CN101816303B - Spirodiclofen hot aerosol and preparation method thereof - Google Patents
Spirodiclofen hot aerosol and preparation method thereof Download PDFInfo
- Publication number
- CN101816303B CN101816303B CN201010174122.4A CN201010174122A CN101816303B CN 101816303 B CN101816303 B CN 101816303B CN 201010174122 A CN201010174122 A CN 201010174122A CN 101816303 B CN101816303 B CN 101816303B
- Authority
- CN
- China
- Prior art keywords
- spirodiclofen
- hot aerosol
- oil
- percent
- solvent
- 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.)
- Expired - Fee Related
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a spirodiclofen hot aerosol and a preparation method thereof. The spirodiclofen hot aerosol and the preparation method thereof are characterized in that: the spirodiclofen hot aerosol comprises the following raw materials in percentage by weight: 5 to 20 percent of spirodiclofen, 2 to 25 percent of surface active agent, 1to 2 percent of organic silicon defoamer, 0.5 to 2 percent of anti-freeze agent, 0.5 to 1 percent of antioxidant, and the balance of solvent. The spirodiclofen hot aerosol has the advantages of wide acarid killing spectrum, killing of egg and larva, strong contact poisoning action, long effective period, high utilization efficiency, no cross resistance with the conventional acaricide, and also suitability for preventing and controlling the harm of eotetranychus sexmaculatus riley to a rubber tree, and a high fruit tree, an ornamental plant, protected agriculture and the like.
Description
Technical field
The present invention relates to technical field of pesticide, especially relate to a kind of spirodiclofen hot aerosol and preparation method thereof.
Background technology
Eotetranychus sexmaculatus (Eotetranychus sexmaculatus Riley) another name rubber yellow spider, belongs to arachnids, Acari, Acariformes, Tetranychidae.Be distributed in the states such as Japan, the U.S. and New Zealand abroad; The domestic provinces and regions such as Guangdong, Guangxi, Hainan, Yunnan, Sichuan, Hunan, Jiangxi and Taiwan that are distributed in.Eotetranychus sexmaculatus 20 diversified economy crop and the wild plants such as rubber, oranges and tangerines, tung oil tree, cashew nut, tea tree, guava, acacia confusa, China tree, mango and pineapple of can causing harm.If to become mite mite and young mite thorn phyllidium meat tissue, draw the green grain of cell sap and leaf.During beginning, along blade back master pulse both sides base portion, endanger and present yellow patch, continuing to extend between lateral vein afterwards, gently making blade lose chlorophyll, affecting photosynthesis, heavy make that blade is withered and yellow to come off, make to tap rubber then to pause a period of time, reduce latex output.In recent years, along with global warming, Eotetranychus sexmaculatus also constantly increases the weight of the harm of rubber.In Hainan, west of Guangdong Province Yuexi, Deng Zhijiao district, Yunnan occur general, the outstanding happiness rubber opening cutting woods of causing harm,, there is area and expand year by year in the wildness that causes harm in some areas.Therefore, take the harm of effective ways prevention and control Eotetranychus sexmaculatus to seem particularly important.
Spiral shell mite ester, trade name is mite danger Envidor (Bayer Bitterfeld GmbH), chemical name: 3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro [4, the 5]-last of the ten Heavenly stems-3-alkene 4-base-2,2-dimethyl butyrate acid esters, molecular formula: C
21h
24cl
2o
4, product type is tetronic acid class miticide tetronic acid.Spiral shell mite ester miticide has action of contace poison, without interior absorption.The mode of action mainly suppresses the Fatty synthesis of mite, the energy metabolism of blocking-up mite, and each developmental stage of mite is all effective, comprises ovum.This medicament novel structure, the mechanism of action are unique, and between existing miticide without cross resistance, be applicable to for control, existing miticide be produced the pest mite class of resistance.The mite that kills of spiral shell mite ester is composed wide, strong adaptability, and two spotted spider mite, yellow spider, Xiu Pi lice, yellow tea mite, Tetranychus cinnabarinus and Tetranychus urticae etc. are all had to fine preventive effect.In addition, it has the well double effect of controlling to insects such as pear sucker, oystershell scale and leafhopper classes.Spiral shell mite ester is the novel miticide in recent years going on the market, effective, and between existing miticide without cross resistance.
At present, existing spiral shell mite ester market sale preparation is mainly suspending agent, aqueous emulsion, not yet occurs spirodiclofen hot aerosol product.Its suspending agent and aqueous emulsion shortcoming separately: suspending agent particle diameter is larger, effectively spread area is little, is not easy to be absorbed, and control efficiency is not good; Aqueous emulsion mainly adopts the organic solvents such as dimethylbenzene as carrier, and environmental pollution is larger.
In addition, although the agricultural chemicals of existing control bamboo grows Eotetranychus sexmaculatus has pyridaben thermal fog and complex preparation thereof, but frequent owing to using, in addition without other novel thermal fog product substitution, use, long-term use causes Eotetranychus sexmaculatus to produce serious pesticide resistance, makes pyridaben thermal fog product control Eotetranychus sexmaculatus poor effect.
In sum, develop new control bamboo grows Eotetranychus sexmaculatus agricultural chemicals and preparation thereof and seem particularly important, there is important practical and be worth.
Summary of the invention
The defect existing in order to overcome above technology, the object of this invention is to provide a kind of spirodiclofen hot aerosol, is intended to make up existing spiral shell mite ester formulation in the deficiency of rubber forest control Eotetranychus sexmaculatus.
Another object of the present invention is to provide above-mentioned a kind of spirodiclofen hot aerosol and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is:
, by the raw material of following percentage by weight, formed:
Spiral shell mite ester 5～20%
Surfactant 5～25%
Silicone defoaming agent 1～2%
Antifreeze 0.5～2%
Antioxidant 0.5～1%
Solvent surplus.
Described surfactant is alkyl benzene calcium sulfonate, the lauryl sulfate calcium of anionic, two or more in the alkylphenol polyoxyethylene of nonionic, sorbitan fatty acid ester class, agriculture breast 600#, Nongru-700 #, peaceful newborn 33#, secondary alcohol APEO, methyl naphthalene sulfonate formaldehyde condensate, benzyl naphthalenesulfonic acid-formaldehyde condensate.
Described sorbitan fatty acid ester class is sorbitan mono-laurate (Span-20) or sorbitan monooleate (Span-80).
Described silicone defoaming agent is dimethicone.
Described antifreeze is ethylene glycol or propane diols.
Described antioxidant is one or more in dibutyl hydroxy toluene, epoxidized soybean oil, tall oil.
Described solvent is aromatic hydrocarbons two wires oil, aromatic hydrocarbons third fractional oil, residual oil, white oil, castor oil, turpentine oil, soybean oil, triethylene glycol, the cyclohexanone of high boiling point, high-flash, two or more in DMF.
The preparation method of described spirodiclofen hot aerosol, it is characterized in that, take proportioning raw material described above, the former medicine of spiral shell mite ester is dropped into and regulated in still, to the solvent that injects solvent total amount 50～60% in still, if dissolve slowly, be suitably heated to 40～50 ℃, open and regulate still agitator to stir, add while stirring surfactant, silicone defoaming agent, antifreeze, antioxidant; Finally inject remaining solvent, continue to stir 20～30 minutes, obtain the oily product of homogeneous transparent, through being up to the standards, package storage.
The present invention not only makes up the deficiency of Traditional Agricultural pharmaceutically dosage form emulsifiable concentrate to control Eotetranychus sexmaculatus such as the tall and big glue woods of trees, orchard, industrialized agricultures, and emphasis solves the harm of Eotetranychus sexmaculatus to bamboo grows.The present invention specifically has the following advantages:
1. kill mite and compose wide, young double the killing of ovum: two spotted spider mite, yellow spider, yellow tea mite, Tetranychus cinnabarinus and Tetranychus urticae etc. are all had to fine preventive effect, if children mite is also had to good action of contace poison simultaneously.And female one-tenth mite is had to good sterilisation-effect.It is quantitatively compressed to spiral shell mite ester in fuming pipe and mixes with high velocity air by hot mist machine, is directed onto in atmosphere.Due to the lightweight of high velocity air and droplet itself the outstanding ability of wafing, droplet is sent to far very high distance, can overcome the feature of the height of tree.In addition by day, " chimney " effect because the interval between trunk causes, can make droplet rise on tree crown, medicament is fully contacted with sick leaf, and be attached on disease leaf, reaches control efficiency.
2. without cross resistance: mixed with existing miticide, can improve the quick-acting of spiral shell mite ester, be also conducive to the resistance management of mite evil.
3. the green formulation of environmental ideals: very safe to crop under different temperature conditions, to people and animals and crop safety, low toxicity.This formulation need not be watered, and directly uses, and by filling the air skyborne medicament, kills pest, therefore, to water resource, can not exert an influence.
4. saving of work and time: because this formulation need not be watered, directly use, particularly easy to use at mountain area plantation.Effect in unit interval, unit are dispenser is conventional 4～6 times of spraying, so dispenser efficiency is high, can reach the object of saving of work and time.
5, thermal fog action of contace poison of the present invention is strong, and the lasting period is long, and utilization ratio is high, and between existing miticide without cross resistance, be applicable to the local control of pest mite such as protected crop, tall and big trees.
Specific implementation method
Below in conjunction with preferred embodiment, the present invention is described in further detail, but the present invention is never limited to following embodiment.
Embodiment mono-
According to following weight proportion 5% spirodiclofen hot aerosol:
Spiral shell mite ester 5kg
Alkylphenol polyoxyethylene OP-4 3kg
Span-20 4kg
Secondary alcohol APEO 1kg
Lauryl sulfate calcium 2kg
Dimethicone 0.5kg
Ethylene glycol 1kg
Dibutyl hydroxy toluene 0.5kg
Triethylene glycol 40kg
Aromatic hydrocarbons two wires oil 43kg
The preparation method of spirodiclofen hot aerosol: press above-mentioned raw materials proportioning the former medicine 5kg of spiral shell mite ester is dropped in stirred tank, in still, inject solvent triethylene glycol 40kg, if dissolve slowly, suitably be heated to 40 ℃, opening stirred tank stirs, add while stirring surfactant alkylphenol polyoxyethylene OP-4 3kg, Span-20 4kg, secondary alcohol APEO 1kg, lauryl sulfate calcium 2kg, silicone defoaming agent dimethicone 0.5kg, antifreeze ethylene glycol 1kg, antioxidant dibutyl hydroxy toluene 0.5kg; Finally inject remaining solvent aromatic hydrocarbons two wires oil 43kg, continue to stir 20 minutes, static, remove by filter impurity, obtain the oily product of homogeneous transparent, through after the assay was approved, carry out package storage.
Embodiment bis-
According to following weight proportion 10% spirodiclofen hot aerosol:
Spiral shell mite ester 10kg
Alkylphenol polyoxyethylene OP-7 4kg
Span-80 5kg
Peaceful newborn 33# 4kg
Benzyl naphthalenesulfonic acid-formaldehyde condensate 2kg
Dimethicone 1kg
Ethylene glycol 1kg
Dibutyl hydroxy toluene 1kg
Triethylene glycol 30kg
Cyclohexanone 10kg
Aromatic hydrocarbons two wires oil 32kg
The preparation method of spirodiclofen hot aerosol: press above-mentioned raw materials proportioning the former medicine 10kg of spiral shell mite ester is dropped in stirred tank, in still, inject solvent triethylene glycol 30kg, cyclohexanone 10kg, if dissolve slowly, suitably be heated to 45 ℃, opening stirred tank stirs, add while stirring surfactant alkylphenol polyoxyethylene OP-74kg, Span-805kg, peaceful newborn 33#4kg, benzyl naphthalenesulfonic acid-formaldehyde condensate 2kg, silicone defoaming agent dimethicone 1kg, antifreeze ethylene glycol 1kg, antioxidant dibutyl hydroxy toluene 1kg; Finally inject remaining solvent aromatic hydrocarbons two wires oil 32kg, continue to stir 25 minutes, static, remove by filter impurity, obtain the oily product of homogeneous transparent, through after the assay was approved, carry out package storage.
Embodiment tri-
According to following weight proportion 15% spirodiclofen hot aerosol:
Spiral shell mite ester 15kg
Alkylphenol polyoxyethylene OP-10 4kg
Span-80 7kg
Peaceful newborn 33# 3kg
Secondary alcohol APEO 3kg
Methyl naphthalene sulfonate formaldehyde condensate 3kg
Dimethicone 1kg
Ethylene glycol 1.5kg
Dibutyl hydroxy toluene 1kg
Triethylene glycol 30kg
Cyclohexanone 15kg
Residual oil 16.5kg
The preparation method of spirodiclofen hot aerosol: press above-mentioned raw materials proportioning the former medicine 15kg of spiral shell mite ester is dropped in stirred tank, in still, inject solvent triethylene glycol 30kg, if dissolve slowly, suitably be heated to 50 ℃, opening stirred tank stirs, add while stirring surfactant alkylphenol polyoxyethylene OP-10 4kg, Span-80 7kg, peaceful newborn 33#3kg, methyl naphthalene sulfonate formaldehyde condensate 3kg, silicone defoaming agent dimethicone 1kg, antifreeze ethylene glycol 1.5kg, antioxidant dibutyl hydroxy toluene 1kg; Finally inject remaining solvent cyclohexanone 15kg, residual oil 16.5kg, continue to stir 30 minutes, static, remove by filter impurity, obtain the oily product of homogeneous transparent, through after the assay was approved, carry out package storage.
Embodiment tetra-
According to following weight proportion 20% spirodiclofen hot aerosol:
Spiral shell mite ester 20kg
Alkylphenol polyoxyethylene OP-10 5kg
Span-80 9kg
Peaceful newborn 33# 3kg
Secondary alcohol APEO 3kg
Benzyl naphthalenesulfonic acid-formaldehyde condensate 5kg
Dimethicone 1kg
Propane diols 1.5kg
Dibutyl hydroxy toluene 1kg
Triethylene glycol 25kg
Cyclohexanone 20kg
Residual oil 6.5kg
The preparation method of spirodiclofen hot aerosol: press above-mentioned raw materials proportioning the former medicine 20kg of spiral shell mite ester is dropped in stirred tank, in still, inject solvent triethylene glycol 25kg, residual oil 6.5kg, if dissolve slowly, suitably be heated to 50 ℃, opening stirred tank stirs, add while stirring surfactant alkylphenol polyoxyethylene OP-105kg, Span-809kg, peaceful newborn 33#3kg, secondary alcohol APEO 3kg, benzyl naphthalenesulfonic acid-formaldehyde condensate 5kg, silicone defoaming agent dimethicone 1kg, antifreeze propane diols 1.5kg, antioxidant dibutyl hydroxy toluene 1kg; Finally inject remaining solvent cyclohexanone 20kg, continue to stir 30 minutes, static, remove by filter impurity, obtain the oily product of homogeneous transparent, through after the assay was approved, carry out package storage.
Biologicall test embodiment field control effectiveness test
Spirodiclofen hot aerosol of the present invention is as follows for preventing and treating field trial and the test of pesticide effectiveness result of bamboo grows Eotetranychus sexmaculatus:
Application crop: bamboo grows is for trying insect: Eotetranychus sexmaculatus
Experimental technique: adopt spirodiclofen hot aerosol control Eotetranychus sexmaculatus of the present invention, use the hot mist machine of 3WF-14G type to spray at rubber forest, by the spraying of effective ingredient consumption 8g/ mu, control Eotetranychus sexmaculatus insect.Investigation insect population radix before spraying, spray time is between 6-9 point in morning, wind condition be calm or gentle breeze situation under use.Rubber forest is to open the glue woods of cutting, and within 3 days, 7 days, 15 days after medicine, observes the borer population amount of living, and statistics preventive effect, in Table 1.
The control efficiency of table 1-spirodiclofen hot aerosol to bamboo grows Eotetranychus sexmaculatus
Data analysis and conclusion: as seen from Table 1, after medicine 3 days, spirodiclofen hot aerosol control efficiency of the present invention on average reached more than 80%, contrast effect of chemical control less than 80%; After medicine 7 days and 15 days, the control efficiency of spiral shell mite ester is on average reached more than 90%, and contrast medicament to be along with passage of time, control efficiency declines to some extent.Therefore, spirodiclofen hot aerosol of the present invention not only can effectively be controlled the harm of Eotetranychus sexmaculatus, and effectively solves a pesticide resistance difficult problem for pyridaben thermal fog.
Above embodiment is concrete detailed description content of the present invention, but is not limited only to above embodiment.Everyly according to the claims in the present invention, make similar or equivalent variations, as done similar variation in scope by weight percentage according to constitutive material of the present invention, all belong to the scope that the present invention is contained.
Claims (6)
1. a spirodiclofen hot aerosol, is characterized in that, described thermal fog is comprised of following raw materials by weight:
2. spirodiclofen hot aerosol according to claim 1, it is characterized in that, described surfactant is alkyl benzene calcium sulfonate, the lauryl sulfate calcium of anionic, two or more in the alkylphenol polyoxyethylene of nonionic, sorbitan fatty acid ester class, agriculture breast 600#, Nongru-700 #, peaceful newborn 33#, secondary alcohol APEO, methyl naphthalene sulfonate formaldehyde condensate, benzyl naphthalenesulfonic acid-formaldehyde condensate.
3. spirodiclofen hot aerosol according to claim 2, is characterized in that, described sorbitan fatty acid ester class is sorbitan mono-laurate or sorbitan monooleate.
4. spirodiclofen hot aerosol according to claim 1, is characterized in that, described antifreeze is ethylene glycol or propane diols.
5. spirodiclofen hot aerosol according to claim 1, it is characterized in that, described solvent is aromatic hydrocarbons two wires oil, aromatic hydrocarbons third fractional oil, residual oil, white oil, castor oil, turpentine oil, soybean oil, triethylene glycol, the cyclohexanone of high boiling point, high-flash, two or more in DMF.
6. the preparation method of spirodiclofen hot aerosol according to claim 1, it is characterized in that, take proportioning raw material claimed in claim 1, the former medicine of spiral shell mite ester is dropped into and regulated in still, to the solvent that injects solvent total amount 50～60% in still, if dissolve slowly, suitably be heated to 40～50 ℃, open and regulate still agitator to stir, add while stirring surfactant, dimethicone, antifreeze, dibutyl hydroxy toluene, finally inject remaining solvent, continue to stir 20～30 minutes, obtain the oily product of homogeneous transparent, through being up to the standards, package storage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010174122.4A CN101816303B (en) | 2010-04-30 | 2010-04-30 | Spirodiclofen hot aerosol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010174122.4A CN101816303B (en) | 2010-04-30 | 2010-04-30 | Spirodiclofen hot aerosol and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101816303A CN101816303A (en) | 2010-09-01 |
| CN101816303B true CN101816303B (en) | 2014-02-12 |
Family
ID=42651706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010174122.4A Expired - Fee Related CN101816303B (en) | 2010-04-30 | 2010-04-30 | Spirodiclofen hot aerosol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101816303B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102511477B (en) * | 2011-11-28 | 2013-11-13 | 华南农业大学 | Pyrethrin hot fogging agent and preparation method and application thereof |
| CN102742594A (en) * | 2012-07-24 | 2012-10-24 | 河南银田精细化工有限公司 | Pharmaceutical composition with insecticidal, bactericidal and acaricidal functions and smoke agent thereof |
| CN113647385A (en) * | 2021-08-23 | 2021-11-16 | 郯城众一科环化工有限公司 | Preparation method of environment-friendly solvent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322490A (en) * | 2008-07-04 | 2008-12-17 | 海南利蒙特生物农药有限公司 | Difenoconazole heat fog agent and preparation thereof |
| CN101518233A (en) * | 2008-02-28 | 2009-09-02 | 北京绿色农华植保科技有限责任公司 | Spirodiclofen water dispersible granule and preparation method thereof |
-
2010
- 2010-04-30 CN CN201010174122.4A patent/CN101816303B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101518233A (en) * | 2008-02-28 | 2009-09-02 | 北京绿色农华植保科技有限责任公司 | Spirodiclofen water dispersible granule and preparation method thereof |
| CN101322490A (en) * | 2008-07-04 | 2008-12-17 | 海南利蒙特生物农药有限公司 | Difenoconazole heat fog agent and preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| 新型杀螨剂螺螨酯的合成;陆一夫 等;《精细化工中间体》;20090430;第39卷(第2期);第19-21页 * |
| 陆一夫 等.新型杀螨剂螺螨酯的合成.《精细化工中间体》.2009,第39卷(第2期),第19-21页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101816303A (en) | 2010-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103875720B (en) | A kind of plant protecting liquid | |
| CN102696693B (en) | Compound type botanical pesticide and manufacturing method and application thereof | |
| CN102283258A (en) | Plant protecting agent for plant source and preparation method thereof | |
| CN101258861A (en) | Use of southernwood extract as plant growth regulator and adverse-resistant agent | |
| CN107251784A (en) | Tealeaves pest and disease damage Ecological preventive way | |
| CN101796968B (en) | Method for preparing preparation for preventing plant aphids by utilizing tomato stem and leaf extract | |
| CN101816303B (en) | Spirodiclofen hot aerosol and preparation method thereof | |
| CN102239845A (en) | Pesticide composition containing cytosinpeptidemycin and glucal | |
| CN109265235A (en) | Special fertilizer with insecticidal activity | |
| CN106116928A (en) | A kind of pear tree foliar fertilizer promotees effect additive and preparation method thereof | |
| CN103141505B (en) | Film diffusing oil agent combined reagent for preventing and treating rice planthopper | |
| CN105985194A (en) | Ginkgo foliage spray fertilizer additive and preparation method thereof | |
| CN102293218A (en) | Insecticidal composition containing spirotetramat and bifenthrin | |
| CN103918659A (en) | Pesticide composite including tolfenpyrad and fluazinam and preparation method and application of pesticide composite | |
| CN107494646A (en) | A kind of Environmental-protection agricultural vegetation insecticide and preparation method thereof | |
| CN106146140A (en) | A kind of defying age Fructus Lycopersici esculenti foliage fertilizer additives and preparation method thereof | |
| CN106490072A (en) | A kind of botanical pesticide of preventing and treating buprestid beetle and preparation method thereof | |
| CN102599168A (en) | Pesticide composition containing Tolfenpyrad and Envidor | |
| CN102246779A (en) | Pesticide composition containing spirotetramat and spinosad | |
| CN102027949A (en) | Brassinolide neem microcapsule | |
| CN105145635A (en) | Composition used for preventing and treating American white moths by helicopter chemical application and preparation method thereof | |
| CN103651432A (en) | Ultra-low volume liquid containing ametoctradin and benzamide fungicide composition and preparation method of ultra-low volume liquid | |
| CN103783043B (en) | Containing the compound insecticidal/miticide composition and uses thereof of spiral shell mite dibasic acid esters | |
| CN101911904A (en) | Prevention and treatment method of eucalyptus buzura suppressaria guenee | |
| CN107410380A (en) | A kind of ornamental plant flowers High-efficiency insecticidal pesticide reagent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140212 Termination date: 20160430 |