CN101945576B - Coated inert granules - Google Patents

Coated inert granules Download PDF

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Publication number
CN101945576B
CN101945576B CN200980105914.1A CN200980105914A CN101945576B CN 101945576 B CN101945576 B CN 101945576B CN 200980105914 A CN200980105914 A CN 200980105914A CN 101945576 B CN101945576 B CN 101945576B
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particle
polymer
dispersant
plant
acid
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CN101945576A (en
Inventor
Y·迪克曼
M·伊沙克
R·多布拉瓦
M·梅尔特奥卢
铃木秀和
F·杰克尔
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BASF SE
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BASF SE
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to coated inert granules whose coating comprises at least one polymer, at least one agriculturally active ingredient and at least one dispersant. It also relates to a process for preparation of said granules comprising the steps (1) treating at least onepolymer, at least one agriculturally active ingredient and at least one dispersant with water, (2) treating inert granules with the aqueous composition of step (1), and (3) drying the composition of step (2). The present invention also relates to a method of combating harmful insects, phytopathogenic fungi and controlling undesired vegetation with said granules.

Description

The inert particle applying
The present invention relates to the inert particle applying, its coating contains at least one polymer, at least one agriculturally active ingredients and at least one dispersant.It also relates to a kind of method of preparing described particle, comprises the steps:
(1) water is processed at least one polymer, at least one agriculturally active ingredients and at least one dispersant;
(2) with the waterborne compositions of step (1), inert particle is processed, and
(3) composition of step (2) is dried.
The invention still further relates to the described particle antagonism of a kind of use insect, plant pathogenic fungi and control the method for undesired plant growth.Other embodiments have been described in claims and specification.
The combination of preferred embodiment and other preferred embodiments is also within scope of the present invention.
WO 00/07443 has described controlled release granule, and it can obtain by the following method: the coating that contains active component is applied on the solid carrier in fluid bed, and described fluid bed has 6000-25, the heat input of 000KJ/KG coated polymeric.Coated polymeric is selected from the copolymer of for example acrylate and methacrylate or the copolymer of vinyl acetate and vinyl pyrrolidone.
WO 99/44421 has described the solid pesticide compositions applying, and it contains be mixed with granular agricultural chemicals with inert carrier together with surfactant.Coating is the thermoplastic polymer of water-emulsifiable, as polyacrylate, polyvinyl acetate.
Unsettled European application EP06125078.3 has described the preparaton that contains agricultural chemicals and copolymer, and described copolymer is the copolymer of vinyl pyrrolidone and (methyl) alkyl acrylate or alkyl vinyl ether or alkyl vinyl ester.It has listed the various examples of solid or liquid adjustments.
Resist rice grub and disease is also known with the granular preparaton of agricultural chemicals.This normally carries out in the following way: described granular preparaton is added in the aqueous medium of paddy growth, typically add in paddy field water either or raising rice seedlings case.
The shortcoming of current granular composition is their preparation technology's difficulty, for example, will in the fluid bed of heating, carry out, and their agriculturally active ingredients discharges slowly or their effect deficiency.
Target of the present invention is to find a kind of agricultural mixture, and it can show faster and/or adjustable agriculturally active ingredients rate of release.Another target be find a kind of can be easily and the cheap preparaton of preparing.Another target is to find a kind of solid formulations, and it shows than the higher effect of other solid formulations with identical agriculturally active ingredients.Finally, another target is to find the preparaton that shows above-mentioned advantage in the agricultural of paddy rice is processed.
The inert particle that described target applies by employing realizes, and its coating contains at least one polymer, at least one agriculturally active ingredients and at least one dispersant, and wherein said polymer contains with polymerized form:
A) vinyl lactam, and
B) there is C 8-C 30n-alkyl or the N of the acrylic or methacrylic acid of alkyl, the acid amides that N-dialkyl group replaces, and
C) mineral salt of acrylic or methacrylic acid; Or
A) vinyl lactam, and
D) C of acrylic or methacrylic acid 8-C 30arrcostab, and
The combination of the mineral salt that E) optionally, contain at least one sulfonic ethylenically unsaturated monomer or its salt and acrylic or methacrylic acid; Or
A) vinyl lactam, and
F) monomer of formula (I):
Wherein
R1 and R2 are H or CH independently 3,
R3 is C 6-C 10aryl or C 7-C 19aralkyl, it can be by identical or different C 1-C 9alkyl and/or C 1-C 5alkoxy substituent replaces,
N is the integer of 1-100; Or
A) vinyl lactam, and
G) C 1-C 30organic acid vinyl esters, and
H) polyether polyols; Or
I) alkyl methacrylate, and
J) methacrylic acid.
Usually, it is 0.1-10mm that the inert particle of coating of the present invention contains granularity, preferably the particle of 0.5-8mm.That described particle can be is spherical, cylindric, sheet or other shapes arbitrarily.
Inert particle is the particle just not in the time not applying any agriculturally active ingredients with agriculture effect.Preferably there is the inert particle higher than the density of water, its density under 20 DEG C and 1013 millibars preferably higher than 1.00g/cm 3.The example of suitable inert particle is natural ore deposit soil, as the mixture of silica gel, silica, silicate, talcum, kaolin, lime stone, lime, chalk, calcite, bole, sand, loess, clay, dolomite, diatomite, calcium sulphate, magnesium sulfate, magnesia or above-mentioned substance.The mixture of preferably clay and silica.
Usually, described inert particle can contain 0-75wt%, and the preferably adhesive of 0.5-10wt%, with respect to the dry weight of described inert particle.The example of adhesive is carbohydrate, protein, lipoid, lignin or synthetic polymer.Preferably synthetic polymer binder, particularly polyvinyl alcohol.In the situation that there is adhesive, term " inert particle " comprises adhesive.
The coating of described inert particle contains at least one polymer, preferred a kind of polymer.Described polymer contains with polymerized form:
A) vinyl lactam, and
B) there is C 8-C 30n-alkyl or the N of the acrylic or methacrylic acid of alkyl, the acid amides that N-dialkyl group replaces, and
C) mineral salt of acrylic or methacrylic acid; Or
A) vinyl lactam, and
D) acrylic acid C 8-C 30arrcostab or methacrylic acid C 8-C 30arrcostab, and
The combination of the mineral salt that E) optionally, contain at least one sulfonic ethylenically unsaturated monomer or its salt and acrylic or methacrylic acid; Or
A) vinyl lactam, and
F) monomer of formula (I):
Wherein
R1 and R2 are H or CH independently 3,
R3 is C 6-C 10aryl or C 7-C 19aralkyl, it can be by identical or different C 1-C 9alkyl and/or C 1-C 5alkoxy substituent replaces,
N is the integer of 1-100; Or
A) vinyl lactam, and
G) C 1-C 30organic acid vinyl esters, and
H) polyether polyols; Or
I) alkyl methacrylate, and
J) methacrylic acid.
In a preferred embodiment, the polymer that applies inert particle of the present invention contains vinyl lactam copolymer with polymerized form.
Suitable vinyl lactam is for example N-caprolactam or NVP, preferably NVP.
There is C 8-C 30n-alkyl or the N of the acrylic acid of alkyl or methacrylic acid, the acid amides that N-dialkyl group replaces is suitable comonomer.Suitable alkyl is for having 8-30, straight chain, side chain or the cyclic alkyl of preferred 8-20 carbon atom.N-alkyl or N, the example of (methyl) acrylamide that N-dialkyl group replaces is N-stearyl acrylamide, N-stearyl Methacrylamide, N-(1-methyl undecyl) acrylamide, N-(1-methyl undecyl) Methacrylamide, N-dodecyl acrylamide, N-dodecyl methyl acrylamide, N-octyl acrylamide, N-octyl group Methacrylamide, N, N-dioctyl acrylamide, N, N-dioctyl Methacrylamide, N-cetyl acrylamide, N-cetyl Methacrylamide, N-myristyl acrylamide, N-myristyl Methacrylamide, N-(2-ethylhexyl) acrylamide, N-(2-ethylhexyl) Methacrylamide.Preferably N-(1-methyl undecyl) acrylamide.
The mineral salt of suitable acrylic or methacrylic acid are for example PAA or Sodium methacrylate, preferably PAA.Above-mentioned monomer also can use with the form of combination of monomers.
Acrylic acid C 8-C 30arrcostab or methacrylic acid C 8-C 30arrcostab is other suitable comonomers.About this point, particular importance for thering is acrylate and the methacrylate of fatty alcohol of chain length of 8-18 carbon atom, that wherein said alkyl can be branching or non-branching; Most preferably there is the chain length of 8-12 carbon atom, that wherein said alkyl can be branching or non-branching.
Especially, 2-ethyl hexyl acrylate, 2-ethylhexyl acrylate, acrylic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, lauryl acrylate, acrylic acid myristyl ester, aliphatic acrylate, stearyl acrylate base ester, acrylic acid oil base ester, acrylic acid docosyl ester, 2-Propenoic acid, 2-methyl-, octyl ester, methacrylic acid 2-ethylhexyl, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, methacrylic acid myristyl ester, methacrylic acid cetyl ester, methacrylic acid stearyl, methacrylic acid oil base ester, methacrylic acid docosyl ester, acrylic acid tert-butylcyclohexyl ester and methacrylic acid tert-butylcyclohexyl ester are suitable.Lauryl acrylate and methacrylic acid stearyl are preferred, and lauryl acrylate is most preferred.
Containing at least one sulfonic ethylenically unsaturated monomer is also suitable comonomer.Described monomer can exist with its sour form and salt form.The example of described monomer is styrene sulfonic acid, vinyl sulfonic acid, allyl sulphonic acid, methallyl sulfonic acid and the defined monomer of following formula (II):
In formula (II)
N is 0,1,2 or 3, particularly 1 or 2;
X is O or NR 5;
R 1for hydrogen or methyl;
R 2, R 3be hydrogen or C independently of one another 1-C 4alkyl, particularly hydrogen or methyl, and
R 5for hydrogen or C 1-C 4alkyl, particularly hydrogen.
The example of the monomer of formula (II) is 2-acrylamido-2-methyl propane sulfonic acid, 2-methacrylamido-2-methyl propane sulfonic acid, 2-acrylamido ethyl sulfonic acid, 2-methacrylamido ethyl sulfonic acid, 2-acryloxy ethyl sulfonic acid, 2-methacryloxy ethyl sulfonic acid, 3-acryloxy propane sulfonic acid and 2-methacryloxy propane sulfonic acid.
If described in contain at least one sulfonic ethylenically unsaturated monomer and exist with the form of its salt, they have corresponding cation as counter ion counterionsl gegenions.Suitable cationic example is that alkali metal cation is as Na +or K +, alkaline-earth metal ions is as Ca 2+and Mg 2+, also have in addition ammonium ion as NH 4 +, tetraalkyl ammonium ion, as tetramethyl-ammonium, tetraethyl ammonium and TBuA, also has protonated primary, secondary and tertiary amine in addition, particularly has 1,2 or 3 and is selected from C 1-C 20those of the group of alkyl and ethoxy, the list of for example protonated form-, two-and tri-n-butylamine, propylamine, diisopropylamine, hexylamine, dodecyl amine, oleyl amine, stearylamine, the oleyl amine of ethoxylation, stearylamine, monoethanolamine, diethanol amine, triethanolamine or the N of ethoxylation, N-dimethylethanolamine.
Preferably containing at least one sulfonic ethylenically unsaturated monomer is defined monomer in formula II, more preferably acrylamido-2-methyl propane sulfonic acid and sodium salt thereof.
Other suitable comonomers are monomers of following formula (I):
In formula (I), radicals R 1 and R2 can have the implication of H and/or methyl in each case independently of one another.Therefore, these are derivatives of acrylic acid and/or methacrylic acid.
Radicals R 3 refers to C 6-C 10aryl, as phenyl or naphthyl; Or C 7-C 19, preferably C 7-C 12aralkyl, as benzyl, phenethyl or phenylpropyl.The defined group of R3 can have one or more, is generally 1-3 identical or different C 1-C 9alkyl and/or C 1-C 5alkoxy substituent, that described substituting group can be straight chain or side chain, or open chain, ring-type or alicyclic.The C that can mention 1-C 9the example of alkyl substituent is: methyl, ethyl, 1-propyl group, 2-propyl group, 1-butyl, 2-butyl, 1,1-dimethyl ethyl, 1-amyl group, 2-amyl group, 1-hexyl, cyclohexyl, 1-heptyl, 1-octyl group, 1-nonyl.The C that can mention 1-C 5the example of alkoxy substituent is: methoxyl group, ethyoxyl, propoxyl group, 2-propoxyl group, 1-butoxy, 2-butoxy, 1,1-dimethyl ethyoxyl, 1-amoxy, 2,2-dimethyl propoxyl group.Preferred R3 group is for example phenyl, p-methylphenyl, benzyl, to hydroxybenzyl, p-hydroxybenzene, p-methoxyphenyl, to methoxy-benzyl or cyclohexyl.
Index n in formula (I) is 0-100, preferably 1-100, the integer of particularly preferably 1-25, particularly 1-10.If n is greater than 1 number, the radicals R 2 of so each repetitive is each has identical implication, or independent of one another, if suitable random distribution is H or CH in each case 3.In this case, the radicals R 2 of preferred about 50-100% is H, and the radicals R 2 of about 0-50% is CH 3.In the preferred embodiment of the present invention, be to be greater than 1 number at n, all groups all have identical implication.Now particularly preferably H of R2.
The comonomer of most preferred formula (I) is acrylic acid phenoxy group ethyl ester and methacrylic acid phenoxy group ethyl ester.
Other suitable comonomers are C 1-C 30organic acid vinyl esters.Be preferably aliphatic C 1-C 30the vinyl esters of carboxylic acid, described carboxylic acid is aliphatic C more preferably 2-C 12carboxylic acid, most preferably acetic acid.The example of carboxylic acid is formic acid, acetic acid, propionic acid branching or non-branching, butyric acid, valeric acid, caproic acid, sad, 2 ethyl hexanoic acid, pelargonic acid, n-capric acid, n-undecane acid, dodecanoic acid, n-tridecane acid, n-teradecanoic acid, n-pentadecane acid, Palmiticacid, n-heptadecane acid and n-octadecane acid and isomer thereof.Most preferably vinyl acetate.
Further, polyether polyols is suitable comonomer.Its example is polyethylene glycol, polypropylene glycol, PolyTHF or polytetramethylene glycol, and described polytetramethylene glycol can be obtained by 2-ethyl oxirane or 2,3-dimethyl ethylene oxide.Suitable polyether polyols is also statistical copolymer or the block-wise copolymers of being prepared by oxirane, expoxy propane or epoxy butane, as PLURONIC F-127.Described block copolymer can be AB or ABA type.Other examples of polyether polyols be on one or two terminal hydroxy group by alkylating those.Suitable alkyl is aliphatic C 1-C 22alkyl, preferable methyl, ethyl, normal-butyl, isobutyl group, amyl group, hexyl, octyl group, nonyl, decyl, dodecyl, octadecyl.Preferred polyether polyols is polyethylene glycol.
In a preferred embodiment, polymer of the present invention contains vinyl pyrrolidone, has C with polymerized form 8-C 30n-alkyl or the N of the acrylic or methacrylic acid of alkyl, acid amides and PAA or Sodium methacrylate that N-dialkyl group replaces.Described polymer can be made up of following material:
● at least 60wt%, the preferred at least vinyl pyrrolidone of 70wt%;
● 1-30wt%, preferably 5-22wt%'s has a C 8-C 30n-alkyl or the N of the acrylic or methacrylic acid of alkyl, the acid amides that N-dialkyl group replaces; And
● 0.5-10wt%, preferably PAA or the Sodium methacrylate of 2-8wt%.
These copolymers can have 5-60, preferably 10-35, and the particularly preferably K value of 12-30, described K value is according to recording under the Fikentscher method condition that concentration is 1% in 0.1mol NaCl solution.This polymer can synthesize by radical polymerization in accordance with known methods, for example, as described in WO2007/017452.
In another preferred embodiment, the C that described polymer contains vinyl pyrrolidone, acrylic or methacrylic acid with polymerized form 8-C 20arrcostab and optionally, the combination of the mineral salt that contain at least one sulfonic ethylenically unsaturated monomer and acrylic or methacrylic acid.Preferably, the C that described polymer contains vinyl pyrrolidone, acrylic or methacrylic acid with polymerized form 8-C 20arrcostab, the mineral salt that contain at least one sulfonic ethylenically unsaturated monomer and acrylic or methacrylic acid.The same preferred C also having containing vinyl pyrrolidone and acrylic or methacrylic acid 8-C 20the copolymer of Arrcostab.
The C that contains vinyl pyrrolidone and acrylic or methacrylic acid at described copolymer 8-C 20in the situation of Arrcostab, described copolymer preferably contains:
● 60-99wt%, preferably 70-95wt%, the particularly preferably vinyl pyrrolidone of 75-90wt%, and
● 1-40wt%, preferably 5-30wt%, the more preferably C of the acrylic or methacrylic acid of 10-25wt% 8-C 20arrcostab, wherein the summation of monomer is 100wt%.
These copolymers can have 5-60, preferably 10-35, and the particularly preferably K value of 12-30, described K value is according to recording under the Fikentscher method condition that concentration is 1% in 0.1mol NaCl solution.This polymer can synthesize by radical polymerization in accordance with known methods, for example, as described in WO2007/017452.Described polymer can be statistical copolymer, block copolymer or graft copolymer.Preferably statistical copolymer and graft copolymer.
The C that contains vinyl pyrrolidone, acrylic or methacrylic acid at described copolymer 8-C 20arrcostab, contain at least one sulfonic ethylenically unsaturated monomer and acrylic or methacrylic acid the situation of mineral salt under, following composition is preferred:
● at least 60wt%, the preferred at least vinyl pyrrolidone of 70wt%,
● 1-30wt%, the preferably C of the acrylic or methacrylic acid of 5-22wt% 8-C 20arrcostab, and
● 0.5-10wt%, the preferably mineral salt that contain at least one sulfonic ethylenically unsaturated monomer and acrylic or methacrylic acid of 1-8wt%; Wherein the summation of monomer is 100wt%.
These copolymers have and are measured as 10,000-100 by GPC method well known by persons skilled in the art, 000g/mol, preferably 10,000-75,000g/mol, particularly preferably 10,000-50, the weight average molecular weight of 000g/mol.This polymer can synthesize by radical polymerization in accordance with known methods, for example, as described in WO 2006/111327.
In another preferred embodiment, the monomer that described polymer contains vinyl pyrrolidone and formula (I) with polymerized form, wherein residue R1 to R3 and n are as hereinbefore defined:
Described polymer can be made up of following material:
● 10-99.5wt%, the preferably vinyl pyrrolidone of 50-99wt%, particularly 90-98wt%, and
● 0.5-90wt%, the preferably monomer of the formula (I) of 1-50wt%, particularly 2-10wt%; Wherein the summation of monomer is 100wt%.
These copolymers can have and are at least 7, preferably 15-50, and the particularly preferably K value of 25-45, described K value is according to recording under the Fikentscher method condition that concentration is 1% in 0.1mol NaCl solution.This polymer can synthesize by radical polymerization in accordance with known methods, for example, as described in WO2006/018135.
In another preferred embodiment, described polymer contains caprolactam, aliphatic C with polymerized form 1-C 30organic acid vinyl esters and polyether polyols are as graft copolymer.Described polymer can be made up of following material:
● at least 20wt%, the preferably caprolactam of 20-80wt%,
● at least 5wt%, the preferably aliphatic C of 19-50wt% 1-C 30organic acid vinyl esters, and
● at least 1wt%, the preferably polyether polyols of 1-61wt%; Wherein the summation of monomer is 100wt%.
These copolymers can have 50,000-500,000g/mol, preferably 100,000-250, the weight average molecular weight of 000g/mol.This polymer can synthesize by radical polymerization in accordance with known methods, for example, as described in WO 2007/051743.
In another preferred embodiment, the polymer that applies inert particle of the present invention contains (methyl) alkyl acrylate and (methyl) acrylic acid with polymerized form.
Suitable (methyl) alkyl acrylate is the Arrcostab of acrylic or methacrylic acid, preferably C1-C12, more preferably C1-C4 Arrcostab.Most preferably methyl acrylate or methyl methacrylate, particularly methyl methacrylate.Suitable (methyl) acrylic acid is acrylic or methacrylic acid, preferable methyl acrylic acid.Particularly preferred (methyl) alkyl acrylate and (methyl) acrylic copolymer are the methacrylic acid copolymers with methyl acrylate or methyl methacrylate.
Described polymer can be made up of following material:
● 90wt% at the most, preferably (methyl) alkyl acrylate of 50wt%, particularly 10-50wt% at the most, and
● at least 10wt%, preferably (methyl) acrylic acid of 50wt%, particularly 50-90wt% at least; Wherein the summation of monomer is 100wt%.
These copolymers can have 500-200000 dalton, preferably the daltonian weight-average molar mass of 1000-100000 dalton, particularly 2000-70000.Described molal weight can be by known method, as gel permeation chromatography.These copolymers can have 5-80, preferably 5-50, and the particularly preferably K value of 10-35, described K value is according to recording under the Fikentscher method condition that concentration is 1% in 0.1mol NaCl solution.This polymer can synthesize by radical polymerization in accordance with known methods.
In the coating of described inert particle, there is at least one agriculturally active ingredients.Optionally, among described inert particle or on or on described coating, for example, in the surface pore of described inert particle, can there are identical or other active components.Based among particle of the present invention or on the total amount of active component, preferably 80wt% at least, more preferably 90wt% at least, particularly 98wt% at least, be especially present in the coating of described particle for all active components.
Within intended scope of the present invention, term " at least one agriculturally active ingredients " represents optional one or more compounds from following group: fungicide, insecticide, nematocide, weed killer herbicide and/or safener or growth regulator; Be preferably selected from the group of fungicide, insecticide or nematocide; Most preferably be selected from the group of insecticide.Also can adopt the mixture of two or more agricultural chemicals in above-mentioned classification.Preferably, the mixture that adopts ethiprole (fipronil) or contain ethiprole.
The example of suitable insecticide is organic (sulfo-) phosphate, hydrogen carbamate, pyrethroid, growth regulator, nicotinic receptor agonists/agonist compounds, GABA agonist compounds, macrolide insecticide, METI I compound, METI II and III compound, uncoupler compound, oxidative phosphorylation inhibitors compound, the agent interfering compound of casting off a skin, mixed-function oxidase inhibitor compound, sodium channel blockers compound.
The example of suitable weed killer herbicide is lipoid biosynthesis inhibitor, ALS inhibitor, photosynthetic inhibitor, protoporphyrinogen-IX oxidase inhibitor, bleaching weed killer herbicide, EPSP synthase inhibitor, glutamine synthase inhibitor, DHP synthase inhibitor, mitotic inhibitor, VLCFA inhibitor, biosynthesis cellulose (cellulose biosynthesis), uncoupler weed killer herbicide, auximone weed killer herbicide, auximone transport inhibitors, safener.
The example of suitable fungicide is strobilurins class (strobilurins), carboxylic acid amides, azole, nitrogen-containing heterocycle compound, carbamate and dithiocarbamate; Other fungicides are as guanidine class, antibiotic, organo-metallic compound, sulfur heterocyclic compound, organic phosphorus compound, organochlorine compound, nitrophenyl derivative, inorganic active compound.
The inert particle of coating of the present invention contains conventionally:
The inert particle of 70-99.3wt%,
The polymer of 0.1-10wt%,
0.1-10wt% dispersant,
The agriculturally active ingredients of 0.1-10wt%,
The gross weight of the inert particle based on described coating.
The inert particle of preferred coating of the present invention contains:
The inert particle of 87-98.4wt%,
The polymer of 0.3-3wt%,
1-7wt% dispersant,
The agriculturally active ingredients of 0.3-3wt%,
The gross weight of the inert particle based on described coating.
The preparation method of particle of the present invention comprises the steps:
(1) water is processed at least one polymer, at least one agriculturally active ingredients and at least one dispersant,
(2) waterborne compositions obtaining by step (1) is processed inert particle, and
(3) composition of drying steps (2).
In step (1), can process described polymer, active component and surfactant system separately or with various order waters.Preferably, step (1) comprises the steps:
(1a) water is processed at least one polymer and at least one dispersant,
(1b) water is processed at least one agriculturally active ingredients and at least one optional dispersant, and
(1c) step (1a) and waterborne compositions (1b) are mixed.
In a preferred embodiment, step (1a) is included in before water processes, first by least one polymer and at least one dispersant.Step (1a) and (1b) in the dispersant that adds can be similar and different.
Described compound can be in solution, emulsion, suspension or suspended emulsion.In a preferred embodiment, in the time that step (1) finishes, described polymer and dispersant are with very large degree, preferably completely soluble in water.Another preferred embodiment in, in the time that step (1) finishes, described active component is suspended in water together with at least one dispersant.
In step (2), adopt known paint-on technique, apply described inert particle with the waterborne compositions of step (1).For example, the waterborne compositions that contains described polymer and active component can be sprayed in described inert particle.Spraying can be carried out in fluidized bed coater or in rotary drum or rotating disk, and described inert particle is rolled therein.In a preferred embodiment, preferably by hybrid mode, described inert particle is processed with the waterborne compositions of step (1).Preferably mixing can be by adding the waterborne compositions of step (1) in uncoated inert particle and complete.Preferred steps (2) is at ambient temperature, more preferably carries out at 15-25 DEG C.In a preferred embodiment, step (2) is to be less than the heat input of 6000kJ/kg coated polymer, is more preferably less than the heat input of 3000kJ/kg, is most preferably to carry out in the situation that there is no heat input.
In step (3), adopt known method, for example apply heat, vacuum and/or air or nitrogen stream, by the composition dries of step (2).For example, described composition is processed in the porous urn that controlled drying medium can be provided.Usually, adopt 30-180 DEG C, preferably the temperature of 35-90 DEG C.
The inert particle applying and their preparation method comprise at least one dispersant.Dispersant is surface active cpd, and it,, by reducing the surface tension between component, contributes to thin solids to be dispersed in liquid.Usually, described dispersant comprises at least one ion, nonionic or ion and non-ionic dispersing agent.Preferably, described dispersant comprises at least one ion dispersant.
Suitable dispersant is lignin sulfonic acid, naphthalene sulfonic acids, phenolsulfonic acid, dibutyl naphthalene sulfonic acids, alkyl aryl sulphonic acid, alkylsurfuric acid, alkyl sulfonic acid, fatty alcohol sulphuric acid, the alkali metal salt of fatty acid and Sulfated fatty alcohol glycol ether, alkali salt and ammonium salt, also has the condensation product of sulfonated naphthalene and naphthalene derivatives and formaldehyde, the condensation product of naphthalene or naphthalene sulfonic acids and phenol and formaldehyde, polyoxyethylene octyl phenol ether, the isooctyl phenol of ethoxylation, octyl phenol, nonyl phenol, alkyl phenol polyethylene glycol ethers, tributyl phenyl polyglycol ether, three stearyl phenyl polyglycol ethers, alkyl aryl polyether alcohol, the condensation product of alcohol and fatty alcohol/oxirane, the castor oil of ethoxylation, polyoxyethylene alkyl ether, the polyoxypropylene of ethoxylation, laruyl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite waste liquor and methylcellulose.Preferred dispersant contains lignosulfonates, is preferably made up of lignosulfonates.
Can add formulation aid at described preparation method's any time point.Term " formulation aid " refers to the auxiliary agent that is suitable for preparing agricultural chemicals within intended scope of the present invention, as other solvents and/or preservative and/or defoamer and/or antifreezing agent, and optional colouring agent and/or adhesive and/or gelling agent and/or thickener.
The example of suitable solvent is water, aromatic solvent is (as Solvesso product, dimethylbenzene), alkane (for example mineral oil fractions, such as kerosene or diesel oil), coal tar and the oil that derives from plant or animal, aliphatic series, ring-type and aromatic hydrocarbon are (as toluene, dimethylbenzene, paraffin, tetrahydronaphthalene, alkylated naphthalene or their derivative), alcohol is (as methyl alcohol, butanols, amylalcohol, benzylalcohol, cyclohexanol), ketone is (as cyclohexanone, gamma-butyrolacton), pyrrolidones (NMP, NEP, NOP), acetic acid esters (ethylene acetate), glycol, fatty acid dimethylformamide, fatty acid and fatty acid ester, isophorone and methyl-sulfoxide.In principle, also can adopt solvent mixture.Preferably in described preparaton, do not add solvent.
Also can in described preparaton, add antifreezing agent, as glycerine, ethylene glycol, hexylene glycol, propane diols and bactericide.
Suitable defoamer is as the defoamer based on silicon or dolomol.
Suitable preservative is as BIT and/or 2-methyl-2H-isothiazole-3-ketone or Sodium Benzoate or benzoic acid.
Thickener (that is, can give described preparaton and flow when behavior-leaves standstill and there is high viscosity with pseudoplastic behavior, under agitated conditions, have low viscosity-compound) example for for example polysaccharide or organic or inorganic layer mineral, as xanthans.
The present invention also comprises agrochemical formulation, the inert particle that the inert particle that it contains coating of the present invention or prepared according to the methods of the invention apply.Described agrochemical formulation can be prepared in the following way: by described particle with formulation aid (as listed above formulation aid) or mix with other agrochemical formulations.Preferably, described auxiliary agent is solid.These solids can be powdery or as preferred, are graininess.Preferably, described agrochemical formulation is made up of the inert particle of coating of the present invention.
All embodiments of above-mentioned application are all called as " preparaton of the present invention " hereinafter.
The present invention also comprises a kind of method of resisting insect and/or plant pathogenic fungi, described method comprise by insect and/or plant pathogenic fungi or can be therein or growing plants, seed, soil or plant growth environment on it, wait to prevent that described insect and/or plant pathogenic fungi invasion and attack or the plant, seed or the soil that infect from contacting with the agrochemical formulation of the present invention of effective dose.Conventionally, veteran can select suitable agriculturally active ingredients to resist described insect and/or fungi, as insecticide and/or fungicide.
Therefore, preparaton of the present invention can be used for controlling various plants disease fungus or the insect on the plant of various cultivations or the seed of weeds and these plants, described plant or weeds are as wheat, rye, barley, oat, paddy rice, corn, dogstail, banana, cotton, soybean, coffee, sugarcane, liane, fruit and ornamental plants, and vegetables are as cucumber, Kidney bean, tomato, potato and cucurbitaceous plant.Especially, described plant is paddy rice.
The present invention also comprises a kind of method of improving plant health, and described method comprises the place that preparaton of the present invention is applied to plant, plant part or plant growth, and its Pesticides is the agricultural chemicals that can give plant health effect.
The present invention also comprises a kind of method of controlling undesired plant growth, and described method comprises makes the agrochemical formulation of the present invention of herbicidally effective amount act on plant, their growing environment or the seed of described plant.Conventionally, veteran can select suitable agriculturally active ingredients for example, to control undesired plant growth, weed killer herbicide.Therefore, preparaton of the present invention is suitable for controlling in useful plant, the particularly common noxious plant in crops or perennial crops, described crops are as oat, barley, millet, corn, paddy rice, wheat, sugarcane, cotton, rape, flax, lentil, sugar beet, tobacco, sunflower and soybean.Especially, crops are rice crop.Control undesirable plant growth and should be understood to refer to elimination weeds.Weeds should be understood to refer to all those local plants of not expecting their growths that are grown in its widest implication.
Therefore, as mentioned above, preparaton of the present invention can apply by variety of way.
In an embodiment of the invention, preparaton of the present invention is carried out to foliage applying, for example, by the mode of dusting; Or described mixture is applied on seed, rice shoot or plant.
Another embodiment of the invention comprises to be processed soil, before by described plant seeding (for example, the mode of watering by soil) or afterwards or before or after described plant emerges, for example, by dusting mode or other modes, described mixture is imposed on to soil.
According to a variant of soil application, another theme of the present invention is a kind of by applying, and is particularly applied to the mode in drilling machine, the method that soil is processed.
According to a variant of soil application, another theme of the present invention is to process for ditch dug with a plow, and it comprises solid or liquid adjustments are applied to and are broadcast in seed-bearing exposed ditch dug with a plow, or seed and preparaton are applied in exposed ditch dug with a plow simultaneously.
In a preferred embodiment, the granular preparaton of agricultural chemicals is used for resisting rice grub and disease.This normally completes in the following way: described granular preparaton is added in the aqueous medium of paddy growth, typically be and add in paddy field water either or raising rice seedlings case.
By the embodiment by below, the present invention is described further, but be not subject to the restriction of these embodiment.
embodimentabbreviation
Ai active component
AMPS 4-acrylamido-2-methyl isophthalic acid-propane sulfonic acid
DMAc DMA
GPC gel permeation chromatography
H hour
Ha hectare
LA lauryl acrylate
MAA methacrylic acid
MMA methyl methacrylate
NaOH sodium hydroxide
PAA polyacrylic acid
PEG 6000 polyethylene glycol, molecular weight is 6000g/mol
PMMA polymethyl methacrylate
POEA acrylic acid phenoxy group ethyl ester
PVA polyvinyl alcohol
T-BPPiv crosses the neopentanoic acid tert-butyl ester
VAc vinyl acetate
VCap caprolactam
VP vinyl pyrrolidone
v50 2, two (2-amidino groups-propane) dihydrochlorides of 2 '-azo
v59 2,2 '-azo two (2-methylbutyronitrile)
5082 are purchased the surfactant mixture from Toho Chemical Industries, its
Contain polyether polyols sulphate, sodium lignin sulfonate, formaldehyde-naphthalene sulfonic acids
Sodium polymer, silica and isopropyl alcohol.
synthesizing of embodiment 1-polymer
Polymer a)
vinyl pyrrolidone/methyl undecyl acrylamide/sodium Acrylate copolymer (85/10/5wt%)
Initial charge (393g ethanol) is sucked together with nitrogen, and be heated to the interior temperature of reactor of 85 DEG C.Then start to add charging 1-3.In 3h, add charging 1 (100g ethanol, 170g VP, 20g methyl undecyl acrylamide) and charging 2 (27g PAA).In 4h, add charging 3 (84g ethanol, 6g v59).Then by mixture again after polymerization 2 hours.Ethanol is removed in distillation, and reactant mixture is carried out to steaming.Obtain molecular weight Mn=7,300g/mol, Mw=22, the polymer of 000g/mol (adopt GPC, using PMMA as standard specimen, measure) in DMAc.
Polymer b)
vinyl pyrrolidone/lauryl acrylate copolymer (90/10wt%)
Initial charge (350g isopropyl alcohol, 10g VP) is sucked together with nitrogen, and be heated to the interior temperature of reactor of 80 DEG C.Then start to add charging 1-3.In 5.5h, add charging 1 (400g isopropyl alcohol, 40g LA), in 6h, add charging 2 (300g isopropyl alcohol, 350g VP), in 6.5h, add charging 3 (19g t-BPPiv 75wt%, 100g isopropyl alcohol).Then by mixture again after polymerization 2 hours.Isopropyl alcohol is removed in distillation, and reactant mixture is carried out to steaming.After distillation, by 200g water dilution for polymer solution.Obtaining k value is 14, molecular weight Mn=4,400g/mol, Mw=7, the polymer of 600g/mol (adopt GPC, taking PMMA as standard specimen, measure in HFIP).
Polymer c)
vinyl pyrrolidone/acrylic acid phenoxy group ethyl ester copolymer (96/4wt%)
Initial charge (420g water, 0.4g Wako V 50,420g ethanol, 1.6g POEA, 34.4gVP) is sucked together with nitrogen, and be heated to the interior temperature of reactor of 75 DEG C.Then start to add charging 1 and 2.In 4h, add charging 1 (12.8g POEA, 60g water, 311.2g VP, 60g ethanol), in 5h, add charging 2 (70.8g water, 70.8g ethanol, 3.2g v50).Then by mixture again after polymerization 2 hours.Then ethanol is removed in distillation, and reactant mixture is carried out to steaming.Obtaining k value is 31, molecular weight Mn=10,400g/mol, Mw=27, the polymer of 600g/mol (adopt GPC, taking PMMA as standard specimen, measure in HFIP).
Polymer d)
methyl methacrylate/methacrylic acid copolymer (25/75wt%)
Initial charge (333.33g isopropyl alcohol, 58.33g charging 1) is sucked together with nitrogen, and be heated to the interior temperature of reactor of 75 DEG C.Then start to add charging 1 and 2.In 5h, add charging 1 (666.67g isopropyl alcohol, 125g MMA, 375g MAA); In 5.5h, add charging 2 (83.33g isopropyl alcohol, 13.33g t-BPPiv).Then by polymerization after mixture 1 hour, then add 25gNaOH (40wt%).Isopropyl alcohol is removed in distillation, and reactant mixture is carried out to steaming.Obtaining k value is 18, molecular weight Mn=12,300g/mol, Mw=62, the polymer of 000g/mol (adopt GPC, taking PAA as standard specimen, (pH 7) measures in water).
Polymer e)
vinyl pyrrolidone/lauryl acrylate/4-acrylamido-2-methyl isophthalic acid-propanesulfonate/PAA (76/20/2/2wt%)
Initial charge (250g isopropyl alcohol, 25g VP, 25g LA) is sucked together with nitrogen, and be heated to the interior temperature of reactor of 75 DEG C.Then, in 3h, add charging 1 (350g isopropyl alcohol, 165g VP, 25g LA), charging 2 (pH is 7 for 222g water, 28g AMPS sodium salt) and charging 3 (27g water, 13g PAA).In 4.5h, add charging 4 (47.5g water, 2.5g v50).After the rear polymerization of 1h, add charging 5 (10g water, 0.65g Wako V 50), then carry out the rear polymerization of 2h.Then isopropyl alcohol is removed in distillation, and reactant mixture is carried out to steaming.Obtaining k value is 22, molecular weight Mn=9,700g/mol, Mw=31, the polymer of 300g/mol (adopt GPC, taking PMMA as standard specimen, measure in DMAc).
Polymer f)
pEG 6000/ vinyl acetate/caprolactam graft copolymer (13/30/57wt%)
Initial charge (50g butyl acetate, 130g PEG 6000,1g charging 3) is sucked together with nitrogen, and be heated to the interior temperature of reactor of 77 DEG C.Then start to add charging 1-3.In 5h, add charging 1 (570g VCap, 120g butyl acetate), in 2h, add charging 2 (300g VAc, 80g butyl acetate), in 5.5h, add charging 3 (12.75g t-BPPiv 75wt%, 117.25g butyl acetate).Then by mixture again after polymerization 4 hours, add 500ml butyl acetate.Volatile compound is removed in distillation, and reactant mixture is carried out to steaming.Obtain molecular weight Mn=44,000g/mol, Mw=140, the polymer of 000g/mol (adopt GPC, taking PMMA as standard specimen, measure) in HFIP.
the preparation (according to method of the present invention) of embodiment 2A-particle
Be prepared as follows coating suspension: the dispersant 1 (sodium lignin sulfonate) of the each polymer that is 0.5g by consumption and 1.35g is dissolved in 5.75g water.In polymer solution, add slurry, described slurry by the 0.5g ethiprole in 1.0g water and 0.17g dispersant 2 ( 5082) composition.
By 5g above-mentioned coating solution was added to 47.5g particle in 100mL flask under stirring at room temperature in 5 minutes, (diameter is 1.2mm, length is 1.5-3mm) on, 47.5g particle is applied, and described particle is made up of the synthetic precipitated silica of 94wt% clay, 2.0wt% polyvinyl alcohol and 4.0wt%.
The wet granular obtaining is dried to 10 minutes at 60 DEG C in baking oven.In an identical manner remaining above-mentioned coating suspension is joined in dry particle, and again in baking oven, at 60 DEG C, be dried 60 minutes.
Obtain the particle (wt% calculates based on initial substance) of the coating being formed by polymer, 2.7wt% dispersant 1,1wt% ethiprole and the 0.3wt% dispersant 2 of 89.3wt% clay, the synthetic precipitated silica of 1.9wt%PVA, 3.8wt%, 1wt%.
embodiment 2B-does not contain the preparation (comparative example does not adopt method of the present invention) of the particle of polymer
Do not contain in contrast the particle of polymer according to the step preparation of embodiment 2A.Adopt identical particle and compound, and adopted identical concentration.Obtain the particle (wt% calculates based on initial substance) being formed by the surfactant of 90.3wt% clay, the synthetic precipitated silica of 1.9wt%PVA, 3.8wt%, 2.7wt% dispersant, 1wt% ethiprole and 0.3wt%.
embodiment 2C-commodity particle (comparative example does not adopt method of the present invention)
Also to the trade name of GR is tested available from the commercial product of BASF Japan, and used as comparative example.Described particle is to be made up of the grains of sand that are coated with 1wt% ethiprole based on gross weight.
the rate of release of embodiment 3-ethiprole
In order to determine the ethiprole rate of release of described particle, at room temperature 100mg particle is put into the beaker that 300mL water is housed.After 6 hours, adopt HPLC to measure the concentration of ethiprole.Result can be referring to table 1.
Table 1
Particle Rate of release [mg/l]
Commodity particle (embodiment 2C, comparative example) 0.07
Not containing polymer (embodiment 2B, comparative example) 0.83
Use polymer a) to apply (embodiment 2A) 1.21
Use polymer b) to apply (embodiment 2A) 1.16
The result of table 1 shows, by means of coating of the present invention, the rate of release of particle can improve.
the rate of release of ethiprole when embodiment 4-changes the content of dispersant
In order to determine the impact of dispersant, under change dispersant, measure rate of release.In order to carry out these tests, according to the method described in embodiment 2A, adopt polymer c) as polymer, and change the content of dispersant 1 (lignosulfonates), prepare particle.Result can be referring to table 2.As calculated in embodiment 2A, the particle of the percetage by weight of lignosulfonates based on final coating.
Table 2
Lignosulfonates [%] Rate of release [mg/l]
0 0.27
0.67 1.21
1.35 1.34
2.7 1.39
2.7 (comparative example, containing polymer coatings c)) 0.72
The result of table 2 shows, the rate of release of ethiprole increases along with the increase of dispersant.Rate of release during not containing polymer is less than dispersant/combination of polymers.This shows that polymer and dispersant have synergistic effect.
the picked-up of embodiment 5-ethiprole
In order to determine the amount of ethiprole of plant picked-up, particle is added in rice, and sowing.The consumption of ethiprole is 100 grams/ha, and this is corresponding to 10kg particle/hectare.After sowing 18 days, harvesting paddy rice, by vegetable material homogenizing, uses GC (adopting N-P to detect) and GC/MS to measure the ethiprole content in vegetable material.Result can be referring to table 3.
Table 3
Particle Ethiprole intake (ppm)
Commodity particle (embodiment 2C, comparative example) 7.0
Not containing polymer (embodiment 2B, comparative example) 9.7
Use polymer a) to apply (embodiment 2A) 11.1
Use polymer b) to apply (embodiment 2A) 12.7
Use polymer c) to apply (embodiment 2A) 11.0
Use polymer d) to apply (embodiment 2A) 10.6
Use polymer e) to apply (embodiment 2A) 10.1
The result of table 3 shows, in the time applying particle of the present invention, the amount of taking in the ethiprole in plant obviously raises.
the prevention and control of embodiment 6-insect
In order to determine the improvement of insect control effect, described particle is added into the rice plant in transplanting stage (being transplanted to basin from raising box).The consumption of ethiprole is 100 grams/ha, corresponding to 10kg particle/hectare.
Transplanting after 33 days, infecting described rice plant with Brown Planthopper.Infect after 1 day, measure the lethality of plant hopper.Insect prevention and control result can be referring to table 4.
Table 4
Particle Plant hopper lethality (%)
Commodity particle (embodiment 2C, comparative example) 33.3
Not containing polymer (embodiment 2B, comparative example) 50.0
Use polymer a) to apply (embodiment 2A) 66.7
Use polymer c) to apply (embodiment 2A) 86.7
The result of table 4 clearly shows, in the time adopting the particle of coating of the present invention, insect control effect has improved.

Claims (13)

1. the inert particle applying, its coating contains at least one polymer, at least one agriculturally active ingredients and at least one dispersant, and wherein said polymer contains with polymerized form:
A) vinyl pyrrolidone of 60-99wt%,
D) C of the acrylic or methacrylic acid of 1-40wt% 8-C 20arrcostab, and
E) mineral salt that contain at least one sulfonic ethylenically unsaturated monomer or its salt and acrylic or methacrylic acid;
The inert particle of wherein said coating contains:
The inert particle of 70-99.3wt%,
The polymer of 0.1-10wt%,
0.1-10wt% dispersant,
The agriculturally active ingredients of 0.1-10wt%,
The gross weight of the inert particle based on described coating;
Wherein said dispersant is ion dispersant;
The inert particle of wherein said coating is prepared by a method comprising the following steps:
(1) water is processed at least one polymer, at least one agriculturally active ingredients and at least one dispersant,
(2) process inert particle with the waterborne compositions of step (1), and
(3) composition of drying steps (2).
2. particle as claimed in claim 1, wherein among described inert particle or on or on described coating, there are identical or other active components.
3. particle as claimed in claim 1, wherein said dispersant comprises lignosulfonates.
4. particle as claimed in claim 2, wherein said dispersant comprises lignosulfonates.
5. the particle as described in any one in claim 1-4, wherein said inert particle has the density higher than water.
6. the particle as described in any one in claim 1-4, wherein at least one agriculturally active ingredients is ethiprole.
7. particle as claimed in claim 5, wherein at least one agriculturally active ingredients is ethiprole.
8. a method of preparing the particle described in any one in claim 1-7, comprises the steps:
(1) water is processed at least one polymer, at least one agriculturally active ingredients and at least one dispersant,
(2) process inert particle with the waterborne compositions of step (1), and
(3) composition of drying steps (2).
9. method as claimed in claim 8, wherein step (2) is carried out under heat input not having.
10. an agrochemical formulation, the inert particle of coating prepared by the inert particle that it contains the coating described in any one in claim 1-7 or method according to claim 8 or claim 9.
11. 1 kinds are resisted the method for insect and/or plant pathogenic fungi, described method comprise by insect and/or plant pathogenic fungi can be therein or growing plants, seed, soil or plant growth environment on it, wait to prevent described insect and/or plant pathogenic fungi invasion and attack or the claim 1-7 of the plant, seed or the soil that infect and effective dose in the particle described in any one or method according to claim 8 or claim 9 particle or the agrochemical formulation claimed in claim 10 prepared contact.
Control the method for undesired plant growth for 12. 1 kinds, described method comprises that particle or agrochemical formulation claimed in claim 10 prepared by the particle described in any one in the claim 1-7 that makes herbicidally effective amount or method according to claim 8 or claim 9 act on plant, their growing environment or the seed of described plant.
13. methods as described in claim 11 or 12, wherein said plant is paddy rice.
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