent is widely applied to crop seeds and obtains quite remarkable economic, social and ecological benefits.
Seed coatings are compositions in which one or more active ingredients, such as insecticides, fungicides, nutrients, microorganisms, plant growth regulators, and the like, are combined with film formers, colorants, fillers, and the like and applied to the surface of the seed. It has important functions in seed sterilization, slow release of pesticide fertilizer, prevention and control of diseases, pests and rats, improvement of crop stress resistance, reduction of environmental pollution and the like.
At present, film forming agents in seed coating agents mainly adopt artificially synthesized high molecular compounds, are difficult to degrade in natural environment, cause great damage to soil structures and environment after being used for a long time in large quantity, and can be rapidly and naturally degraded after the ideal film forming agents play a role in further reducing the pollution of the seed coating agents to the environment. The natural high molecular compound is easy to biodegrade, is compatible with seeds, most bactericides, insecticides and additives, and has higher safety and environmental protection.
The chitosan is derived from chitin in the nature, is rich in raw materials, is natural high-molecular basic aminopolysaccharide, and is a good compound carrier. Has the characteristics of no toxicity, easy biodegradation, good compatibility with seeds and active ingredients and the like. In addition, the chitosan has good film forming property, the chitosan oligosaccharide with low molecular weight also has the functions of antibacterial property and biological stimulin, has good effect on improving the stress resistance and development of seeds and seedlings, and has the advantages of high elasticity, low density, high toughness, low price, no toxicity, no harm, no secondary pollution and the like, is a well-known environment-friendly material, and has wide application prospect in the aspect of being used as a seed coating film forming agent.
Disclosure of Invention
The invention aims to solve the technical problem of providing a biodegradable suspended seed coating agent and a preparation method thereof, wherein chitosan is properly crosslinked to be used as a film forming agent of the seed coating agent, and the crosslinking agent is one of glyoxal and glutaraldehyde.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a cross-linked chitosan suspension seed coating agent comprises the following components in parts by mass: 0.5-3% of film forming agent, wherein the film forming agent is chitosan with different crosslinking degrees; 2-20% of pesticide, 2-15% of bactericide, 0.5-5% of trace elements, 0.5-5% of growth regulator, 0.1-2% of thickening agent, 0.5-3% of wetting agent, 0.1-2% of dispersing agent, 0.1-2% of defoaming agent, 0.1-5% of antifreezing agent, 0.1-2% of preservative, 0-2% of pigment, 0-40% of filler and the balance of aqueous solution containing sodium acetate, wherein the content of sodium acetate is 1.5-4.0%.
On the basis of the technical scheme, the invention can further have the following specific selection or optimized selection.
Specifically, the molecular weight of the chitosan is 1-100 ten thousand.
Specifically, the pesticide includes but is not limited to one or more of imidacloprid, thiamethoxam, phoxim, methyl sulfur cyclo-phos, cyfluthrin, acetamiprid and tefluthrin; the bactericide comprises but is not limited to one or more of carbendazim, thiram, tebuconazole, myclobutanil, triadimefon, triadimenol and carboxin; the trace elements comprise one or more of potassium dihydrogen phosphate, boron fertilizer, zinc fertilizer, manganese fertilizer and molybdenum fertilizer; the growth regulator comprises one or more of but not limited to chitosan oligosaccharide, gibberellic acid, indoleacetic acid and humic acid; the thickening agent comprises one or more of but not limited to polyacrylamide, polyvinyl alcohol and polyethylene glycol; the wetting agent includes, but is not limited to, one or more of alkyl naphthalene sulfonate, sulfosuccinate, sodium lauryl sulfate, silicone spreader; the dispersing agent comprises one or more of lignin sulfonic acid, gelatin, Arabic gum and sodium alginate; the antifoaming agent includes, but is not limited to, one or more of isooctanol, isoamyl alcohol, stearic acid, lauric acid, tributyl phosphate; the antifreeze comprises one or more of but not limited to ethylene glycol, propylene glycol, glycerol and urea; the preservative includes but is not limited to one or more of sodium salicylate, sodium benzoate; the pigment includes but is not limited to one or more of fuchsin, indigo blue, turmeric, gentian violet and fruit green; the filler includes, but is not limited to, one or more of diatomaceous earth, bentonite, attapulgite, precipitated calcium carbonate, white carbon and china clay, limestone, gypsum, inorganic slag.
It should be noted that the term "includes, but is not limited to" means that one or more of the following exemplary substances are necessarily included, and that other substances may be further included.
In addition, the invention also provides a method for preparing the cross-linked chitosan suspension seed coating agent, which comprises the following steps:
1) dissolving chitosan in an aqueous solution containing acetic acid with the mass fraction of 2%, adding a cross-linking agent, stirring for reaction, and adopting NaHCO3Adjusting the pH value to be neutral to obtain a cross-linked chitosan solution, wherein the cross-linked chitosan solution contains 1.5-4.0 mass percent of sodium acetate;
2) sequentially adding a defoaming agent, a thickening agent, a wetting agent and a dispersing agent into the crosslinked chitosan solution obtained in the step 1), sequentially adding an insecticide, a bactericide, a trace element and a growth regulator after uniformly stirring for the first time, sequentially adding an antifreezing agent, a preservative, a pigment and a filler after uniformly stirring for the second time, and uniformly stirring for the third time to obtain a suspension, namely the crosslinked chitosan suspension seed coating agent.
Specifically, in the step 1), the adopted cross-linking agent is one of glyoxal and glutaraldehyde; the dosage of the cross-linking agent is 0.05-0.5 times of the amount of the substance of the sugar units in the chitosan.
Specifically, in the step 1), the stirring reaction is carried out for 1-5 hours at the temperature of 20-50 ℃.
Compared with the prior art, the invention has the beneficial effects that: the chitosan has strong water-absorbing swelling property, and is difficult to maintain the form of the seed coating agent and lose efficacy when meeting water environment after film forming, so the water-absorbing swelling property of the chitosan needs to be reduced so as to adapt to the performance requirement of a film forming agent used as the seed coating agent. The chitosan molecule is rich in amino and hydroxyl, can perform crosslinking reaction under the action of bifunctional aldehyde or anhydride and the like, has mild reaction conditions, and can obviously reduce the water absorption expansibility and increase the film forming firmness by improving the crosslinking degree. Therefore, the invention adopts the cross-linking agent to modify the solubility and the film-forming property of the chitosan, and explores the proper formula of the film-forming agent and other substances, so as to obtain the cross-linked chitosan suspended seed coating agent which is easy to biodegrade.
Detailed Description
For better understanding of the present invention, the following examples are given for further illustration of the present invention, but the present invention is not limited to the following examples.
The first embodiment is as follows:
a cross-linked chitosan suspension seed coating agent and a preparation method thereof. Dissolving 0.5% chitosan in 35.6% aqueous solution containing 2% acetic acid, adding glyoxal in an amount of 0.5 times of the number of saccharide units in chitosan, stirring at 50 deg.C for 3 hr, and adding NaHCO3Adjusting pH to neutral to prepare a cross-linked chitosan solution with certain viscosity, taking the solution as a film forming agent, sequentially adding 1.5 percent of isooctanol as a defoaming agent, 1 percent of polyacrylamide, 0.5 percent of polyvinyl alcohol as a thickening agent and 0.5 percent of organic solventThe preparation method comprises the following steps of taking a silicon spreader as a wetting agent, taking 1% lignosulfonic acid as a dispersing agent, stirring and mixing uniformly, sequentially adding 5% of imidacloprid as an insecticide, 10% of carbendazim as a bactericide, 0.5% of monopotassium phosphate as a trace element and 3% of chitosan oligosaccharide as a growth regulator, stirring and mixing uniformly, then adding 0.5% of glycerol as an antifreezing agent, 0.2% of sodium salicylate as an antiseptic, 0.2% of fuchsin as a pigment, finally adding 40% of bentonite as a filler, and mixing uniformly to obtain a suspension, namely the crosslinked chitosan suspension seed coating agent.
Example two:
a cross-linked chitosan suspension seed coating agent and a preparation method thereof. Dissolving 1% chitosan in 50% aqueous solution containing 2% acetic acid, adding glutaraldehyde in an amount of 0.4 times the number of saccharide units in chitosan, stirring at 45 deg.C for 3 hr, and adding NaHCO3Adjusting pH to be neutral to prepare a cross-linked chitosan solution with certain viscosity, taking the solution as a film forming agent, sequentially adding 1 percent of tributyl phosphate as a defoaming agent, 0.5 percent of polyacrylamide, 0.5 percent of polyvinyl alcohol as a thickening agent, 1 percent of alkyl naphthalene sulfonate, 0.2 percent of organic silicon spreader as a wetting agent and 1 percent of gelatin as a dispersing agent, stirring and mixing uniformly, sequentially adding 2% phoxim, 2% cyfluthrin as pesticide, 5% thiram as bactericide, 1% boron fertilizer as microelement and 0.5% gibberellic acid as growth regulator, stirring and mixing uniformly, then adding 2% of glycol, 0.5% of glycerol as an antifreezing agent, 0.5% of sodium salicylate as an antiseptic and 0.3% of indigo as a pigment, finally adding 30% of pottery clay as a filler, and uniformly mixing to obtain a suspension, namely the crosslinked chitosan suspension seed coating agent.
Example three:
a cross-linked chitosan suspension seed coating agent and a preparation method thereof. Dissolving 1.5% chitosan in 59.1% aqueous solution containing 2% acetic acid, adding glyoxal in an amount of 0.3 times the number of saccharide units in chitosan, stirring at 40 deg.C for 3 hr, and adding NaHCO3Adjusting pH to neutral to obtain cross-linked chitosan solution with certain viscosity, and sequentially adding 0.3% isoamyl alcohol, 0.3% lauric acid as defoaming agent and 0.2% polypropylene by using the solution as film forming agentEnamide, 0.2% of polyvinyl alcohol, 0.2% of polyethylene glycol as a thickening agent, 1% of sodium dodecyl sulfate, 0.2% of organic silicon spreading agent as a wetting agent and 0.5% of Arabic gum as a dispersing agent are stirred and mixed uniformly, then 2% of imidacloprid, 2% of phoxim and 2% of cyfluthrin as insecticides, 3% of carbendazim, 2% of thiram as a bactericide, 2% of zinc fertilizer as a trace element and 0.5% of indoleacetic acid as a growth regulator are sequentially added, after stirring and mixing uniformly, 1% of propylene glycol, 1% of urea as an antifreezing agent, 0.5% of sodium salicylate, 0.2% of sodium benzoate as a preservative, 0.3% of turmeric as a pigment are added, and finally 20% of diatomite as a filler is added, and the suspension obtained after mixing uniformly is the crosslinked chitosan suspension seed coating agent.
Example four:
a cross-linked chitosan suspension seed coating agent and a preparation method thereof. Dissolving 2% chitosan in 58.5% aqueous solution containing 2% acetic acid, adding glutaraldehyde in an amount of 0.2 times of the number of saccharide units in chitosan, stirring at 35 deg.C for 3 hr, and adding NaHCO3Adjusting pH to be neutral to prepare a cross-linked chitosan solution with certain viscosity, taking the solution as a film forming agent, sequentially adding 0.2 percent of isooctanol, 0.2 percent of stearic acid as a defoaming agent, 0.2 percent of polyvinyl alcohol, 0.2 percent of polyethylene glycol as a thickening agent, 0.5 percent of alkyl naphthalene sulfonate, 0.5 percent of sulfosuccinate, 0.5 percent of lauryl sodium sulfate as a wetting agent and 0.5 percent of sodium alginate as a dispersing agent, stirring and mixing uniformly, sequentially adding 5 percent of cyfluthrin as an insecticide, 2 percent of carbendazim, 2 percent of thiram, 2 percent of tebuconazole, 2 percent of carboxin as a bactericide, 1 percent of monopotassium phosphate, 0.5 percent of boron fertilizer as a trace element and 3 percent of humic acid as a growth regulator, stirring and mixing uniformly, then adding 1 percent of glycerol, 2 percent of urea as an antifreezing agent, 0.2 percent of sodium salicylate, 0.5 percent of sodium benzoate as a preservative and 0.5 percent of gentian violet as a pigment, and finally, adding 5% of diatomite, 5% of light calcium carbonate and 5% of limestone as fillers, and uniformly mixing to obtain a suspension, namely the crosslinked chitosan suspension seed coating agent.
Example five:
cross-linked chitosan suspension seed coating agent and preparation method thereof. Dissolving 2.5% chitosan in 59.5% aqueous solution containing 2% acetic acid, adding glyoxal in an amount of 0.1 times the number of saccharide units in chitosan, stirring at 30 deg.C for 3 hr, and adding NaHCO3Adjusting pH to be neutral to prepare a cross-linked chitosan solution with certain viscosity, taking the solution as a film forming agent, sequentially adding 0.1% isoamyl alcohol, 0.1% stearic acid, 0.1% tributyl phosphate as a defoaming agent, 0.1% polyacrylamide, 0.1% polyethylene glycol as a thickening agent, 2% alkyl naphthalene sulfonate as a wetting agent, 0.5% gelatin and 0.5% Arabic gum as dispersing agents, stirring and mixing uniformly, sequentially adding 5% acetamiprid, 5% tefluthrin as an insecticide, 5% thiram, 3% tebuconazole, 2% carboxin as a bactericide, 1% zinc fertilizer, 1% manganese fertilizer, 1% molybdenum fertilizer as a trace element, 1.5% chitosan oligosaccharide and 1.5% humic acid as a growth regulator, stirring and mixing uniformly, then adding 0.5% ethylene glycol, 0.5% glycerol, 0.5% urea as an antifreezing agent, 1% sodium benzoate as a preservative, and 1% fruit green as a pigment, and finally, adding 3% of gypsum and 2% of inorganic slag as fillers, and uniformly mixing to obtain a suspension, namely the crosslinked chitosan suspension seed coating agent.
Example six:
a cross-linked chitosan suspension seed coating agent and a preparation method thereof. Dissolving 3% chitosan in 76.1% aqueous solution containing 2% acetic acid, adding glutaraldehyde in an amount of 0.05 times the number of saccharide units in chitosan, stirring at 25 deg.C for 3 hr, and adding NaHCO3Adjusting the pH value to be neutral to prepare a cross-linked chitosan solution with certain viscosity, taking the solution as a film forming agent, sequentially adding 0.1% of isooctanol, 0.1% of lauric acid, 0.1% of tributyl phosphate as an antifoaming agent, 0.2% of polyacrylamide as a thickening agent, 3% of sodium dodecyl sulfate as a wetting agent, 0.5% of sodium lignosulfonate and 0.5% of sodium alginate as dispersing agents, stirring and mixing uniformly, sequentially adding 2% of imidacloprid, 2% of thiamethoxam, 2% of thiophosphoryl methyl, 2% of cyfluthrin as an insecticide, 2% of carboxin as a bactericide, 0.5% of dipotassium hydrogen phosphate, 0.5% of boron fertilizer, 0.5% of zinc fertilizer, 0.5% of manganese fertilizer, 0.5% of molybdenum fertilizer as a trace element, 0.2% of gibberellic acid and 0.2% of indoleacetic acid as growth regulators, stirring and mixingAfter the mixture is uniform, 2% of urea serving as an antifreezing agent and 1.5% of sodium benzoate serving as a preservative are added, pigments and fillers are not added, and the suspension obtained after uniform mixing is the cross-linked chitosan suspension seed coating agent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The cross-linked chitosan suspension seed coating agent is characterized by comprising the following components in parts by mass: 0.5-3% of film forming agent, 2-20% of insecticide, 2-15% of bactericide, 0.5-5% of trace elements, 0.5-5% of growth regulator, 0.1-2% of thickening agent, 0.5-3% of wetting agent, 0.1-2% of dispersing agent, 0.1-2% of defoaming agent, 0.1-5% of antifreezing agent, 0.1-2% of preservative, 0-2% of pigment, 0-40% of filler and the balance of aqueous solution containing sodium acetate, wherein the content of the sodium acetate is 1.5-4.0%; the film forming agent is chitosan with different crosslinking degrees.
2. The cross-linked chitosan suspension seed coating agent of claim 1, wherein: the molecular weight of the chitosan is 1-100 ten thousand.
3. The cross-linked chitosan suspension seed coating agent of claim 1, wherein: the pesticide includes but is not limited to one or more of imidacloprid, thiamethoxam, phoxim, thiophosphoryl methyl, cyfluthrin, acetamiprid and tefluthrin; the bactericide comprises but is not limited to one or more of carbendazim, thiram, tebuconazole, myclobutanil, triadimefon, triadimenol and carboxin; the trace elements comprise but are not limited to one or more of potassium dihydrogen phosphate, boron fertilizer, zinc fertilizer, manganese fertilizer and molybdenum fertilizer.
4. The cross-linked chitosan suspension seed coating agent of claim 1, wherein: the growth regulator comprises one or more of but not limited to chitosan oligosaccharide, gibberellic acid, indoleacetic acid and humic acid; the thickening agent comprises one or more of but not limited to polyacrylamide, polyvinyl alcohol and polyethylene glycol; the wetting agent includes, but is not limited to, one or more of alkyl naphthalene sulfonate, sulfosuccinate, sodium lauryl sulfate, silicone spreader.
5. The cross-linked chitosan suspension seed coating agent according to any one of claims 1 to 4, wherein: the dispersing agent comprises one or more of lignin sulfonic acid, gelatin, Arabic gum and sodium alginate; the antifoaming agent includes, but is not limited to, one or more of isooctanol, isoamyl alcohol, stearic acid, lauric acid, tributyl phosphate; the antifreeze agent comprises one or more of but not limited to ethylene glycol, propylene glycol, glycerol and urea.
6. The cross-linked chitosan suspension seed coating agent of claim 5, wherein: the preservative includes but is not limited to one or more of sodium salicylate, sodium benzoate; the pigment includes but is not limited to one or more of fuchsin, indigo blue, turmeric, gentian violet and fruit green.
7. The cross-linked chitosan suspension seed coating agent of claim 5, wherein: the filler includes, but is not limited to, one or more of diatomaceous earth, bentonite, attapulgite, precipitated calcium carbonate, white carbon and china clay, limestone, gypsum, inorganic slag.
8. A method for preparing the cross-linked chitosan suspension seed coating agent as claimed in any one of claims 1 to 7, comprising the steps of:
1) dissolving chitosan in an aqueous solution containing acetic acid with the mass fraction of 2%, adding a cross-linking agent, stirring for reaction, and adopting NaHCO3Adjusting the pH value to be neutral to obtain a cross-linked chitosan solution, wherein the cross-linked chitosan solution contains 1.5-4.0 mass percent of sodium acetate;
2) sequentially adding a defoaming agent, a thickening agent, a wetting agent and a dispersing agent into the crosslinked chitosan solution obtained in the step 1), sequentially adding an insecticide, a bactericide, a trace element and a growth regulator after uniformly stirring for the first time, sequentially adding an antifreezing agent, a preservative, a pigment and a filler after uniformly stirring for the second time, and uniformly stirring for the third time to obtain a suspension, namely the crosslinked chitosan suspension seed coating agent.
9. The method for preparing the cross-linked chitosan suspension seed coating agent according to claim 8, wherein in the step 1), the cross-linking agent is one of glyoxal and glutaraldehyde; the dosage of the cross-linking agent is 0.05-0.5 times of the amount of substances of the sugar units in the chitosan.
10. The preparation method of the crosslinked chitosan suspended seed coating agent according to claim 8, wherein the stirring reaction is a stirring reaction at 20-50 ℃ for 1-5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010978458.XA CN112136826A (en) | 2020-09-15 | 2020-09-15 | Cross-linked chitosan suspension seed coating agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010978458.XA CN112136826A (en) | 2020-09-15 | 2020-09-15 | Cross-linked chitosan suspension seed coating agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112136826A true CN112136826A (en) | 2020-12-29 |
Family
ID=73892968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010978458.XA Pending CN112136826A (en) | 2020-09-15 | 2020-09-15 | Cross-linked chitosan suspension seed coating agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112136826A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114436702A (en) * | 2022-03-11 | 2022-05-06 | 陕西科技大学 | Degradable mulberry seed coating film agent and preparation method and use method thereof |
| EP4206168A1 (en) * | 2021-12-31 | 2023-07-05 | SABIC Global Technologies B.V. | Nano bio-carrier with plant additives coated on chemical fertilizers |
| EP4206167A1 (en) * | 2021-12-31 | 2023-07-05 | SABIC Global Technologies, B.V. | Nano bio-carrier with micronutrients coated on chemical fertilizers |
| WO2023126895A1 (en) * | 2021-12-31 | 2023-07-06 | Sabic Global Technologies B.V. | Nano bio-carrier with plant additives coated on chemical fertilizers |
| CN116584495A (en) * | 2023-07-14 | 2023-08-15 | 山东寿光蔬菜种业集团有限公司 | Cucumber seed coating agent and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103329890A (en) * | 2013-07-04 | 2013-10-02 | 黑龙江省新兴农药有限责任公司 | Film-forming agent of flowable seed coating formulation and preparation method thereof |
| CN105010347A (en) * | 2015-07-06 | 2015-11-04 | 江苏艾津农化有限责任公司 | Fenclorim-contained seed-coating suspension and application thereof |
| CN105961425A (en) * | 2016-07-29 | 2016-09-28 | 惠州市银农科技股份有限公司 | Suspended seed coating agent containing fludioxonil and thiamethoxam and preparation method of suspended seed coating agent |
| CN106857584A (en) * | 2017-01-19 | 2017-06-20 | 佛山市盈辉作物科学有限公司 | A kind of suspension seed-coating agent containing ethiprole and Tebuconazole and preparation method thereof |
| CN109601545A (en) * | 2018-11-22 | 2019-04-12 | 吴学民 | A kind of dispersible oil seeds inorganic agent of environmental protection and preparation method thereof |
-
2020
- 2020-09-15 CN CN202010978458.XA patent/CN112136826A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103329890A (en) * | 2013-07-04 | 2013-10-02 | 黑龙江省新兴农药有限责任公司 | Film-forming agent of flowable seed coating formulation and preparation method thereof |
| CN105010347A (en) * | 2015-07-06 | 2015-11-04 | 江苏艾津农化有限责任公司 | Fenclorim-contained seed-coating suspension and application thereof |
| CN105961425A (en) * | 2016-07-29 | 2016-09-28 | 惠州市银农科技股份有限公司 | Suspended seed coating agent containing fludioxonil and thiamethoxam and preparation method of suspended seed coating agent |
| CN106857584A (en) * | 2017-01-19 | 2017-06-20 | 佛山市盈辉作物科学有限公司 | A kind of suspension seed-coating agent containing ethiprole and Tebuconazole and preparation method thereof |
| CN109601545A (en) * | 2018-11-22 | 2019-04-12 | 吴学民 | A kind of dispersible oil seeds inorganic agent of environmental protection and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 常晓春: "悬浮种衣剂中壳聚糖成膜性效果研究", 《现代农业科技》 * |
| 王浩: "壳聚糖的改性研究进展及其应用", 《成都纺织高等专科学校学报》 * |
| 赵书言: "改性壳聚糖农药缓释载体的研究", 《中国优秀硕士学位论文全文数据库(工程科技辑)》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4206168A1 (en) * | 2021-12-31 | 2023-07-05 | SABIC Global Technologies B.V. | Nano bio-carrier with plant additives coated on chemical fertilizers |
| EP4206167A1 (en) * | 2021-12-31 | 2023-07-05 | SABIC Global Technologies, B.V. | Nano bio-carrier with micronutrients coated on chemical fertilizers |
| WO2023126895A1 (en) * | 2021-12-31 | 2023-07-06 | Sabic Global Technologies B.V. | Nano bio-carrier with plant additives coated on chemical fertilizers |
| WO2023126894A1 (en) * | 2021-12-31 | 2023-07-06 | Sabic Global Technologies B.V. | Nano bio-carrier with plant additives combined with chemical fertilizers |
| CN114436702A (en) * | 2022-03-11 | 2022-05-06 | 陕西科技大学 | Degradable mulberry seed coating film agent and preparation method and use method thereof |
| CN116584495A (en) * | 2023-07-14 | 2023-08-15 | 山东寿光蔬菜种业集团有限公司 | Cucumber seed coating agent and preparation method thereof |
| CN116584495B (en) * | 2023-07-14 | 2023-11-21 | 山东寿光蔬菜种业集团有限公司 | Cucumber seed coating agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112136826A (en) | Cross-linked chitosan suspension seed coating agent and preparation method thereof | |
| CN102173928B (en) | Wood non-woven fabric container nursery biological-type medium | |
| CN101233861A (en) | High active biological drought resisting seed coating agent and preparation and using method thereof | |
| CN109762571B (en) | Soil drought-resistant water-retaining agent, preparation method and use method thereof | |
| CN117003593A (en) | Liquid mulching film formed by taking livestock manure as main material and preparation method and using method thereof | |
| CN105523855A (en) | Organic nutrient soil for green agricultural cultivation | |
| CN110143836A (en) | Using phosphoric acid as regulating acid agent and the rice seedling-growth soil regulator of phosphorus source and its preparation method and application | |
| AU2018101439A4 (en) | Special film-coated controlled release pesticide for peanut and preparation process thereof | |
| CN1268290A (en) | Granulating method of pesticide water-dispersing granules preparation | |
| CN107087451B (en) | method for improving severe soda saline-alkali soil | |
| CN112075445A (en) | Cross-linked sodium carboxymethylcellulose suspension seed coating agent and preparation method thereof | |
| KR101174501B1 (en) | Environmental-friendly Functional Horticulture Pot | |
| CN111606760B (en) | Fertilizer composite film material and special slow/controlled release fertilizer for ratoon rice in southern red soil region | |
| CN104892258B (en) | A kind of starch base compound seed coating material | |
| CN116477984A (en) | Coating agent for granular nitrogen fertilizer, slow-release nitrogen fertilizer and preparation method thereof | |
| CN114436702A (en) | Degradable mulberry seed coating film agent and preparation method and use method thereof | |
| CN116253974A (en) | Biodegradable weeding mulching film product and preparation method thereof | |
| CN108821851A (en) | A kind of raising wheat yield sustained release base manure and preparation method thereof | |
| CN105295935A (en) | Applications of etherified corn starch, sand fixation water retention agent, and preparation method of sand fixation water retention agent | |
| CN115093297A (en) | Compound fertilizer for preventing soil hardening and preparation method thereof | |
| CN113826618A (en) | Agricultural microbial hydrogel agent with disease resistance and yield increase | |
| CN113461456A (en) | Organic fertilizer and preparation method thereof | |
| CN102659483A (en) | Slow-released fertilizer for fruit trees | |
| WO2020222368A1 (en) | Eco-friendly biodegradable pulp mulching paper and manufacturing method therefor | |
| CN105272598A (en) | Wheat seed dressing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201229 |