CN105432652A - Insecticidal composition containing benclothiaz and dinotefuran - Google Patents

Insecticidal composition containing benclothiaz and dinotefuran Download PDF

Info

Publication number
CN105432652A
CN105432652A CN201510921880.0A CN201510921880A CN105432652A CN 105432652 A CN105432652 A CN 105432652A CN 201510921880 A CN201510921880 A CN 201510921880A CN 105432652 A CN105432652 A CN 105432652A
Authority
CN
China
Prior art keywords
benclothiaz
mti
pesticidal combination
insecticidal composition
dinotefuran
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
Application number
CN201510921880.0A
Other languages
Chinese (zh)
Inventor
张英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jinan Shunhao Biotechnology Co Ltd
Original Assignee
Jinan Shunhao Biotechnology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jinan Shunhao Biotechnology Co Ltd filed Critical Jinan Shunhao Biotechnology Co Ltd
Priority to CN201510921880.0A priority Critical patent/CN105432652A/en
Publication of CN105432652A publication Critical patent/CN105432652A/en
Pending legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms

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 insecticidal composition containing benclothiaz and dinotefuran. The insecticidal composition is characterized in that active components of the insecticidal composition are benclothiaz and dinotefuran and the rest is auxiliary components used in preparation of pesticide formulation; a weight ratio of the active component benclothiaz to the active component dinotefuran is 1-30: 1-30; the dosage form of the insecticidal composition may be a wettable powder, a suspending agent, a soluble liquid, an emulsion in water and a water dispersible granule; and the total weight of the active components benclothiaz and dinotefuran accounts for 5 to 40% of the total weight of the insecticidal composition. The active components benclothiaz and dinotefuran in the insecticidal composition have obvious synergistic effect; so an insecticidal spectrum is broadened, the usage amount of the insecticidal composition is reduced, prevention efficiency is improved, few residues are left, the action period of the insecticidal spectrum is long, resistance generation of insects is delayed, and environmental protection is benefited.

Description

A kind of Pesticidal combination containing benclothiaz and MTI-446
Technical field
The present invention relates to technical field of pesticide combination, be specifically related to a kind of Pesticidal combination containing benclothiaz and MTI-446.
Background technology
Benclothiaz is considered to nematocide usually, thinks the highest to nematode activity, and since compound structure is announced, seldom see the activity research to other field or other insects, the more rare application in agriculture chemical compounding field, its chemical structural formula is as follows:
The third generation nicotinic insecticide that MTI-446 (dinotefuran) is developed for Mitsui chemical company.The chemical constitution of itself and existing nicotinic insecticide is far from each other, and its tetrahydrofuran base instead of former chloro-pyridine base, chloro-thiazole base, not containing halogen.Meanwhile, also different with nicotine at aspect of performance, current people are referred to as " furans nicotine ".This medicament insecticidal spectrum is wide, has remarkable interior suction osmosis, and namely shows very high insecticidal activity at very low dosage.Its chemical structural formula is:
MTI-446 resembles brown planthopper, white-backed planthopper, small brown rice planthopper, rice leafhopper, rice spider rafter stinkbug, star stinkbug, green rice bug, redly the control of bearing the rice grub such as mixed worm, rice cylinder water snout moth's larva of fleahopper, rice must have efficient effect; To Phytophthira, aleyrodid class, a red-spotted lizard class, unaspis shield kuwana, the green stinkbug of Zhu, peach fruit borer, tangerine lyonetid, the thin moth of tea, striped flea-beetle, beans veterinary antibiotics insects such as fly of diving, also there is efficient effect.
The insecticide that Long-Time Service is single, insect is easy to develop immunity to drugs, and pesticide dosage is increased, and cause the adverse consequencess such as high poison, consumption are large, residual many, drug effect is poor, and effect field is more single.And research and develop the agricultural chemical compound that seems, then the R&D cycle is long, and screening compounds arrangement works is very numerous and diverse, and non-general research and development institution can bear.But the different mechanism of action and without the insecticide rational mixture by a certain percentage of cross resistance, crop disease prevention effect can be improved, reduce dosage, residual few, reduce environmental pollution, effectively reducing the pesticide resistance of crop, is the study hotspot of current medium and small research and development institution.
Summary of the invention
According to the deficiencies in the prior art; the present invention proposes a kind of Pesticidal combination containing benclothiaz and MTI-446; said composition contains benclothiaz and MTI-446 two kinds of effective active components, and can be prepared into the preparation being suitable for agricultural application, and this Pesticidal combination has notable synergistic effect; expand insecticidal spectrum; decrease pesticide volume, improve preventive effect, residual few; lasting period is long, and the pesticide resistance being conducive to delaying insect produces and environmental protection.
The application is a kind of Pesticidal combination containing benclothiaz and MTI-446, its feature is that in this Pesticidal combination, active component is benclothiaz and MTI-446, all the other are the auxiliary element of the preparation formulations of pesticide, and wherein the ratio of weight and number of active component benclothiaz and MTI-446 is 1 ~ 30: 1 ~ 30.
In above-described Pesticidal combination, the ratio of weight and number of active component benclothiaz and MTI-446 is 5 ~ 20: 5 ~ 20.
The formulations of pesticide that above-described Pesticidal combination can be prepared into are wetting powder, suspending agent, soluble liquid, aqueous emulsion and water dispersible granules.
In the above formulations of pesticide, active component benclothiaz and MTI-446 total weight parts account for 5% ~ 40% of formulation total weight parts.
In the above formulations of pesticide, active component benclothiaz and MTI-446 total weight parts account for 5% ~ 20% of formulation total weight parts.
Pesticidal combination described in the application may be used for preventing and treating the insect on paddy rice, cotton, wheat, fruit tree, vegetables, to preventing and treating Noctuidae, Pyralidae, Carposinidae, tortricid, miller section, diamond-back moth section, Gracilariidae, aphid section, Aleyrodidae, Cicadellidae, Delphacidae insect and nematode, acarid Be very effective, brown planthopper, white-backed planthopper, small brown rice planthopper, rice leafhopper, rice spider rafter stinkbug, star stinkbug, green rice bug being resembled, redly the control of bearing the rice grub such as mixed worm, rice cylinder water snout moth's larva of fleahopper, rice must have efficient effect; To Phytophthira, aleyrodid class, a red-spotted lizard class, unaspis shield kuwana, the green stinkbug of Zhu, peach fruit borer, tangerine lyonetid, the thin moth of tea, striped flea-beetle, beans veterinary antibiotics insects such as fly of diving, also there is efficient effect.
When the application's Pesticidal combination is prepared as wetting powder, the parts by weight of each component are:
Benclothiaz1 ~ 30 part
MTI-446 1 ~ 30 part
Dispersant 3 ~ 9 parts
Wetting agent 3 ~ 8 parts
Filler 40 ~ 70 parts.
The concrete procedure of processing of this Pesticidal combination wetting powder is: by above-mentioned formula by benclothiaz and MTI-446 and the mixing of dispersant, wetting agent and filler, uniform stirring in stirred tank, mixing after airslide disintegrating mill, namely can be made into the wetting powder of the present composition.
When the application's Pesticidal combination is prepared as suspending agent, the parts by weight of each component are:
Benclothiaz1 ~ 30 part
MTI-446 1 ~ 30 part
Dispersant 2 ~ 5 parts
Antifreezing agent 1 ~ 4 part
Thickener 0.1 ~ 4 part
Defoamer 0.1 ~ 1 part
Water surplus.
The concrete production stage of this suspending agent is for first to mix other auxiliary agents, mix through high speed shear, add benclothiaz and MTI-446, abrading-ball 2 ~ 3 hours in ball crusher, make a diameter all at below 5mm, the aqueous suspension formulations of obtained Pesticidal combination described in the application.
When the application's Pesticidal combination is prepared as aqueous emulsion, the parts by weight of each component are:
Benclothiaz1 ~ 30 part
MTI-446 1 ~ 30 part
Emulsifier 3 ~ 6 parts
Solvent 3 ~ 7 parts
Stabilizing agent 2 ~ 7 parts
Antifreezing agent 1 ~ 4 part
Defoamer 0.1 ~ 8 part
Thickener 0.2 ~ 2 part
Water surplus.
The concrete production stage of this aqueous emulsion is: first former medicine benclothiaz and MTI-446, solvent and emulsifier, cosolvent are added together, and makes to be dissolved into uniform oil phase; By part water, antifreeze, other the insecticides adjuvant such as antimicrobial mixes uniformly aqueous phase; While high-speed stirred, oil phase is added aqueous phase in a kettle., slowly add water until reach phase inversion point, open clipper and carry out high speed shear, and add remaining water, shear about half an hour, form the aqueous emulsion of oil-in-water type.
When the application's Pesticidal combination is prepared as water dispersible granules, the parts by weight of each component are:
Benclothiaz1 ~ 30 part
MTI-446 1 ~ 30 part
Dispersant 2 ~ 7 parts
Wetting agent 3 ~ 7 parts
Disintegrant 2 ~ 8 parts
Filler 40 ~ 70 parts.
The concrete procedure of processing of this Pesticidal combination water dispersible granules is: benclothiaz, MTI-446 and dispersant, wetting agent, disintegrant and filler are mixed by above-mentioned formula, pulverize with micro jet, through mediating, then add in fluidized-bed granulation dryer and carry out through sample analysis after granulation, drying, screening, be i.e. the water dispersible granules of obtained Pesticidal combination.
Described emulsifier is selected from the mixture that calcium dodecyl benzene sulfonate and aliphatic acid polyethenoxy ether form.
Described solvent is methyl alcohol.
Described dispersant is selected from lignosulfonates.
Described wetting agent is selected from the one in lauryl sodium sulfate, spaonin powder.
Described disintegrant is selected from the one in bentonite, aluminium chloride.
Described thickener is selected from the one in xanthans, CMC, hydroxyethylcellulose, methylcellulose.
Described stabilizing agent is selected from the one in sodium citrate, resorcinol.
Described antifreezing agent is selected from the one in ethylene glycol, propane diols, glycerine.
Described defoamer is selected from silicone oil, silicone compound, C 10-20saturated fat acid compounds, C 8-10one in aliphatic alcohols compound.
Described filler is selected from the one in kaolin, diatomite, bentonite, attapulgite, white carbon, starch, precipitated calcium carbonate.
In addition, the Pesticidal combination of the application compares similar medicament also has other obvious advantages a lot, the first, compares single dose sphere of action wider, can expand insecticidal spectrum; The second, greatly delay the generation of pest resistance to insecticide, decreased agricultural chemicals Reusability number of times, reduce Pesticide use amount, reduce agricultural cost; 3rd, the residual quantity of this Pesticidal combination is lower, more friendly to environment, is significant to the increasing both production and income of agricultural region.
Embodiment:
Clearly understand to make object of the present invention, technical scheme and advantage; the following specific embodiment of the present invention is described; following examples are the preferred embodiment of the application, do not represent only test example, and the application's protection domain is as the criterion with claims.
Indoor biometrics screening and field experiment:
The method that the present invention adopts indoor bioassay and field trial to combine.If no special instructions, the ratio (comprising percentage) below mentioned is all ratio of weight and number.
Determination of activity example:
(1) reagent agent
The former medicine of benclothiaz, Syngenta Co., Ltd, the former medicine of MTI-446, Chemical Co., Ltd. Shandong Hailier provides.
(2) for examination worm source
Indoor diamondback moth larvae of for many generations raising, indoor conditions: temperature (26 ± 2) oc, relative moisture 68% ± 5%, periodicity of illumination 16/8h (L/D).
(3) single dose assay method
Adopt dip method respectively two groups of former medicines all to be used a small amount of acetone solution, then be diluted to into the dense solution of 5 of equal difference with the Tween solution of 0.1%, be diluted in for subsequent use in beaker, and with clear water in contrast.
Diamondback moth larvae of the same size is flooded 5S in the liquid of leaching worm cage, and being placed on diameter after sucking unnecessary liquid is in the culture dish of 9cm, is placed with fresh vegetable leaf and adds a cover in ware.Every concentration process 10, repeats 4 times, if blank.Check lethality keep 24h in (27 ± 1) DEG C illumination box after, it is dead for touching polypide nonresponder by pulling needle.Lethality Abbott formula correction, then according to log concentration---lethality probit value analyzes (Bliss) method, obtains virulence regression equation and puts dead middle amount LC 50value.
(4) the joint toxicity measuring method of different ratio
According to the toxicity test result of single dose, by active ingredient ratio of weight and number benclothiaz: MTI-446 is respectively 2:16,4:14,6:12,8:10,10:8.
Adopt above-mentioned 1.3 methods to carry out toxicity test, calculate LC 50, and press abundant method calculating co-toxicity coefficient (CTC) of Sun Yun.
(5) toxicity test result and analysis
Table 1benclothiaz, MTI-446 are to the indoor measurement result of diamond-back moth
As can be seen from the table, in the mixture of different proportion, its co-toxicity coefficient is all greater than 120, shows certain synergistic effect, wherein benclothiaz: synergistic effect when MTI-446 is 6: 12 is the most obvious, and co-toxicity coefficient is 196.45.Result of the test shows, MTI-446, benclothiaz two kinds of medicaments all have higher activity to diamond-back moth in room conditions, the result of the test of different proportion proportioning shows, by active ingredient benclothiaz: when MTI-446 is 2:16,4:14,6:12,8:10,10:8, all show stronger synergistic effect, wherein with benclothiaz: when MTI-446 is 6: 12, synergistic effect is best.Suggestion carries out further field control effectiveness test to the mixture preparation of suitable proportion about 6:12 scope, to evaluate its field practical application effect.
Field experiment example: field experiment control rice pest
(1) test method
Test is carried out at the double-ridged horn in Luo Wan village, journey market town, Jianli County, Jingzhou City of Hubei Province, and experimental field soil is loam, middle fertility, and irrigation and drainage are convenient, and surrounding all plants double cropping rice.For before the medication of examination paddy rice, the rice is doing well.The Zhu little Ni ridge, minizone is in case string is filled with, and during dispenser, there is 3 ~ 4cm shoaling layer in field, water conservation 7d after medicine, tests four (2) for rice fulgorid low instar nymphs occurrence in peak period medication in afternoon 1 time, to water 50kg/hm 2, evenly slightly spray with workers and peasants 16 type knapsack hand sprayer, time paddy rice be in grouting mid-term, secondly field is mainly white-backed planthopper, is small brown rice planthopper, and 1 ~ 3 age nymph account for 90%.Dispenser same day is fine day, mean temperature of air 28 DEG C; After medicine, 7d is all without rain, weather on this test substantially without impact.
(2) investigation method
Investigate 4 times altogether, investigation insect population radix before medicine, 2d after medicine, 7d after medicine, after medicine, 14d investigates 1 time respectively.Take the parallel great-jump-forward random sampling 30 in every community point, 2 clumps often, totally 60 clumps of rice, clap with basin the borer population alive that method records white-backed planthopper, small brown rice planthopper respectively, then calculate its Rectifying efficacies (hereinafter referred to as preventive effect).
(3) drug effect computational methods
Preventive effect (%)= × 100;
(4) poisoning investigation method
After medicine, 2,7,14d observe paddy growth situation, estimate medicament to paddy rice all without poisoning.
(5) field control effectiveness test result of the test
Table 2 treatment agent prevents and treats rice hoppers field control effectiveness test result
As can be seen from Table 2, the mixture of 6%benclothiaz+12% MTI-446 combines the successful preventing and treating rice hoppers and is better than 20% MTI-446 SC contrast single dose, 6%benclothiaz+12% MTI-446 insecticidal effect of 14 days after medicine is respectively 94.1%, 93.63% and 93.85%, insecticidal effect increases progressively along with the increase of consumption, estimate according to field, substantially disease is not had with the paddy rice of 6%benclothiaz+12% MTI-446, and growth fraction is more vigorous, and occur that disease is more with the paddy rice of 20% MTI-446 SC single dose, the disease plant much about about 12% of ratio complex preparation.
In addition within the scope of test dose, plant growth is normal, and the poisoning phenomenon to paddy rice does not all appear in each treatment agent, illustrates that it is safe to paddy rice.

Claims (7)

1. one kind contains the Pesticidal combination of benclothiaz and MTI-446, it is characterized in that: in this Pesticidal combination, active component is benclothiaz and MTI-446, all the other are the auxiliary element of the preparation formulations of pesticide, and wherein the ratio of weight and number of active component benclothiaz and MTI-446 is 1 ~ 30: 1 ~ 30.
2. a kind of Pesticidal combination containing benclothiaz and MTI-446 according to claim 1, is characterized in that: in described Pesticidal combination, the ratio of weight and number of active component benclothiaz and MTI-446 is 5 ~ 20: 5 ~ 20.
3. a kind of Pesticidal combination containing benclothiaz and MTI-446 according to claim 1 and 2, is characterized in that: the formulations of pesticide that described Pesticidal combination can be prepared into are wetting powder, suspending agent, soluble liquid, aqueous emulsion and water dispersible granules.
4. a kind of Pesticidal combination containing benclothiaz and MTI-446 according to claim 3, is characterized in that: in the formulations of pesticide, active component benclothiaz and MTI-446 total weight parts account for 5% ~ 40% of formulation total weight parts.
5. a kind of Pesticidal combination containing benclothiaz and MTI-446 according to claim 1 or 2 or 4, is characterized in that: in the formulations of pesticide, active component benclothiaz and MTI-446 total weight parts account for 5% ~ 20% of formulation total weight parts.
6. a kind of Pesticidal combination containing benclothiaz and MTI-446 according to claim 1 or 2 or 4, is characterized in that: this Pesticidal combination may be used for preventing and treating the insect on paddy rice, cotton, wheat, fruit tree, vegetables.
7. a kind of Pesticidal combination containing benclothiaz and MTI-446 according to claim 6, is characterized in that: this Pesticidal combination may be used for preventing and treating Noctuidae, Pyralidae, Carposinidae, tortricid, miller section, diamond-back moth section, Gracilariidae, aphid section, Aleyrodidae, Cicadellidae, Delphacidae insect and nematode, acarid.
CN201510921880.0A 2015-12-14 2015-12-14 Insecticidal composition containing benclothiaz and dinotefuran Pending CN105432652A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510921880.0A CN105432652A (en) 2015-12-14 2015-12-14 Insecticidal composition containing benclothiaz and dinotefuran

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510921880.0A CN105432652A (en) 2015-12-14 2015-12-14 Insecticidal composition containing benclothiaz and dinotefuran

Publications (1)

Publication Number Publication Date
CN105432652A true CN105432652A (en) 2016-03-30

Family

ID=55543647

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510921880.0A Pending CN105432652A (en) 2015-12-14 2015-12-14 Insecticidal composition containing benclothiaz and dinotefuran

Country Status (1)

Country Link
CN (1) CN105432652A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5447945A (en) * 1990-04-23 1995-09-05 Ciba-Geigy Corporation Nematicidal compositions
CN104137849A (en) * 2014-07-31 2014-11-12 海利尔药业集团股份有限公司 Nematode killing composition containing iprodione and dinotefuran

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5447945A (en) * 1990-04-23 1995-09-05 Ciba-Geigy Corporation Nematicidal compositions
CN104137849A (en) * 2014-07-31 2014-11-12 海利尔药业集团股份有限公司 Nematode killing composition containing iprodione and dinotefuran

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
袁会珠等主编: "《现代农药应用技术图解》", 30 June 2013 *

Similar Documents

Publication Publication Date Title
CN103749531B (en) A kind of Pesticidal combination containing matrine
CN103004818A (en) Insecticide composition containing fipronil and spirotetramat
CN105340910A (en) Insecticide composition containing benclothiaz and flonicamid
CN105360133A (en) Insecticide composition containing o-phenylenediamine insecticide and chlorantraniliprole
CN106342843A (en) Insecticide composition containing haloxyfop furanone
CN105340924A (en) Insecticide composition containing o-phenylenediamine pesticide and sophocarpidine
CN105432652A (en) Insecticidal composition containing benclothiaz and dinotefuran
CN105475336A (en) Insecticidal combination containing benclothiaz and imidacloprid
CN105454278A (en) Insecticidal combination containing o-phenylenediamine insecticide and dinotefuran
CN105340948A (en) Insecticide composition containing benclothiaz and efficient cyhalothrin
CN105340950A (en) Insecticide composition containing o-phenylenediamine pesticide and efficient cyhalothrin
CN105454259A (en) Insecticidal combination containing o-phenylenediamine insecticide and abamectin
CN103749530B (en) A kind of Pesticidal combination containing Avermectin
CN105432624A (en) Insecticidal composition containing benclothiaz and bromoantraniliprole
CN105340906A (en) Insecticide composition containing benclothiaz and pymetrozine
CN105475305A (en) Insecticidal combination containing benclothiaz and matrine
CN105340907A (en) Insecticide composition containing benclothiaz and flubendiamide
CN105325422A (en) Insecticidal combination containing o-phenylenediamine insecticide and flonicamid
CN105360139A (en) Insecticidal composition containing benclothiaz and chlorantraniliprole
CN105454248A (en) Insecticidal combination containing o-phenylenediamine insecticide and pymetrozine
CN105475293A (en) Insecticidal combination containing o-phenylendiamine insecticide and bromoantraniliprole
CN105325416A (en) Insecticidal combination containing o-phenylenediamine insecticide and flubendiamide
CN105309448A (en) Insecticide composition containing benclothiaz and pleocidin
CN103704262B (en) A kind of Pesticidal combination containing pymetrozine
CN105340909A (en) Insecticide composition containing benclothiaz and chlorfenapyr

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20160330

RJ01 Rejection of invention patent application after publication