CN113875763A - Chelerythrine suspending agent and preparation method and application thereof - Google Patents
Chelerythrine suspending agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN113875763A CN113875763A CN202111276526.9A CN202111276526A CN113875763A CN 113875763 A CN113875763 A CN 113875763A CN 202111276526 A CN202111276526 A CN 202111276526A CN 113875763 A CN113875763 A CN 113875763A
- Authority
- CN
- China
- Prior art keywords
- chelerythrine
- suspending agent
- preparation
- agent
- xanthan gum
- 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.)
- Granted
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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic 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
- 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
Landscapes
- 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
Chelerythrine suspending agent, and a preparation method and application thereof, and belongs to the technical field of vegetable biological pesticides. In order to find an environment-friendly, low-toxicity and efficient prevention and treatment method for the rice flax spot disease, chelerythrine original drug, a dispersing agent Atlox 49134%, a wetting agent GenapolX 0802%, glycerol 5%, magnesium aluminum silicate 0.5%, xanthan gum 0.1%, Sag15220.2% and deionized water are compounded, and the suspending agent with the characteristics of fine particle size, high suspension rate, no dust and the like is obtained through mixing, shearing and grinding. The suspending agent is applied to the prevention and treatment of the rice black sesame leaf spot, shows good prevention and treatment effect, has the advantages of high efficiency, low toxicity, no public hazard, easy degradation and no environmental pollution, and meets the current requirements of developing green food and sustainable development of agriculture.
Description
Technical Field
The invention relates to a chelerythrine suspending agent, a preparation method and application thereof, and belongs to the technical field of biological pesticides.
Technical Field
Plant diseases seriously threaten global grain safety and ecological systems, and chemical pesticides play an important role. However, the hazards associated with the long term repeated use of chemical pesticides are becoming more acute. Therefore, how to weaken the dependence on chemical pesticides and develop environment-friendly plant-derived pesticides is a necessary measure for sustainable development of agricultural economy, and has important ecological benefits, social benefits and economic benefits.
Plants are always regarded as natural treasury, the research of plant secondary metabolites in the agricultural pest control is more and more emphasized, the chemical structures of the plants are various, and alkaloids, flavonoid compounds and the like are rich resources for developing plant-derived pesticides. The alkaloid has wide pharmacological activities including anticancer, antibacterial, insecticidal, antioxidant, etc. Wherein, the chelerythrine can effectively prevent and treat diseases of crops such as fusarium wilt, anthracnose, botrytis cinerea and the like in agricultural production, but the prevention and treatment research on rice diseases is less.
The bacterial strain fungi imperfecti sporotrichum belongs to helminthosporium umbiliciformis (Cochliobolus miyabenus) and can cause the rice flax leaf spot, the diseases can occur from the seedling stage to the harvest stage, the overground part of a rice plant can be damaged, and the number of leaves is large. The infected leaves of the adult plants are brown spots at the beginning of disease, and gradually expand into oval spots, such as sesame grain size, the central brown of the diseased spots is gray, the edges are brown, yellow halos with different depths are arranged around the diseased spots, and the diseased spots are connected into irregular large spots when the diseased spots are serious. The pathogenic bacteria overwinter on the disease residues or seeds with mycelium, which becomes the initial infection source in the next year. Generally, the yield loss is 10-30%, the yield is reduced by more than 50% when the disease is serious, and the most serious disease field is almost no harvest. At present, chelerythrine is not developed into a suspending agent to prevent and treat the rice flax spot disease.
Disclosure of Invention
The invention provides a chelerythrine suspending agent aiming at an environment-friendly, low-toxicity and efficient prevention and treatment method for rice flax spot disease, which comprises the following raw materials: by mass, the chelerythrine raw medicine is 10%, the dispersing agent Atlox 49134%, the wetting agent GenapolX 0802%, the glycerol is 5%, the magnesium aluminum silicate is 0.5%, the xanthan gum is 0.1%, the Sag 15220.2%, and the balance is deionized water.
Further defined, the xanthan gum is added with the kalong as a preservative during the preparation process.
The invention also provides a preparation method of the chelerythrine suspending agent, which comprises the following steps:
(1) weighing the dispersant Atlox4913, the wetting agent GenapolX080, glycerol, magnesium aluminum silicate, Sag1522 and deionized water according to mass fraction, and mixing and shearing;
(2) weighing chelerythrine raw medicine according to the mass fraction, adding the chelerythrine raw medicine into the material obtained in the step (1) until the chelerythrine raw medicine is uniformly sheared;
(3) grinding by a sand mill to obtain a material;
(4) and (4) adding xanthan gum into the material obtained in the step (3), and shearing to obtain the chelerythrine suspending agent.
Further limiting, the rotation speed of the sand mill in the step (3) is 2000r/min, and the grinding time is 1-1.5 h.
The particle size of the material in the step (3) is further limited to 3.50-4.00 for D50 and 10.00-10.50 for D90.
The invention also provides application of the chelerythrine suspending agent in prevention and treatment of rice black sesame leaf spot.
Further limiting, when the rice grows to 3-5 days before and after the heading stage, spraying the chelerythrine suspending agent twice.
Further limiting, the interval time of the two spraying is 8-12 days.
Further limiting, the dosage of chelerythrine used as a raw medicine for each spraying is 7.5ppm to 30 ppm.
The inspection of the chelerythrine suspending agent obtained by the invention shows that the chelerythrine suspending agent is qualified, and the quality control indexes are as follows: the pH value is 5-7, the suspension percentage is more than 97.24%, the wet sieve test (75 mu m) is more than 99%, the foaming performance is maintained for one minute, the particle size is 4mL, the particle size is D50-3.84, the particle size is D90-10.22, the dispersibility is qualified, the low-temperature stability is qualified, and the pourability is 0.36 mL.
The invention has the beneficial effects that:
the chelerythrine suspending agent obtained by the invention is beneficial to improving the adhesion, wettability and permeability of the medicament on the surface of crops, and compared with dosage forms such as missible oil and the like, the water-based agent type suspending agent has the characteristics of fine particle size, high suspension rate, no dust and the like, and is efficient and environment-friendly. And the effective component of the suspending agent is chelerythrine, so that the suspending agent is not easy to generate drug resistance, has the advantages of high efficiency, low toxicity, no public hazard, easy degradation, no environmental pollution and the like, and has certain competitive advantage in the market under the current requirements of developing green food and sustainable development of agriculture.
When the chelerythrine suspending agent disclosed by the invention is used for spraying rice, the remarkable prevention and treatment effect on the rice flax leaf spot is achieved, and the prevention and treatment effect of a medicament with the content of 7.5ppm is 45.2%; the control effect of the medicament with the content of 15ppm is as high as 62.5 percent; the control effect of the pesticide with the content of 30ppm is 77.3 percent, the control effect is higher than that of the common pesticide of 20 percent tricyclazole, and the chelerythrine suspending agent has good control effect on the rice flax spot.
Detailed Description
The raw materials used in the invention are as follows:
dispersing and wetting agent: atlox4913 (Poa, England), GenapolX080 (Craiden chemical Co., Ltd.), Dispersogen1494liq (Craiden chemical Co., Ltd.), UltrazineNA (Baligy industries, Ltd.), SOPROPHORSC (Solvay group), Ethylan NS-500LQ (Acksonobel), Lutensol XL-80 (Basff (China) Co., Ltd.); defoaming agent: sag1522 (mai pu high new materials group); thickening agent: magnesium aluminum silicate SK-05 (Suzhou middlings mineral materials Co., Ltd.), xanthan gum (commercially available), Kathon (commercially available); an antifreezing agent: urea (commercially available), glycerol (commercially available); deionized water.
The apparatus used in the present invention is as follows:
small vertical sand mill (100mL, laboratory), SYP intelligent glass constant temperature water bath (gu yu zuhua instrument factory), KQ-500DE type numerical control ultrasonic cleaner (kunshan ultrasonic instruments ltd.), GHP-9080 water-proof constant temperature incubator (shanghai-heng scientific instruments ltd.), IKARW20DS25 digital display top type stirrer (guangzhou instrumental laboratories technology ltd.), CP1502C electronic balance (aohao instruments ltd., shanghai, precision 0.01g), AL204/01 analytical balance (mettler-toli instruments ltd., precision 0.0001g), magnetic stirrer, agilent HPLC (agilent technologies ltd.), agilent technologies ltd., kyo 2221PH (italian hana), FYL-YS-100 full italian cold storage (beifu jiri ltd.), 325 standard auspicious sieve (beiwei yu instruments ltd), maje auspicious sieve (beiwei instruments ltd), An SHB-III circulating type multi-purpose vacuum pump (Zhengzhou Changcheng science and trade company, Ltd.), a DFY-300 swing type high-speed traditional Chinese medicine pulverizer (Wenling Dade traditional Chinese medicine machinery company, Ltd.), a BT-2002 laser particle size distribution instrument (Dandong Baite science and technology company, Ltd.), an IKA/T25 digital display type high-speed dispersion machine (Guangzhou instruments laboratory technology company, Ltd.), and a measuring cylinder (250mL and 500mL, Beijing glass station).
Example 1: screening of chelerythrine suspending agent formula
(1) Selection of wetting dispersant: the flow point of the wetting dispersant is measured by adopting a flow point method, and the auxiliary agent with good effect is selected. The screening results are shown in table 1.
TABLE 1 pour points of different wetting dispersants
(2) Selection of a basic formula: the wetting dispersants Atlox4913, Dispersogen1494liq and GenapolX080 with better flow points are selected to screen out the base formula with better effect by measuring the flow, and the results are shown in Table 2.
TABLE 2 flowability measurements for different formulations
According to the results shown in table 2, 6# was selected as the base formulation.
(3) Selection of the thickener: the fluidity and thermal storage water evolution of the sample were observed, and the results are shown in Table 3.
TABLE 3 flowability and Heat storage drainage behavior of the different thickeners
According to the results shown in table 3, the thickener was chosen to be xanthan gum + magnesium aluminum silicate (0.1% + 0.5%).
(4) Selection of antifreeze: common antifreezing agents (propylene glycol, glycerol and urea) are selected to prepare samples, low-temperature stability is observed, and results show that the low-temperature stability is qualified and is not frozen.
From the above experimental results, it was determined that the formulation of chelerythrine suspension is shown in table 4.
TABLE 4 Chelerythrine suspension formulation
Example 2: preparation method of chelerythrine suspending agent
(1) Preparing chelerythrine suspending agent according to the formula obtained in example 1, weighing dispersant Atlox4913, wetting agent GenapolX080, glycerol, magnesium aluminum silicate and deionized water according to mass fraction, mixing and shearing;
(2) weighing chelerythrine raw medicine according to the mass fraction, adding the chelerythrine raw medicine into the material obtained in the step (1) until the chelerythrine raw medicine is uniformly sheared;
(3) grinding by a sand mill to obtain a material, wherein the rotation speed of the sand mill is 2000r/min, the grinding time is 1h, the particle size of the material is D50-3.84, and D90-10.22;
(4) and (4) adding xanthan gum into the material obtained in the step (3), and shearing to obtain the chelerythrine suspending agent.
The chelerythrine suspending agent prepared in example 2 is subjected to quality identification, and the identification result shows that the suspending agent is a suspension liquid which is orange red, flowable, free of caking and easy to measure in volume, the content of active ingredients is 10% ± 1.0%, the pH value is 5-7, the suspension rate is more than 97.24%, a wet sieve test (75 microns) is more than 99%, 4mL is obtained after one minute of lasting foamability, the particle size is D50 ═ 3.84, the particle size is D90 ═ 10.22, the dispersibility is qualified, the low-temperature stability is qualified, and the pourability is 0.36 mL.
Example 3: application of chelerythrine suspending agent
The chelerythrine suspending agent prepared in the embodiment 2 is used for spraying rice 3-5 days before and after heading stage, the spraying is carried out twice, the time interval between the two spraying is 8-12 days, the prevention and treatment effect is obvious, and when the dose of the chelerythrine raw drug is 7.5ppm (namely, the chelerythrine suspending agent is diluted by 200 times), the prevention and treatment effect of the pesticide is 45.2%; when the dose of the chelerythrine raw drug is 15ppm (namely, the chelerythrine suspending agent is diluted by 100 times), the prevention and treatment effect of the drug is as high as 62.5%; when the dose of the chelerythrine raw pesticide is 30ppm (namely, the chelerythrine suspending agent is diluted by 50 times), the prevention and treatment effect of the pesticide is 77.3%, the prevention and treatment effect is higher than that of a common pesticide, namely 20% tricyclazole, and the chelerythrine suspending agent has a good prevention and treatment effect on rice flax leaf spot.
Claims (9)
1. The chelerythrine suspending agent is characterized by comprising the following raw materials: by mass, the chelerythrine raw medicine is 10%, the dispersing agent Atlox 49134%, the wetting agent Genapol X0802%, the glycerol is 5%, the magnesium aluminum silicate is 0.5%, the xanthan gum is 0.1%, the Sag 15220.2%, and the balance is deionized water.
2. The chelerythrine suspension concentrate according to claim 1, wherein said xanthan gum is added with a carob as a preservative during the preparation process.
3. A process for the preparation of chelerythrine-suspending agents according to claim 1 or 2, characterized in that it comprises the following steps:
(1) weighing the dispersant Atlox4913, the wetting agent Genapol X080, glycerol, magnesium aluminum silicate, Sag1522 and deionized water according to the mass fraction, and mixing and shearing;
(2) weighing chelerythrine raw medicine according to the mass fraction, adding the chelerythrine raw medicine into the material obtained in the step (1) until the chelerythrine raw medicine is uniformly sheared;
(3) grinding by a sand mill to obtain a material;
(4) and (4) adding xanthan gum into the material obtained in the step (3), and shearing to obtain the chelerythrine suspending agent.
4. The preparation method of claim 3, wherein the rotation speed of the sand mill in the step (3) is 2000r/min, and the grinding time is 1-1.5 h.
5. The preparation method of claim 4, wherein the particle size of the material in the step (3) is 3.50-4.00D 50-10.00D 90.
6. Use of the chelerythrine suspension concentrate according to claim 1 for controlling rice leaf spot.
7. The use as claimed in claim 6, wherein the spraying with chelerythrine suspension concentrate is carried out twice a total of 3-5 days before and after the heading date of the rice.
8. The application of the traditional Chinese medicine composition for treating the chronic bronchitis is characterized in that the interval time between two spraying is 8-12 days.
9. The use according to claim 7, characterized in that the dose of chelerythrine used as a raw drug per spray application is 7.5ppm to 30 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111276526.9A CN113875763B (en) | 2021-10-29 | 2021-10-29 | Chelerythrine suspending agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111276526.9A CN113875763B (en) | 2021-10-29 | 2021-10-29 | Chelerythrine suspending agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113875763A true CN113875763A (en) | 2022-01-04 |
| CN113875763B CN113875763B (en) | 2022-07-22 |
Family
ID=79014545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111276526.9A Active CN113875763B (en) | 2021-10-29 | 2021-10-29 | Chelerythrine suspending agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113875763B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114431248A (en) * | 2022-02-07 | 2022-05-06 | 陕西先农生物科技有限公司 | Suspending agent containing abamectin and chlorantraniliprole |
| CN115119847A (en) * | 2022-06-28 | 2022-09-30 | 黑龙江省农业科学院植物保护研究所 | Chelerythrine wettable powder and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102334478A (en) * | 2011-11-16 | 2012-02-01 | 南通联农农药制剂研究开发有限公司 | Suspoemulsion containing Envidor and preparation methods thereof |
| CN102657192A (en) * | 2012-05-22 | 2012-09-12 | 芜湖市多威农化有限责任公司 | Biological bactericide chelerythrine suspending agent and preparation method thereof |
| CN102701841A (en) * | 2012-05-22 | 2012-10-03 | 芜湖市多威农化有限责任公司 | Biological antimicrobial chelerythrine aqueous emulsion and preparation method thereof |
| CN103461329A (en) * | 2013-09-30 | 2013-12-25 | 浙江海正化工股份有限公司 | Pesticide composite dispersing agent and application of pesticide composite dispersing agent in preparation of pesticide suspending agent |
| CN103493804A (en) * | 2013-09-30 | 2014-01-08 | 浙江海正化工股份有限公司 | Compound pesticide wetting agent and application of compound pesticide wetting agent in preparation of pesticide preparations |
-
2021
- 2021-10-29 CN CN202111276526.9A patent/CN113875763B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102334478A (en) * | 2011-11-16 | 2012-02-01 | 南通联农农药制剂研究开发有限公司 | Suspoemulsion containing Envidor and preparation methods thereof |
| CN102657192A (en) * | 2012-05-22 | 2012-09-12 | 芜湖市多威农化有限责任公司 | Biological bactericide chelerythrine suspending agent and preparation method thereof |
| CN102701841A (en) * | 2012-05-22 | 2012-10-03 | 芜湖市多威农化有限责任公司 | Biological antimicrobial chelerythrine aqueous emulsion and preparation method thereof |
| CN103461329A (en) * | 2013-09-30 | 2013-12-25 | 浙江海正化工股份有限公司 | Pesticide composite dispersing agent and application of pesticide composite dispersing agent in preparation of pesticide suspending agent |
| CN103493804A (en) * | 2013-09-30 | 2014-01-08 | 浙江海正化工股份有限公司 | Compound pesticide wetting agent and application of compound pesticide wetting agent in preparation of pesticide preparations |
Non-Patent Citations (2)
| Title |
|---|
| 张彦辉 等: "12%甲维盐·虫螨腈悬浮剂的研制", 《农药》 * |
| 王晋阳 等: "40%甲基硫菌灵·三环唑悬浮剂的配方研制", 《农药》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114431248A (en) * | 2022-02-07 | 2022-05-06 | 陕西先农生物科技有限公司 | Suspending agent containing abamectin and chlorantraniliprole |
| CN114431248B (en) * | 2022-02-07 | 2023-09-01 | 陕西先农生物科技有限公司 | Suspending agent containing avermectin and chlorantraniliprole |
| CN115119847A (en) * | 2022-06-28 | 2022-09-30 | 黑龙江省农业科学院植物保护研究所 | Chelerythrine wettable powder and preparation method and application thereof |
| CN115119847B (en) * | 2022-06-28 | 2023-09-19 | 黑龙江省农业科学院植物保护研究所 | Chelidonine wettable powder and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113875763B (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113875763B (en) | Chelerythrine suspending agent and preparation method and application thereof | |
| CN102165956A (en) | Pesticide composite containing bispyribac-sodium and penoxsulam and application thereof | |
| CN105475303B (en) | A kind of composition pesticide containing kasugarnycin and gold alloy hydride | |
| CN104381314A (en) | Botanical insecticide | |
| CN109042690B (en) | Topramezone dispersible oil suspending agent and application thereof | |
| CN111328819A (en) | Low-temperature-resistant suspending agent containing spirotetramat and preparation method thereof | |
| CN106386796B (en) | Bispyribac-sodium cyhalofop-butyl suspension emulsion and preparation method thereof | |
| CN108293723B (en) | Method for controlling soil heavy metal cadmium lead pollution flowering cabbage | |
| CN109329292A (en) | A kind of pinoxaden and the dispersible oil-suspending agent of fluroxypyr and its preparation method and application | |
| CN114514930A (en) | Bactericidal composition for preventing and treating crop bacterial diseases | |
| CN113508823A (en) | Trichoderma atroviride dispersible oil suspending agent containing indolebutyric acid and amino-oligosaccharin, preparation method and application of trichoderma atroviride dispersible oil suspending agent in pathogenic nematode prevention and control | |
| CN109627104B (en) | Water-soluble fertilizer for fruit tree planting and preparation method and application thereof | |
| CN103858931B (en) | Eucommia leaf growth conditioning agent | |
| WU et al. | Effect of intercropping with tillered onion on mineral nutrient uptake and gray mold disease occurrence of tomato | |
| CN112335667B (en) | Oil suspending agent containing isoprothiolane and propiconazole and preparation method and application thereof | |
| CN103392703A (en) | Weed killer composition used for cassava field | |
| CN111109263A (en) | Herbicide for preventing and controlling weeds in ophiopogon root lawn | |
| CN104322499B (en) | A kind of composite bactericide | |
| CN114304173B (en) | Pesticide composition for preventing and treating sclerotinia rot and application thereof | |
| CN108432780A (en) | A kind of cornfield herbicidal and preparation method thereof | |
| CN116250529A (en) | Suspending agent containing fluazinam and cyazofamid and preparation method thereof | |
| CN106665595A (en) | Bactericidal composition containing flutianil and application of bactericidal composition | |
| CN111387196B (en) | Multi-phase preparation for treating diseases and pests and treating seeds | |
| CN114190386B (en) | Compound composition of propamidine and sabinenol, bactericide and application | |
| CN117778252A (en) | Soil remediation microbial inoculum for preventing and treating bighead atractylodes rhizome continuous cropping obstacle as well as preparation method and application 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |