CN106614607A - Insecticide composition containing tolfenpyrad and cyantraniliprole - Google Patents
Insecticide composition containing tolfenpyrad and cyantraniliprole Download PDFInfo
- Publication number
- CN106614607A CN106614607A CN201610870297.6A CN201610870297A CN106614607A CN 106614607 A CN106614607 A CN 106614607A CN 201610870297 A CN201610870297 A CN 201610870297A CN 106614607 A CN106614607 A CN 106614607A
- Authority
- CN
- China
- Prior art keywords
- tolfenpyrad
- composition
- insect amide
- bromine cyanogen
- cyanogen insect
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to an insecticide composition containing tolfenpyrad and cyantraniliprole, belonging to the field of chemical control. The insecticide composition contains the effective components including tolfenpyrad and cyantraniliprole, and auxiliaries, and has an excellent synergistic effect to the control of rice leaf folders. An indoor bioassay experiment shows that the synergistic effect ratio of the insecticide composition on the rice leaf folders is (80 to 1)-(1 to 80). A field experiment shows that different dosage forms of the composition containing the two components present excellent control effects on the rice leaf folders, and the control effect on the rice leaf folders is 88% or above after the composition is used for 7 days, is 91% or above after the composition is used for 14 days and is remarkably higher than the control effect of a common insecticide, namely Coragen. The insecticide composition has the characteristics that the synergistic effect is remarkable, the control effect is good, the dosage is low, and the composition is safe to the environment and target organisms and has multiple treatment effects; and the composition can be used for simultaneously treating other insect attacks (such as striped rice borer and tryporyza incertulas) on the rice and has a very good effect of delaying the drug resistance of the rice leaf folders to chlorantraniliprole.
Description
Technical field
The invention belongs to Chemical Control of Harmful Insects field, and in particular to one kind preventing and treating rice grub, especially rice leaf roller
Compounded pesticides.
Background technology
Rice leaf roller（Cnaphalocrocis medinalis Guenee）For the moving property insect of paddy rice two, newly hatched larvae
Young leaves is taken food, as worm age increases, leaf roll piece is indulged into cylindric worm bud, larva to be hidden oneself and gnaw mesophyll in it, leaves epidermis in vain
Vitta spot.When serious " worm bud is innumerable, Bai Yeman fields ".With impaired maximum of pregnant, heading stage.Adult has phototaxis, perches concealment
Property and spawning become tender property.The multiplex health width of rice leaf roller is prevented and treated now, and its resistance to the action of a drug can not be ignored.
Tolfenpyrad, is new pyrazole heterocycle class insecticidal/acaricidal agent, and its main mechanism is the oxygen for preventing insect
Change phosphorylation, also with ovicidal, suppression food, oviposition deterrence and bactericidal action.
Bromine cyanogen insect amide, also known as cyanogen insect amide, are second generation ryanodine receptors that E.I.Du Pont Company develops after chlorantraniliprole
Inhibitor insecticides, insecticidal range is wider, by the ryanodine receptor for activating target pest, discharges striated muscle and smooth muscle is thin
The calcium of intracellular, causes insect paralysis dead, can effectively prevent and treat Lepidoptera, Semiptera and coleopteran pest.
So far, the evils such as the insecticides preventing and treating rice leaf roller of Tolfenpyrad and bromine cyanogen insect amide are not yet found
The report of worm.
The content of the invention
It is an object of the invention to provide a kind of insecticides of preventing and treating rice leaf roller, by Tolfenpyrad and bromine cyanogen
The mixture of insect amide, makes the insecticide of certain proportioning, and for preventing and treating rice leaf roller, effect is good, and dosage is low, can be fine
Preventing and treating rice leaf roller and rice terrace other insects.
The technical solution used in the present invention is as follows：
A kind of insecticides containing Tolfenpyrad and bromine cyanogen insect amide, it is characterised in that：By active ingredient Tolfenpyrad, bromine
Cyanogen insect amide and auxiliary material component are constituted, and wherein the mass ratio of Tolfenpyrad and bromine cyanogen insect amide is 80:1~1:80, active ingredient
Gross weight percentage composition is 1% ~ 80%.
In the compounded pesticides, the mass ratio of Tolfenpyrad and bromine cyanogen insect amide optimization is 10:1~1:80.
In the compounded pesticides, the mass ratio that Tolfenpyrad and bromine cyanogen insect amide further optimize is 10:1~1:10.
The compounded pesticides can be processed into missible oil, suspending agent, water-dispersible granules, wettable according to techniques known in the art
Property pulvis, aqueous emulsion, micro-capsule suspension.
When the present invention is missible oil, the weight percentage of each component is：
Tolfenpyrad：1-30%
Bromine cyanogen insect amide：1-30%
Solvent：3-30%
Emulsifying agent：5-10%
The concrete procedure of processing of this insecticides missible oil is：It is by above-mentioned formula solvent that Tolfenpyrad and bromine cyanogen insect amide is molten
Solution, adds emulsifying agent, stirs in stirred tank, you can prepare the cream preparation of this composition.
When the present invention is wettable powder, the weight percentage of each component is：
Tolfenpyrad 1-40%
Bromine cyanogen insect amide 1-40%
Dispersant 3-10%
Wetting agent 1-8%
Filler polishing is to 100%
The concrete procedure of processing of this insecticides wettable powder is：By above-mentioned formula by Tolfenpyrad and bromine cyanogen insect amide with
And dispersant, wetting agent and filler mix, the uniform stirring in stirred tank is well mixed Jing after airslide disintegrating mill, you can prepare
The wettable powder of inventive composition.
When the present invention is water dispersible granules, the weight percentage of each component is：
Tolfenpyrad 1-40%
Bromine cyanogen insect amide 1-40%
Dispersant 2-8%
Wetting agent 2-8%
Disintegrant 2-4%
Filler polishing is to 100%
The concrete procedure of processing of this insecticides water dispersible granules is：By above-mentioned formula by Tolfenpyrad, bromine cyanogen insect amide and
Dispersant, wetting agent, disintegrant and filler are well mixed, and are crushed with micro jet, and Jing is mediated, and is subsequently adding fluidisation
Granulated in bed granulating and drying machine, be dried, sieve after Jing sample analysis, the moisture of prepared Pesticidal combination of the present invention
Shot agent.
When the present invention is suspending agent, the weight percentage of each component is：
Tolfenpyrad 1-40%
Bromine cyanogen insect amide 1-40%
Dispersant 3-6%
Wetting agent 1 ~ 4%
Antifreezing agent 0.5-4%
Thickener 0.1-3%
Defoamer 0.1-0.5%
Water polishing is to 100%
The procedure of processing of this insecticides suspending agent is：First auxiliary agent is mixed, Jing high speed shears are well mixed, add azoles worm
Acid amides and bromine cyanogen insect amide active compound, grind 3 ~ 4 hours in sand mill, make diameter of particle all in 5 below m, and institute of the present invention is obtained
The insecticides suspending agent stated.
When the invention is aqueous emulsion, the weight percentage of each component is：
Tolfenpyrad 1-40%
Bromine cyanogen insect amide 1-40%
Emulsifying agent 2-6%
Solvent 3-5%
Antifreezing agent 1-3%
Thickener 0.1-5%
Defoamer 0.1-1%
Water polishing is to 100%
The procedure of processing of this Pesticidal combination aqueous emulsion is：Tolfenpyrad and bromine cyanogen insect amide, solvent and emulsifying agent are added in into one
Rise, dissolve uniformly oil phase；Water, antifreezing agent etc. are mixed into uniformly water phase；Simultaneously by water phase under high-speed stirred
In adding oil phase, high speed shear 5-10min forms oil-in-water type aqueous emulsion.Insecticides of the present invention are obtained
Aqueous emulsion.
When the present invention is micro-capsule suspension, the weight percentage of component is：
Tolfenpyrad 1-40%
Bromine cyanogen insect amide 1-40%
Capsule leather material 0.5-4%
Solvent 1-3%
Dispersant 1-4%
Emulsifying agent 2-4%
Thickener 1-2%
PH adjusting agent 0-2%
Water polishing is to 100%
（1）Tolfenpyrad and bromine cyanogen insect amide are dissolved in solvent, add capsule leather material to be uniformly mixing to obtain oil phase；（2）
Emulsifying agent, adjuvant is added to be uniformly mixing to obtain water phase in water；（3）Water is added in oil phase, high speed homogenizing formation oil-in-water
Emulsion；（4）Under 450 revs/min of speed conditions, polyamine is added to participate in interface polymerization reaction, reaction temperature rises to 25 DEG C -70
DEG C, keep 2-24 hours solidification encystation；（5）Dispersant, thickener are added, stirs the microcapsule suspending agent that make.
Emulsifying agent of the present invention be alkylbenzene naphthalene sulfonate, APES phosphate, diphenyl phenol gather
Oxygen ethene polyethenoxy ether, styrenated phenol APEO, APES formaldehyde condensation product, diphenyl phenol polyoxy second
In alkene polyformaldehyde condensation product, castor oil ethylene oxide adduct, NNO, NP, agriculture breast 500, agriculture breast 600, Tween-80, polyvinyl alcohol
One or more.
Dispersant of the present invention is lignosulfonates, fatty acid amide N methyl taurine sodium salt, alkyl phenol polyoxy second
In alkene ether sulphate, polyoxyethylene polyoxypropylene block copolymer, APES, AEO one
Plant or several.
Wetting agent of the present invention is selected from：Lauryl sodium sulfate, calcium dodecyl benzene sulfonate, Nekal BX, alkyl
One or more in benzene sulfonic acid sodium salt, polyoxyethylene tri-styryl phosphenylic acid salt, spaonin powder.
Disintegrant of the present invention is selected from：Bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, bicarbonate
One or more in sodium.
Filler of the present invention is selected from：Kaolin, diatomite, bentonite, attapulgite, white carbon, starch, lightweight carbon
One or more in sour calcium.
Thickener of the present invention is aluminium-magnesium silicate, xanthans, hydroxymethyl cellulose, gum arabic, polyvinyl pyrrole
One kind in alkanone or several.
Antifreezing agent of the present invention is selected from：One or more in ethylene glycol, propane diols, glycerine, polyethylene glycol.
Defoamer of the present invention is selected from：Silicone oil, silicone compound, C10-20 saturated fat acids compounds, C8-
One or more in 10 aliphatic alcohols compounds and polyoxyethylene glycerol ether.
Capsule leather material of the present invention is tolyl isocyanate, many toluene diisocyanates of polymethylene, diphenylmethyl
One or more in alkane diisocyanate, Lauxite.
Solvent of the present invention be toluene, dimethylbenzene, ethanol, N,N-dimethylformamide, chloroform, cyclohexanone,
One or more in hexamethylene, acetone.
PH adjusting agent of the present invention mainly have hydrochloric acid, glacial acetic acid, citric acid, NaOH, ammoniacal liquor, ethylenediamine, three
One kind in monoethanolamine, triethylamine.
The Pesticidal combination of the present invention compared with prior art, produces following beneficial effect：(1) compared with single dose, the group
Compound is to rice leaf roller notable synergistic, hence it is evident that improve prevention effect, significantly reduces drug cost；（2）Insect can be slowed down
The resistance to the action of a drug to medicament, extends the service life of medicament；（3）Have quick-acting and long-acting functions concurrently to rice leaf roller；(4) may be used
Field dosage is greatly reduced, environmental pollution and residues of pesticides are effectively reduced；(5) poison to other non-target organisms is reduced
Property.
Experimental data
First, reagent agent：Tolfenpyrad active compound；Bromine cyanogen insect amide active compound
2nd, for examination insect：Rice leaf roller
3rd, assay method：
The method combined using Toxicity Determination and field test.
First the co-toxicity coefficient of the built agent to rice leaf roller of different ratio is drawn by Toxicity Determination, then passed through
Clear and definite its prevention effect of field control effectiveness test, determines the formula rate and optimum amount of built agent.
Toxicity Determination：Using dip method.Active compound is calculated into dosage by active ingredient, mother liquor is configured to, plus clear water is dilute
5 ~ 7 gradient concentrations are interpreted as, control is processed as with clear water, each process sets 3 repetitions.Select growth conditions it is basically identical 3
Instar larvae 15, input is filled in the experiment bucket of liquid, adds a cover gauze（Preventing and treating is escaped）, it is placed in 25 DEG C of insulating boxs, after 24 h
Investigation death condition, records dead borer population.
Field efficacy：The formula that indoor bioassay gained has synergistic effect is made into missible oil（EC）, suspending agent（SE）, can
WP（WP）, water-dispersible granules（WDG）, aqueous emulsion（EW）, micro-capsule suspension（CS）Tested.Cell spray is set
After dispenser agent, check preventive effect and determine suitable dosage.
Table 1 gives the toxicity test result of 2 kinds of medicaments and mixture to rice leaf roller；
It can be seen from Table 1 that, bromine cyanogen insect amide shows good indoor virulence effect, LC to rice leaf roller50For
0.192 mg/L, Tolfenpyrad is slightly worse to the virulence result of rice leaf roller, and the compounding of Tolfenpyrad and bromine cyanogen insect amide is 80:
1~1:120 are all higher than to the co-toxicity coefficient of rice leaf roller in the range of 80, it is shown that synergistic effect well.
The Tolfenpyrad of table 1 is with bromine cyanogen insect amide different proportion mixture to rice leaf roller（3 ages）Virulence
Specific embodiment
The present invention is elaborated below by embodiment, by Tolfenpyrad and bromine cyanogen insect amide with 80:1~1:80 ratios
Example is processed into formulation, and the percentage in embodiment is weight percentage；But the invention is not limited in this.
Embodiment 1：30% Tolfenpyrad bromine cyanogen insect amide missible oil
Tolfenpyrad 25%, bromine cyanogen insect amide 5%, acetone 30%, cyclohexanone 10%, agriculture breast 600# 3%, the condensation of castor oil polyethylene glycol
Thing 4%, dimethylformamide complements to 100%, stirs, and 30% Tolfenpyrad bromine cyanogen insect amide missible oil is obtained.
Embodiment 2：30% Tolfenpyrad bromine cyanogen insect amide wettable powder
Tolfenpyrad 25%, bromine cyanogen insect amide 5%, fatty acid amide N methyl taurine sodium salt 8%, spaonin powder 8%, ammonium sulfate 5%, two
Silica 15%, precipitated calcium carbonate is mended to 100%, is crushed with airslide disintegrating mill after mixing, and 30% Tolfenpyrad bromine cyanogen worm acyl is obtained
Amine wettable powder.
Embodiment 3：30% Tolfenpyrad bromine cyanogen insect amide water dispersible granules
Tolfenpyrad 25%, bromine cyanogen insect amide 5%, fatty acid amide N methyl taurine sodium salt 4%, Methyl fatty acid amides benzene sulfonic acid sodium salt
3%, polyoxyethylene tri-styryl phosphenylic acid salt 5%, urea 2%, bentonite is supplied to 100%, and mixing granulation is obtained 30% azoles worm acyl
Amine bromine cyanogen insect amide water dispersible granules.
Embodiment 4：30% Tolfenpyrad bromine cyanogen insect amide suspending agent
Tolfenpyrad 25%, bromine cyanogen insect amide 5%, APES 4%, NNO3%, aluminium-magnesium silicate 1%, xanthans 0.15%,
Ethylene glycol 1%, polyoxyethylene glycerol ether 0.5%, water is supplied to 100%, and after uniform mixing sand mill is put into, and is ground to the m of particle diameter 5,
Make 30% Tolfenpyrad bromine cyanogen insect amide suspending agent.
Embodiment 5：30% Tolfenpyrad bromine cyanogen insect amide aqueous emulsion
Tolfenpyrad 25%, bromine cyanogen insect amide 5%, NP-10 4%, dimethylformamide 5%, cyclohexanone 3%, aluminium-magnesium silicate 3%, urea
2%, polyoxyethylene glycerol ether 0.5%, water is supplied to 100%.Active compound is dissolved with solvent, slowly adds solution under constant rotational speed
Enter in water phase, 30% Tolfenpyrad bromine cyanogen insect amide aqueous emulsion is obtained.
Embodiment 6：30% Tolfenpyrad bromine cyanogen insect amide micro-capsule suspension
Tolfenpyrad 25%, bromine cyanogen insect amide 5%, dimethylformamide 5%, the % of methyl diphenylene diisocyanate 0.5, polyethylene
Alcohol 2%, fatty acid amide N methyl taurine sodium salt 1%, hexamethylene diamine 1%, gum arabic 2%, water complements to 100%, as stated above
30% Tolfenpyrad bromine cyanogen insect amide micro-capsule suspension is obtained.
The method that rice leaf roller is prevented and treated using above-mentioned composition pesticide is in rice leaf roller early period of origination（Moth peak period
Or roll up at the beginning of blade tip）Add water and be made into suspension spray and use or uniformly spread fertilizer over the fields inside seedbed or rice field, preventing and treating rice leaf roller and
Other harmful organisms, its effect is shown in Table 2.
The methaldehyde of table 2 preparation different from emamectin benzoate prevents and treats the field efficacy of Pomacea canaliculata
It can be seen from Table 2 that, to cnaphalocrocis during the difference preparation 5g/ mu times liquid dispensers of 30% Tolfenpyrad bromine cyanogen insect amide
Snout moth's larva shows good preventive effect.7 days preventive effects are more than 88% after medicine, after medicine 14 days preventive effects more than 91%, under Isodose
Preventive effect is significantly better than comparison medicament health width, is the good compound drug for preventing and treating rice leaf roller.
Visible above, Tolfenpyrad, two kinds of medicament mixtures of bromine cyanogen insect amide have good in terms of preventing and treating rice leaf roller
Application prospect.
In addition, the formula can also be fabricated to ultra low volume liquids is used for for air-spraying and thermal fog, aerosol formulations
The Field information of atomizing sprayer and hot mist machine.
Claims (4)
1. a kind of insecticides containing Tolfenpyrad and bromine cyanogen insect amide, it is characterised in that：By active ingredient Tolfenpyrad,
Bromine cyanogen insect amide and auxiliary material component are constituted, and the mass ratio of Tolfenpyrad and bromine cyanogen insect amide is 80:1~1:80.
2. insecticides according to claim 1, it is characterised in that：In the insecticides Tolfenpyrad and
The mass ratio of bromine cyanogen insect amide is 20:1~1:20.
3. insecticides according to claim 1, it is characterised in that：In the insecticides methaldehyde and
The mass ratio of emamectin benzoate is 20:1~5:1.
4. insecticides according to claim 1, it is characterised in that：The formulation of the insecticides is breast
Oil, suspending agent, water-dispersible granules, wettable powder, aqueous emulsion, micro-capsule suspension.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610870297.6A CN106614607B (en) | 2016-10-06 | 2016-10-06 | A kind of insecticide composition containing Tolfenpyrad and bromine cyanogen insect amide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610870297.6A CN106614607B (en) | 2016-10-06 | 2016-10-06 | A kind of insecticide composition containing Tolfenpyrad and bromine cyanogen insect amide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106614607A true CN106614607A (en) | 2017-05-10 |
| CN106614607B CN106614607B (en) | 2018-12-14 |
Family
ID=58854068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610870297.6A Active CN106614607B (en) | 2016-10-06 | 2016-10-06 | A kind of insecticide composition containing Tolfenpyrad and bromine cyanogen insect amide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106614607B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1988803A (en) * | 2004-07-26 | 2007-06-27 | 杜邦公司 | Mixtures of anthranilamide invertebrate pest control agents |
| CN106417308A (en) * | 2016-09-21 | 2017-02-22 | 江西省农业科学院植物保护研究所 | Synergistic insecticidal composition containing cyantraniliprole and application thereof |
-
2016
- 2016-10-06 CN CN201610870297.6A patent/CN106614607B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1988803A (en) * | 2004-07-26 | 2007-06-27 | 杜邦公司 | Mixtures of anthranilamide invertebrate pest control agents |
| CN106417308A (en) * | 2016-09-21 | 2017-02-22 | 江西省农业科学院植物保护研究所 | Synergistic insecticidal composition containing cyantraniliprole and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106614607B (en) | 2018-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104472511B (en) | A kind of molluscicide compositions containing the methaldehyde and emamectin benzoate | |
| US11612165B2 (en) | Pesticide composition for controlling Spodoptera frugiperda | |
| CN102113496B (en) | Bactericidal composition containing dicyclanil and methomyl | |
| CN103155929B (en) | Binary pesticide composition and application thereof | |
| CN103004821A (en) | Insecticidal composition containing thiodicarb and spinosad | |
| CN105638690B (en) | A kind of composition pesticide containing emamectin benzoate and niclosamide ethanolamine salt | |
| CN105532710A (en) | Clothianidin-containing seed-treating composition | |
| CN104920407A (en) | Composition for preventing and treating underground insects | |
| CN106472530A (en) | A kind of Synergistic insecticidal compositions comprising AVM and the methaldehyde | |
| CN110521729A (en) | A kind of composition pesticide and its application | |
| CN106614607A (en) | Insecticide composition containing tolfenpyrad and cyantraniliprole | |
| CN104585230A (en) | Nematicidal composition containing fosthiazate and fluopyram | |
| CN106665614A (en) | Weeding composition containing penoxsulam, bispyribac-sodium and mefenacet | |
| CN106538557A (en) | Bactericidal composition comprising BIT class and azoles mepanipyrim | |
| CN106719732A (en) | Paddy rice special pesticide composition | |
| CN108719295A (en) | A kind of molluscicide composition containing Tea Saponin | |
| CN104488889A (en) | Nematicidal composition containing fluensulfone and fluopyram | |
| CN105028465B (en) | A kind of composition for killing sanitary insect pest | |
| CN106665625A (en) | Insecticidal composition and application thereof | |
| CN104186533B (en) | A kind of composite insecticide and application thereof preventing and treating leaf-roller | |
| CN103636632B (en) | A kind of Pesticidal combination containing chlorine chlorfenapyr and Aphox | |
| CN112021319B (en) | Weeding composition containing pentoxazone and dithiopyr | |
| CN107047588A (en) | A kind of Pesticidal combination comprising flonicamid and benzoyl urea compound | |
| CN107455384B (en) | A kind of pesticide synergistic composition containing phenthoate dimephenthoate cidial | |
| CN104322534A (en) | Insecticidal composition containing clothianidin and chromafenozid |
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 |