CN107372516A - A kind of hygienic biocide granule and preparation method thereof - Google Patents

A kind of hygienic biocide granule and preparation method thereof Download PDF

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Publication number
CN107372516A
CN107372516A CN201710616294.4A CN201710616294A CN107372516A CN 107372516 A CN107372516 A CN 107372516A CN 201710616294 A CN201710616294 A CN 201710616294A CN 107372516 A CN107372516 A CN 107372516A
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film forming
forming agent
type film
quick
granule
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CN201710616294.4A
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CN107372516B (en
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黄昌建
姚志牛
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NANTONG FINE CHEMICAL CO Ltd
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NANTONG FINE CHEMICAL CO Ltd
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    • 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
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N25/00Biocides, 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
    • A01N25/08Biocides, 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 solids as carriers or diluents
    • 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
    • A01N25/00Biocides, 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
    • A01N25/12Powders or granules
    • 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
    • A01N43/90Biocides, 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
    • 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
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/14Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
    • 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
    • A01N63/00Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates

Abstract

The present invention relates to a kind of hygienic biocide granule and preparation method thereof, include each component of following parts by weight:Active components A 0.1 10%, active component B0.1 40%, solvent 0.2 20%, emulsifying agent 0.1 5.0%, dispersant 0.1 5.0%, spacetabs type film forming agent 0.1 5.0%, quick-releasing type film forming agent 0.1 5.0%, adsorbent 0.1 10%, porous carrier complements to 100%.The active components A is slow-acting type medicament Bacillus thuringiensis subsp. israelensis Bti or Nylar;The active component B is quick-acting neurotoxicity medicament Entex, Swebate, chlopyrifos, pirimiphos-methyl, AVM, ivermectin, the emamectin-benzoate being selected from the group;The active components A is used to adsorb in porous carrier, and active component B is wrapped in outside porous carrier;The spacetabs type film forming agent is hydrophobic polymer polymer;The quick-releasing type film forming agent is high molecular weight water soluble polymer.Specific spacetabs type film forming agent, the quick-releasing type film forming agent that the present invention selects, further especially there is excellent compatibility with corresponding active insecticidal components with the composite slow release type film forming agent of special ratios compounding, compound quick-releasing type film forming agent, more preferable quick-release and slow release effect can be played.

Description

A kind of hygienic biocide granule and preparation method thereof
Technical field
The present invention relates to a kind of hygienic insecticide field, particularly a kind of health kill mosquitos and flies larva composition and It is applied.
Background technology
Bacillus thuringiensis subsp. israelensis(Bti)It is search time is relatively early, research contents is relatively deep, application is wider one Kind Dipel subspecies, it is widely used in the control of mosquito, fly quantity as biological culicide.Bti is a kind of gram sun Performance forms the rods of gemma, and it can produce a kind of crystalline protein, become toxalbumin after being ingested by larva, and toxalbumin is led to The specific receptor crossed on junctional epithelium cell wall, causes membrane perforation, last lethal, in addition, it can also secrete Soviet Union The various active composition such as Yun Jinsu, exotoxin, chitinase, action site is very more, will not develop immunity to drugs.
Juvenoid Nylar, its specific mechanism of action, which is currently not, to be well aware of, but it has efficient, peace Entirely, the characteristics of lasting period is long, husking and breeding can be disturbed, the emergence of larva is thoroughly blocked, almost without the resistance to the action of a drug.
Organophosphorus insecticides Entex, Swebate, chlopyrifos, pirimiphos-methyl are acetylcholinesteraseinhibitors inhibitors, greatly Cyclic lactone insecticides AVM, ivermectin, emamectin-benzoate are r- aminobutyric acid inhibitor, two Person is never poison, and speed of action is very fast, can suppress the activity of larva and death quickly in 24h.
For a long time, the formulation for preventing and treating hygienic mosquitos and flies larva is mainly the granule of single dose, missible oil, aqueous emulsion, wettable The more single preparation type such as pulvis, organophosphorus insecticides or macrolide insecticide is used alone, although desinsection is fast Degree is very fast, but it is short the lasting period to be present, development of drug resistance quickly the shortcomings that;And although the insect growth regulator, IGR lasting period is used alone Longer, the resistance to the action of a drug is low, but can not quickly reduce insect density.
In granule part, prior art is also no lack of the granule for being related to two layers of setting, wherein CN201510456298.1 A kind of slow controlled release granular pesticide is disclosed, inside and outside double-layer structure is included in its structure, its core is slow-releasing granules, and The rapid release layer being coated on outside slow release layer, pesticide activity component are organic phosphates, nicotinoids etc., and it is first by pesticide activity component It is wrapped in sustained release stratum nucleare(Diameter 1.2-2mm), then will be sustained stratum nucleare throwing circle using leftover materials and form rapid release layer(Thickness 0.3-0.5mm), i.e., in the prior art, and the active component of different releasing layers is not differentiated between, more different releasing layers is controlled Rate of release selects different slowly-released film forming agents.CN201610353235.8 discloses a kind of sustained releasing pesticide granule and its preparation Method, it sets 3 layers of active ingredient layer altogether, and each layer pesticide activity component may be the same or different, and each layer uses different crosslinking agents, the One layer of crosslinking agent is high molecular weight water soluble polymer such as polyvinylpyrrolidone, and second layer crosslinking agent is cellulose or cellulosate Such as sodium carboxymethylcellulose, carboxyethyl cellulose, methylcellulose, third layer crosslinking agent are borax, and each layer is not by using With crosslinking agent and suitable proportioning is set, to promote the release of pesticide activity component, be finally reached quick-acting, middle effect and long-acting release Put.
Although quick-release and slow release layer be present as can be seen that being related in the prior art in granule, but and it is not concerned with each Use which kind of active component in releasing layer, does not pay close attention to for different activities composition, using different auxiliary agents.
Applicant studies for a long period of time discovery, by different quick-acting medicament and slow-acting type medicament with it is each adaptable specific Film forming agent coordinates, while compounds in granule, quick-acting medicament is faster played speed and kills effect, reduces medication Amount, it is quick to reduce weight mouth density;The performance slow release effect of slow-acting type medicament then longer time, thoroughly kill residual larva or blocking It is sprouted wings, and reduces the Phosphorus insecticide of machine or the development of drug resistance of macrolide insecticide, and dispenser is convenient, realizes even more ideal Insecticidal effect.
The content of the invention
It is an object of the invention to provide a kind of overcome the deficiencies in the prior art, there is provided one kind can reach simultaneously as needed The hygienic biocide granule of quick-release effect and slow release effect, realize that quick killing mosquitos and flies larva is to reduce insect density simultaneously, with And long-acting suppression larval growth, thoroughly kill residual larva or prevent its emergence, reduce drug-fast effect.
To realize the purpose of the present invention, the present invention provides a kind of hygienic biocide granule, it is characterised in that the granule It is made up of following component by weight:
Active components A 0.1-10%
Active component B 0.1-10%
Solvent 0.2-20%
Emulsifying agent 0.1-5.0%
Dispersant 0.1-5.0%
Spacetabs type film forming agent 0.1-5.0%
Quick-releasing type film forming agent 0.1-5.0%
Adsorbent 0.1-10%
Porous carrier complements to 100%
The active components A is slow-acting type medicament Bacillus thuringiensis subsp. israelensis Bti or Nylar;The active component B is The quick-acting neurotoxicity medicament Entex that is selected from the group, Swebate, chlopyrifos, pirimiphos-methyl, AVM, Yi Wei bacterium Element, emamectin-benzoate;The active components A is used to adsorb in porous carrier, and active component B is wrapped in Outside porous carrier;
The spacetabs type film forming agent is hydrophobic polymer polymer;It is selected from good film-forming property, and spacetabs type can be excellent, and viscosity is fitted Preferably, film forming fastness is strong:Polyvinyl acetate, butyl polyacrylate, styrene/vinyl acetate co-polymer, styrene/vinegar One or more in vinyl acetate/butyl acrylate copolymer, styrene/acrylamide/butyl acrylate copolymer;
The quick-releasing type film forming agent is high molecular weight water soluble polymer;It is selected from good film-forming property, and disintegrating property is excellent, and viscosity is fitted Preferably, film forming fastness is strong:In hydroxyethyl cellulose, pre-gelatinized starch, sodium carboxymethyl starch, Arabic gum, polyvinyl alcohol It is one or more of.
Preferably, active component B is Entex, Swebate or ivermectin;
Preferably, spacetabs type film forming agent is polyvinyl acetate, styrene/ethylene acetate/acrylic acid acrylate copolymer or benzene One or both of ethylene/propylene acrylamide/vinyl acetate co-polymer;It is highly preferred that spacetabs type film forming agent is weight ratio is 1:2-4 polyvinyl acetate and the composite slow release type film forming agent of styrene/acrylamide/butyl acrylate copolymer, it is more excellent It is 1 to select the weight ratio of the two:3.
Preferably, quick-releasing type film forming agent is the one or more in Arabic gum, sodium carboxymethyl starch, polyvinyl alcohol;More Preferably, the quick-releasing type film forming agent is weight than 1:1-3 sodium carboxymethyl starch and the compound quick-releasing type film forming of polyvinyl alcohol Agent, more preferably the weight ratio of the two are 1:1.5.
The porous carrier is selected from concave-convex rod particle, volcanic rock particle, common brick particle, coal with preferable absorption property One or more in spoil particle, medical stone granule, zeolite granular, corn cob granule, walnut shell particle etc., it is preferably bumps Any of rod particle, volcanic rock particle, corn cob granule.
The solvent is selected from aromatic solvent naphtha, C6-C30 isoparaffins or Porous deproteinized bone solvent naphtha;Methyl laurate, oleic acid first Single esters solvent such as ester, isopropyl myristate, Ethylhexyl stearate, benzyl acetate;Dimethyl adipate, adipic acid diisopropyl The di esters solvent such as ester, diethyl maleate, dibutyl malonate;Tributyl phosphate, ATBC, acetyl tributyl citrate three The esters solvent of butyl ester etc. three;N, N- dimethyl certain herbaceous plants with big flowers acid amides, the amide solvent such as N, N- dimethyloctanamides;Cyclohexanone, methyl are different One or more in the ketones solvents such as butyl ketone, isophorone, it is preferably low toxicity tasteless non-stimulated monoesters, dibasic acid esters or three esters Class solvent.
The emulsifying agent is selected from calcium dodecyl benzene sulfonate, sulfosuccinic acid diisooctyl sulfosuccinate, aliphatic alcohol polyethenoxy Ether, APES, castor oil polyoxyethylene ether, phenethyl phenol APEO, ethylene oxide propylene oxide are embedding One or more in section copolymer, preferably calcium dodecyl benzene sulfonate, AEO, alkylphenol-polyethenoxy Anionic and nonionic compound in ether, ethylene oxide propylene oxide block copolymer;
The dispersant be selected from phenethyl phenol APEO and its phosphate or salt, polycarboxylate,(Alkyl)Naphthalene sulfonate One or more in formaldehyde condensation products, lignosulfonates, it is preferably(Alkyl)Naphthalenesulfonate formaldehyde condensation compound, sulfomethylated lignin Hydrochlorate;
One or more of the adsorbent in white carbon, attapulgite, bentonite, diatomite etc., preferably white carbon Or attapulgite.
Described hygienic biocide granule composite and preparation method thereof, it is characterised in that comprise the following steps:
A, the preparation of kernel is adsorbed:Active components A is dissolved in 0.1-10 weight % solvent by formula rate, adds 0.05- 2.5 weight % emulsifying agent and 0.05-2.5 weight % dispersant stir evenly, and then add in porous carrier aforesaid liquid and fill Point absorption, add spacetabs type film forming agent in roller pelletizer fully roll coating, dry spacetabs type inner core particles are standby;
B, quick-acting medicament is coated:Active component B and residual solvent, emulsifying agent, dispersant are fully mixed by formula rate, used The adsorbent absorption fully mixes into powder and then with quick-releasing type film forming agent, delays again in roller pelletizer with above-mentioned drying The type inner core particles of releasing fully roll coating;
C, dry or dry again and produce the granule.
Further, the present invention provides the application of described hygienic biocide granule preventing and treating sanitary insect pest, the health evil Worm is wriggler, preferably fly maggot, wriggler.
Explained on principle:Applicant studies for a long period of time discovery, the present invention by two kinds of mechanisms of action it is entirely different it is effective into Divide compounding in same preparation, one of which is that speed of action is slow, but long-term killing rate is very high, and resistance risk is extremely low Specific Dipel subspecies or Nylar;Another kind is very fast for speed of action, the obvious organophosphor of 24h density reduced rates or big Cyclic lactone class medicament;First, both compound the resistance risk for greatly reducing organophosphor or macrolides medicament, and together When reached the purpose of quick reduction pest density;Secondly, applicant is had found by numerous studies, when this kind of specific spacetabs type When medicament is with above-mentioned specific spacetabs type film forming agent formulated in combination inner core particles, the compatibility of the two is preferable, in production practices It can reach more preferable slow releasing function compared to using other film forming agents;Simultaneously when this kind of specific quick-releasing type medicament with it is above-mentioned specific Quick-releasing type film forming agent combination when, the two equally has excellent compatibility, in production practices compared to use other film forming agents More preferable quick-release effect can be reached.
Compared with prior art, beneficial effects of the present invention are:
(1)The present invention has been greatly reduced using the pesticide activity component with different physicochemical properties, on the one hand both compoundings The resistance risk of machine phosphorus or macrolides medicament, on the other hand, reaching the same of the purpose of quick reduction pest density When, also with slow release effect
(2)Compared with juvenoid or Dipel single dose, there is faster desinsection speed, with organophosphor or big ring Lactone single dose is compared, and has the longer lasting period;
(3)It is preferred that the porous carrier with preferable absorption property, is realized to the more preferable absorption of spacetabs type medicament and control release, Extend the lasting period.
(4)Due to porous carrier absorption is used alone, spacetabs type energy can't be highly desirable, of the invention and preferably specific thin Aqueous prolonged release type film forming agent is coated to the porous particle for adsorbing slow-acting type medicament, realizes more efficient control release, simultaneously By fast-acting type medicament in more outer layer coating without adsorbing the effect into internal influence quick-acting by porous material.
(5)It is preferred that particular hydrophilic quick-releasing type film forming agent is coated to fast-acting type medicament, fast-acting type medicament is realized faster Release, accelerating mosquitos and flies larval density reduces speed.
(6)A new complex composition and formulation is added for domestic hygienic biocide field, drug effect is notable, can obtain Extensive popularization and application.
(7)Specific spacetabs type film forming agent, the quick-releasing type film forming agent that the present invention selects, are especially further compounded with special ratios Composite slow release type film forming agent, compound quick-releasing type film forming agent there is excellent compatibility with corresponding active insecticidal components, can Play more preferable quick-release and slow release effect.
Embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope All alternatives, improvement project and equivalents.
First, embodiment is prepared
Prepare embodiment 1:
Nylar 0.5g is dissolved in 2.5g methyl oleates, adds emulsifying agent(Calcium dodecyl benzene sulfonate 0.2g, fatty alcohol polyoxy Vinethene 0.3g)Stir evenly, disperseed with the 0.5g of naphthalenesulfonate formaldehyde condensation compound containing dispersant suitable quantity of water, aforesaid liquid is existed In roller pelletizer with appropriate concave-convex rod particle carry out fully roll absorption 30min, then add containing styrene/acrylamide/ Butyl acrylate copolymer 1.0g dilution, fully roll cladding 30min after, dry spacetabs type inner core particles are standby;
Entex 4.5g is dissolved in 1.5g diethylene adipates, adds emulsifying agent(Calcium dodecyl benzene sulfonate 0.5g, alkyl phenol APEO 1.5g)Stir evenly, after being mixed with the 1.0g polycarboxylate salt dispersants of suitable quantity of water dissolving, adsorbed with 5g white carbons, then Mixed with the dilution of the 2.0g containing polyvinyl alcohol, cladding is fully rolled with above-mentioned spacetabs type inner core particles in roller pelletizer 30min, drying 100g 5% Nylar Entex granule.
Prepare embodiment 2:
80000IU/ml Bacillus thuringiensis subsp. israelensis suspending agent 0.25ml is dissolved in appropriate lignosulfonates containing 1.0g In the water of dispersant, aforesaid liquid with appropriate volcanic rock particle fully roll in roller pelletizer and adsorbs 30min, so The dilution containing styrene/acrylamide/butyl acrylate copolymer 1.5g is added afterwards, after fully rolling cladding 30min, drying It is standby to obtain spacetabs type inner core particles;
Ivermectin 0.1g is dissolved in 1.0g dimethyl adipates, adds emulsifying agent(AEO 0.2g, epoxy Ethane epoxy propane block copolymer 0.4g)Stir evenly, mixed with the 0.5g naphthalenesulfonate formaldehyde condensation compound dispersants of suitable quantity of water dissolving After even, adsorbed with 1.0g white carbons, then mixed with the dilution of the 0.5g containing sodium carboxymethyl starch, in roller pelletizer with it is above-mentioned Spacetabs type inner core particles fully roll cladding 30min, drying 100g Dipel containing 200IU/g and 0.1% Yi Wei bacterium The granular insecticide of element.
Prepare embodiment 3:
Nylar 1.0g is dissolved in 2.0g diisopropyl adipates, adds emulsifying agent(Calcium dodecyl benzene sulfonate 0.1g, epoxy Ethane epoxy propane block copolymer 0.4g)Stir evenly, with the phenol polyoxyethylene phosphonate triethanolamine of phenethyl containing dispersant Salt 1.0g suitable quantity of water is disperseed, and aforesaid liquid with appropriate corn cob granule fully roll in roller pelletizer and inhaled Attached 30min, the dilution containing styrene/acrylamide/butyl acrylate copolymer 2.0g is then added, fully roll cladding After 30min, dry spacetabs type inner core particles are standby;
Swebate 1.0g is dissolved in 1.0g tributyl phosphates, adds emulsifying agent(Calcium dodecyl benzene sulfonate 0.2g, castor oil gather Oxygen vinethene 0.8g)Stir evenly, after being mixed with the 0.2g lignin sulfonic acids dipersant of suitable quantity of water dissolving, inhaled with 2.0g white carbons It is attached, then mixed with the dilution of the 0.2g containing Arabic gum, fully rolled with above-mentioned spacetabs type inner core particles in roller pelletizer Coat 30min, drying 100g 2% Nylar Swebate granule.
Prepare embodiment 4:
Nylar 0.4g is dissolved in 2.0g ATBCs, adds emulsifying agent(Calcium dodecyl benzene sulfonate 0.2g, alkyl phenol APEO 0.4g)Stir evenly, disperseed with the 0.8g of lignosulfonates containing dispersant suitable quantity of water, aforesaid liquid is being rolled With appropriate concave-convex rod particle fully roll in cylinder comminutor and adsorb 30min, then add 40% polyvinyl acetate emulsion 5.0g, fully roll cladding 30min after, dry spacetabs type inner core particles are standby;
Ivermectin 0.1g is dissolved in 1.5g diethylene adipates, adds emulsifying agent(Calcium dodecyl benzene sulfonate 0.5g, alkyl Phenol polyethenoxy ether 1.5g)Stir evenly, after being mixed with the 0.5g polycarboxylate salt dispersants of suitable quantity of water dissolving, adsorbed with 5g white carbons, The dilution with the 1.0g containing polyvinyl alcohol is mixed again, and cladding is fully rolled with above-mentioned spacetabs type inner core particles in roller pelletizer 30min, drying 100g 0.5% Nylar ivermectin granule.
Prepare embodiment 5:In addition to spacetabs type active component is Bacillus thuringiensis subsp. israelensis, remaining is the same as preparation embodiment 1;
Prepare embodiment 6:In addition to quick-releasing type active component is chlopyrifos, remaining is the same as preparation embodiment 1;
Prepare embodiment 7:In addition to quick-releasing type active component is pirimiphos-methyl, remaining is the same as preparation embodiment 1;
Prepare embodiment 8:In addition to quick-releasing type active component is AVM, remaining is the same as preparation embodiment 1;
Prepare embodiment 9:In addition to quick-releasing type active component is emamectin-benzoate, remaining is the same as preparation embodiment 1;
Prepare embodiment 10:Except spacetabs type film forming agent is 1:2 polyvinyl acetate and styrene/acrylamide/acrylic acid fourth Outside the composite slow release type film forming agent of ester copolymer, remaining is the same as preparation embodiment 1;
Prepare embodiment 11:Except spacetabs type film forming agent is 1:4 polyvinyl acetate and styrene/acrylamide/acrylic acid fourth Outside the composite slow release type film forming agent of ester copolymer, remaining is the same as preparation embodiment 1;
Prepare embodiment 12:Except spacetabs type film forming agent is 1:3 polyvinyl acetate and styrene/acrylamide/acrylic acid fourth Outside the composite slow release type film forming agent of ester copolymer, remaining is the same as preparation embodiment 1;
Prepare embodiment 13:Except quick-releasing type film forming agent is 1:1 sodium carboxymethyl starch and the compound quick-releasing type film forming of polyvinyl alcohol Outside agent, remaining is the same as preparation embodiment 1;
Prepare embodiment 14:Except quick-releasing type film forming agent is 1:3 sodium carboxymethyl starch and the compound quick-releasing type film forming of polyvinyl alcohol Outside agent, remaining is the same as preparation embodiment 1;
Prepare embodiment 15:Except quick-releasing type film forming agent is 1:The compound quick-releasing type of 1.5 sodium carboxymethyl starch and polyvinyl alcohol into Outside film, remaining is the same as preparation embodiment 1.
Comparing embodiment 1:
Nylar 0.5g is dissolved in 2.5g methyl oleates, adds emulsifying agent(Calcium dodecyl benzene sulfonate 0.2g, fatty alcohol polyoxy Vinethene 0.3g)Stir evenly, disperseed with the 0.5g of naphthalenesulfonate formaldehyde condensation compound containing dispersant suitable quantity of water, aforesaid liquid is existed With appropriate concave-convex rod particle fully roll in roller pelletizer and adsorb 30min, then add the dilute of the polyvinyl alcohol containing 2.0g Liquid is released, after fully rolling cladding 30min, dries to obtain 0.5% Nylar granule.
Comparing embodiment 2:
Entex 4.5g is dissolved in 1.5g diethylene adipates, adds emulsifying agent(Calcium dodecyl benzene sulfonate 0.5g, alkyl phenol APEO 1.5g)Stir evenly, after being mixed with the 1.0g polycarboxylate salt dispersants of suitable quantity of water dissolving, adsorbed with 5g white carbons, then Mixed with the dilution of the polyvinyl alcohol containing 2.0g in right amount, with appropriate concave-convex rod particle fully roll in roller pelletizer and inhale Attached 30min, dry to obtain 4.5% Entex granule.
Comparing embodiment 3:
80000IU/ml Bacillus thuringiensis subsp. israelensis suspending agent 0.25ml is dissolved in appropriate lignosulfonates containing 1.0g In the water of dispersant, aforesaid liquid with appropriate volcanic rock particle fully roll in roller pelletizer and adsorbs 30min, so Add the dilution of the sodium carboxymethyl starch containing 0.5g afterwards, fully roll cladding 30min after, dry 200 IU/g Su Yun gold bars Bacterium granule.
Comparing embodiment 4:
Ivermectin 0.1g is dissolved in 1.0g dimethyl adipates, adds emulsifying agent(AEO 0.2g, epoxy Ethane epoxy propane block copolymer 0.4g)Stir evenly, mixed with the 0.5g naphthalenesulfonate formaldehyde condensation compound dispersants of suitable quantity of water dissolving After even, adsorbed with 1.0g white carbons, then mixed with the dilution of the sodium carboxymethyl starch containing 0.5g, with appropriate in roller pelletizer Volcanic rock particle fully rolls absorption 30min, dries to obtain 0.1% ivermectin granule.
Comparing embodiment 5:
Nylar 0.5g is dissolved in 2.5g methyl oleates, adds emulsifying agent(Calcium dodecyl benzene sulfonate 0.2g, fatty alcohol polyoxy Vinethene 0.3g)Stir evenly, disperseed with the 0.5g of naphthalenesulfonate formaldehyde condensation compound containing dispersant suitable quantity of water, by aforesaid liquid Carry out fully rolling absorption 30min, Ran Houjia with appropriate common river sand particle in roller pelletizer after the absorption of 2.0g white carbons Enter the dilution containing styrene/ethylene acetate/acrylic acid acrylate copolymer 1.0g, after fully rolling cladding 30min, dry Spacetabs type inner core particles are standby;
Entex 4.5g is dissolved in 1.5g diethylene adipates, adds emulsifying agent(Calcium dodecyl benzene sulfonate 0.5g, alkyl phenol APEO 1.5g)Stir evenly, after being mixed with the 1.0g polycarboxylate salt dispersants of suitable quantity of water dissolving, adsorbed with 5g white carbons, then Mixed with the dilution of the polyvinyl alcohol containing 2.0g, cladding is fully rolled with above-mentioned spacetabs type inner core particles in roller pelletizer 30min, drying 100g the Nylar Entex granule of common river sand 5%.
Comparing embodiment 6:In addition to spacetabs type film forming agent is not added with, remaining is the same as preparation embodiment 1;
Comparing embodiment 7:In addition to quick-releasing type film forming agent is not added with, remaining is the same as preparation embodiment 1;
Comparing embodiment 8:In addition to spacetabs type film forming agent is polyvinylpyrrolidone, remaining is the same as preparation embodiment 1;
Comparing embodiment 9:In addition to spacetabs type film forming agent is polyacrylate, remaining is the same as preparation embodiment 1;
Comparing embodiment 10:In addition to quick-releasing type film forming agent is sodium carboxymethylcellulose, remaining is the same as preparation embodiment 1;
Comparing embodiment 11:In addition to quick-releasing type film forming agent is polyvinylpyrrolidone, remaining is the same as preparation embodiment 1.
Application Example 1:Prevent and treat culex pipiens pallens larvae indoor pharmacodynamic test(One)
Test method:
3L dechlorination running water is added in ceramic whiteware basin, by preparation with 20g/m3Dosage input, stir, be put into healthy 3 ages children Worm 30, is raised by normal method, and that the 2h death rates, the 24h death rates and pyriproxyfen-containing medicament are observed after input test worm encumbers plumage Rate;Experiment in triplicate, and sets blank control.
During experiment, interval 2d complementary testings water to initial water graduation mark.
Lasting period is observed:Added for 3 ages to test group and blank control group respectively at 1d, 15d, 30d, 60d, 90d, 120d Larva 30, by above-mentioned steps, viewing test result.
Test data is as follows:
The Nylar Entex granule of table -1 5% is with single dose to culex pipiens pallens larvae drug effect contrasts result
5% Nylar Entex granule of the invention and the Nylar granule of single dose 0.5% are can be seen that from the efficacy data of table -1 Compare, due to there is spacetabs type film former component, encumbering the eclosion rate lasting period is obviously prolonged, and granule 90d of the present invention encumbers emergence Eclosion rate is encumbered when rate is higher than without 0.5% Nylar granule 60d of spacetabs type film forming agent;5% Nylar Entex of the invention Granule is compared with the Entex granule of single dose 4.5%, and because medicament is not adsorbed by porous carrier, rate of release is fast, experiment The same day 2h death rate reaches 100%, and the Entex granule 24h of single dose 4.5% death rate also only has 94.4%;The present invention 5% Nylar Entex granule with using the present invention outside imporosity do not have absorption property common river sand prepare comparison 5% Nylar Entex granule of embodiment 5 is compared, because quick-acting medicament is not by porous carrier in terms of quick-acting Absorption, effect is suitable with not having 5% Nylar Entex granule of the common river sand of absorption property preparation, but encumbers emergence Especially there is obvious advantage in 90d in terms of the lasting effect of rate;Comparing embodiment 6 is not added with spacetabs type film forming agent, and it is compared The embodiment of the present invention is worse in terms of sustained release, and comparing embodiment 7 is not added with quick-releasing type film forming agent, and it is compared to the embodiment of the present invention in speed It is worse to release aspect.
This illustrates present invention compounding to prepare in terms of quick-acting and lasting effect with single dose and non-invention preparation method Granule compared to being respectively provided with clear superiority, certainly, other juvenoids and organophosphor or macrolides medicament Compounding also has similar effect.
Application Example 2:Prevent and treat culex pipiens pallens larvae indoor pharmacodynamic test(Two)
Test method:
3L dechlorination running water is added in ceramic whiteware basin, the preparation of embodiment 2 will be prepared with 20g/m3Dosage input, stir, Healthy 3 instar larvae 30 is put into, is raised by normal method, the 24h death rates and the 96h death rates are observed after putting into test worm;Experiment weight Again three times, and blank control is set.
During experiment, interval 2d complementary testings water to initial water graduation mark.
Lasting period is observed:Respectively at 1d, 15d, 30d, 60d, 90d 3 instar larvaes are added to test group and blank control group 30, by above-mentioned steps, viewing test result.
Test data is as follows:
The Bti ivermectins granule of table -2 is with single dose to culex pipiens pallens larvae drug effect contrasts result
The desinsection of Dipel containing 200IU/g of the invention and 0.1% ivermectin is can be seen that from the efficacy data of table -2 Granula, due to there is spacetabs type film former component, there is one compared with single dose 200IU/g Dipel granules in terms of lasting effect It is of a relatively high to culex pipiens pallens larvae 96h killing rates to determine advantage, 30d and 60d;With the ivermectin granule phase of single dose 0.1% Than the same day 24h death rates of experiment for the first time can reach 100%, have the quick effect for reducing insect density, and dead in 15d Rate can reach 100%, and the speed for having given full play to AVM kills effect;Substantially, Bti and other macrolides medicaments Or organic phosphates composite reagent also has similar effect.
Physicochemical property is tested:Hygienic biocide granule rate of release experiment of the present invention
The accurate 10g that weighs is placed in liquid filter bag for examination granule, closes sack, liquid filter bag is placed in 150mL beakers, Deionized water 100mL is added, liquid filter bag is totally submerged in deionized water, then beaker is placed in 25 DEG C of thermostats.1, 3rd, 1mL solution is taken out from the middle body of container respectively after 7,14,21 days, in order that the solution in container is homogeneous, after earthquake Take out, and supplemented with equal amount deionized water, total liquid volume is kept constant.The method according to as defined in GB28128-2011, Using the content of high effective liquid chromatography for measuring release solution Pesticides active component, dissolution rate is calculated.As a result it is as shown in table 3.
Test prepares embodiment 1,10-15(Following referred to as system 1,10-15 processed), comparative example 1-2,5-11(Following letter Claim to 1-2,5-11)The dissolution rate of middle Nylar and Entex.
The granular insecticide rate of release result of the test of the present invention of table 3
In the rate of release experiment of granular insecticide of the present invention, for slow release effect, compared to conventional Nylar single dose To 1, using other porous carriers to 5, and be not added with sustained release agent to 6, even add other sustained release agents to 8-9, this Inventive embodiments are more excellent in terms of sustained release performance;In the dissolution of spacetabs type insecticide Nylar, when selection is specific compound slow When releasing type film forming agent, such as its slow release effect of preparation embodiment 10-12 is more excellent, particularly when composite slow release type film forming agent is specific ratio During example combination, embodiment 12 is such as prepared, its effect is optimal.Likewise, in terms of quick-release effect, compared to the Entex single dose of routine To 2, using other porous carriers to 5, and be not added with quick-release agent to 5, even add other quick-release agent to 10- 11, the embodiment of the present invention is more excellent in quick-release aspect of performance;In addition, when the specific compound quick-releasing type film forming agent of selection, such as prepare Its quick-release effect of embodiment 13-15 is more excellent, particularly when compound quick-releasing type film forming agent is that special ratios combine, such as prepares and implements Example 15, its effect are optimal.
The Application Example of the present invention only illustrates the present composition and its preparation side with the contrast effect of the medicament Advantage of the method in terms of quick-acting and lasting effect, it is other it is described compound, described spacetabs type film forming agent, described quick-releasing type into The use of film, described porous carrier also has similar effect, does not outline one by one herein.
A kind of hygienic biocide granule of the present invention and preparation method thereof is described by specific example, this Art personnel can use for reference the ring such as present invention, appropriate feed change, process conditions, active ingredient compounded combination or ratio Save to realize corresponding other purposes, its correlation changes all without departing from present disclosure, all similar replacements and change It will become apparent to those skilled in the art that it is considered as being included within the scope of the present invention.

Claims (10)

1. a kind of hygienic biocide granule, it is characterised in that the granule is made up of following component by weight:
Active components A 0.1-10%
Active component B 0.1-10%
Solvent 0.2-20%
Emulsifying agent 0.1-5.0%
Dispersant 0.1-5.0%
Spacetabs type film forming agent 0.1-5.0%
Quick-releasing type film forming agent 0.1-5.0%
Adsorbent 0.1-10%
Porous carrier complements to 100%
The active components A is slow-acting type medicament Bacillus thuringiensis subsp. israelensis Bti or Nylar;The active component B is The quick-acting neurotoxicity medicament Entex that is selected from the group, Swebate, chlopyrifos, pirimiphos-methyl, AVM, Yi Wei bacterium Element, emamectin-benzoate;The active components A is used to adsorb in porous carrier, and active component B is wrapped in Outside porous carrier;
The spacetabs type film forming agent is hydrophobic polymer polymer;It is selected from polyvinyl acetate, butyl polyacrylate, benzene second Alkene/vinyl acetate co-polymer, styrene/ethylene acetate/acrylic acid acrylate copolymer, styrene/acrylamide/acrylic acid One or more in acrylate copolymer;
The quick-releasing type film forming agent is high molecular weight water soluble polymer;It is selected from hydroxyethyl cellulose, pre-gelatinized starch, carboxymethyl One or more in sodium starch, Arabic gum, polyvinyl alcohol.
2. granule according to claim 1, it is characterised in that the active component B is Entex, Swebate or Yi Wei Rhzomorph.
3. granule according to claim 1, it is characterised in that the spacetabs type film forming agent is polyvinyl acetate, benzene Ethylene/vinyl acetate/butyl acrylate copolymer or one kind in styrene/acrylamide/vinyl acetate co-polymer or Two kinds.
4. the granule according to claim/3, it is characterised in that the spacetabs type film forming agent is that weight ratio is 1:2-4's The composite slow release type film forming agent of polyvinyl acetate and styrene/acrylamide/butyl acrylate copolymer.
5. granule according to claim 1, it is characterised in that the quick-releasing type film forming agent is Arabic gum, carboxymethyl One or more in sodium starch, polyvinyl alcohol.
6. granule according to claim 5, it is characterised in that the quick-releasing type film forming agent is weight than 1:1-3 carboxylic The compound quick-releasing type film forming agent of methyl starch sodium and polyvinyl alcohol.
7. granule according to claim 1, it is characterised in that the porous carrier, which is selected from, has preferable absorption property Concave-convex rod particle, volcanic rock particle, common brick particle, coal gangue particle, medical stone granule, zeolite granular, corn cob granule, core One or more in peach shell particle.
8. granule according to claim 7, it is characterised in that the porous carrier is concave-convex rod particle, volcanic rock Any of particle, corn cob granule.
9. according to the preparation method of any granule of claim 1 to 8, it is characterised in that comprise the following steps:
A, the preparation of kernel is adsorbed:Active components A is dissolved in 0.1-10 weight % solvent by formula rate, adds 0.05- 2.5 weight % emulsifying agent and 0.05-2.5 weight % dispersant stir evenly, and then add in porous carrier aforesaid liquid and fill Point absorption, add spacetabs type film forming agent in roller pelletizer fully roll coating, dry spacetabs type inner core particles are standby;
B, quick-acting medicament is coated:Active component B and residual solvent, emulsifying agent, dispersant are fully mixed by formula rate, used The adsorbent absorption fully mixes into powder and then with quick-releasing type film forming agent, delays again in roller pelletizer with above-mentioned drying The type inner core particles of releasing fully roll coating;
C, dry or dry again and produce the granule.
10. kill the purposes of sanitary insect pest according to any granule of claim 1 to 8, the sanitary insect pest be wriggler or Fly maggot.
CN201710616294.4A 2017-07-26 2017-07-26 Sanitary insecticidal granules and preparation method thereof Active CN107372516B (en)

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WO2019005700A1 (en) * 2017-06-26 2019-01-03 Merial, Inc. Dual active parasiticidal granule compositions, methods and uses thereof
CN109221107A (en) * 2018-09-12 2019-01-18 绩溪农华生物科技有限公司 A kind of sustained releasing pesticide granule and preparation method thereof
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CN110326613A (en) * 2019-08-05 2019-10-15 安徽金敦福农业科技有限公司 A kind of released granular pesticide and preparation method thereof
CN111296489A (en) * 2018-12-12 2020-06-19 江苏功成生物科技有限公司 Sanitary insecticidal composition containing bacillus sphaericus and organic phosphorus
CN111296488A (en) * 2018-12-12 2020-06-19 江苏功成生物科技有限公司 Sanitary insecticidal composition containing bacillus sphaericus and application thereof
CN111296491A (en) * 2018-12-12 2020-06-19 江苏功成生物科技有限公司 Sanitary insecticidal composition for preventing and treating mosquito larvae and application thereof
CN114600876A (en) * 2022-03-14 2022-06-10 中国科学院动物研究所 Mosquito killing method, poison bait and device
CN115868497A (en) * 2023-02-01 2023-03-31 山东瑞可佳农业科技发展有限公司 Insecticidal composition containing pyriproxyfen and dinotefuran and application method thereof

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US11147273B2 (en) 2017-06-26 2021-10-19 Boehringer Ingelheim Animal Health USA Inc. Dual active parasiticidal granule compositions, methods and uses thereof
CN109221107A (en) * 2018-09-12 2019-01-18 绩溪农华生物科技有限公司 A kind of sustained releasing pesticide granule and preparation method thereof
CN109042641A (en) * 2018-09-14 2018-12-21 河北威远生物化工有限公司 A kind of emamectin benzoate B2a/B2b benzoate granule and preparation method thereof
CN109258632A (en) * 2018-09-29 2019-01-25 绩溪农华生物科技有限公司 A kind of nano pesticide composition and preparation method thereof
CN111296489A (en) * 2018-12-12 2020-06-19 江苏功成生物科技有限公司 Sanitary insecticidal composition containing bacillus sphaericus and organic phosphorus
CN111296488A (en) * 2018-12-12 2020-06-19 江苏功成生物科技有限公司 Sanitary insecticidal composition containing bacillus sphaericus and application thereof
CN111296491A (en) * 2018-12-12 2020-06-19 江苏功成生物科技有限公司 Sanitary insecticidal composition for preventing and treating mosquito larvae and application thereof
CN110326613A (en) * 2019-08-05 2019-10-15 安徽金敦福农业科技有限公司 A kind of released granular pesticide and preparation method thereof
CN114600876A (en) * 2022-03-14 2022-06-10 中国科学院动物研究所 Mosquito killing method, poison bait and device
CN115868497A (en) * 2023-02-01 2023-03-31 山东瑞可佳农业科技发展有限公司 Insecticidal composition containing pyriproxyfen and dinotefuran and application method thereof

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