CN103202293A

CN103202293A - Coated inert granules

Info

Publication number: CN103202293A
Application number: CN 201310090361
Authority: CN
Inventors: 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
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-02-21
Filing date: 2009-02-19
Publication date: 2013-07-17
Also published as: CN101945576A; WO2009103760A2; WO2009103760A3; JP5562258B2; JP2011512385A; CN101945576B; CN103190396A

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 that applies

The application is to be on February 19th, 2009 applying date, and application number is 200980105914.1, and denomination of invention is divided an application for the application of " inert particle of coating ".

The inert particle that the present invention relates to apply, its coating contain at least a polymer, at least a agriculturally active ingredients and at least a dispersant.It also relates to a kind of method for preparing described particle, comprises the steps:

(1) water is handled at least a polymer, at least a agriculturally active ingredients and at least a dispersant;

(2) with the waterborne compositions of step (1) inert particle is handled, and

(3) composition to step (2) carries out drying.

The invention still further relates to the method for the described particle antagonism of a kind of usefulness insect, plant pathogenic fungi and control undesired plant growth.Other embodiments have been described in claims and specification.

The combination of preferred embodiment and other preferred embodiments also is within the scope of the present invention.

WO00/07443 has described controlled release granule, and it can obtain by the following method: the coating that will contain active component is applied on the solid carrier that is in the fluid bed, and described fluid bed has 6000-25, the heat input of 000KJ/KG coated polymeric.Coated polymeric is selected from for example copolymer or vinyl acetate and the vinylpyrrolidone copolymers of acrylate and methacrylate.

WO99/44421 has described the solid pesticide compositions that applies, and it contains with inert carrier and surfactant and to be mixed with granular agricultural chemicals.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 also is 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 the raising rice seedlings case.

The shortcoming of present granular composition is their preparation technology's difficulty, for example will carry out in the fluid bed of heating, and their agriculturally active ingredients discharges slowly or their effectiveness deficiency.

Target of the present invention is to seek a kind of agricultural mixture, and it can show faster and/or adjustable agriculturally active ingredients rate of release.Another target be seek a kind of can be easily and the cheap preparaton for preparing.Another target is to seek a kind of solid formulations, and it shows than the higher effectiveness of other solid formulations with identical agriculturally active ingredients.At last, another target is to seek the preparaton that shows above-mentioned advantage in the agricultural of paddy rice is handled.

Described target realizes that by adopting the inert particle that applies its coating contains at least a polymer, at least a agriculturally active ingredients and at least a dispersant, and wherein said polymer contains with polymerized form:

A) vinyl lactam and

B) has C ₈-C ₃₀The acid amides that N-alkyl or the N of the acrylic or methacrylic acid of alkyl, N-dialkyl group replace and

C) mineral salt of acrylic or methacrylic acid; Perhaps

A) vinyl lactam and

D) C of acrylic or methacrylic acid ₈-C ₃₀Arrcostab and

E) randomly, contain the combination of the mineral salt of at least one sulfonic ethylenically unsaturated monomer or its salt and acrylic or methacrylic acid; Perhaps

A) vinyl lactam and

F) monomer of formula (I):

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; Perhaps

A) vinyl lactam and

G) C ₁-C ₃₀The organic acid vinyl esters and

H) polyether polyols; Perhaps

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, the particle of preferred 0.5-8mm.That described particle can be is spherical, cylindric, sheet or other shapes arbitrarily.

Inert particle is the particle that just not has agriculture effect when not applying any agriculturally active ingredients.Preferably have the inert particle higher than the density of water, its density preferably is higher than 1.00g/cm under 20 ℃ and 1013 millibars ³The 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 adhesive of preferred 0.5-10wt% is with respect to the dry weight of described inert particle.The example of adhesive is carbohydrate, protein, lipoid, lignin or synthetic polymer.Preferred synthetic polymer binder, particularly polyvinyl alcohol.Exist under the situation of adhesive, term " inert particle " comprises adhesive.

The coating of described inert particle contains at least a polymer, preferred a kind of polymer.Described polymer contains with polymerized form:

A) vinyl lactam and

C) mineral salt of acrylic or methacrylic acid; Perhaps

A) vinyl lactam and

D) acrylic acid C ₈-C ₃₀Arrcostab or methacrylic acid C ₈-C ₃₀Arrcostab and

A) vinyl lactam and

F) monomer of formula (I):

Formula (I)

Wherein

R1 and R2 are H or CH independently ₃,

N is the integer of 1-100; Perhaps

A) vinyl lactam and

G) C ₁-C ₃₀The organic acid vinyl esters and

H) polyether polyols; Perhaps

I) alkyl methacrylate and

J) methacrylic acid.

In preferred embodiment, the polymer that applies inert particle of the present invention contains the vinyl lactam copolymer with polymerized form.

Suitable vinyl lactam is for example N-caprolactam or N-vinyl pyrrolidone, preferred N-vinyl pyrrolidone.

Has C ₈-C ₃₀N-alkyl or the N of the acrylic acid of alkyl or methacrylic acid, the acid amides that the 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 the 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, the 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.Preferred N-(1-methyl undecyl) acrylamide.

The mineral salt of suitable acrylic or methacrylic acid are for example PAA or Sodium methacrylate, preferred 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, that acrylate and the methacrylate of fatty alcohol for chain length with 8-18 carbon atom of particular importance, wherein said alkyl can be branching or non-branching; That the chain length that most preferably has 8-12 carbon atom, 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, the acrylic acid cetyl ester, 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, the methacrylic acid cetyl ester, the 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 also is 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):

Formula (II)

In formula (II)

N is 0,1,2 or 3, particularly 1 or 2;

X is O or NR ⁵

R ¹Be hydrogen or methyl;

R ², R ³Be hydrogen or C independently of one another ₁-C ₄Alkyl, particularly hydrogen or methyl, and

R ⁵Be 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 at least one sulfonic ethylenically unsaturated monomer that contains exists with the form of its salt, they have corresponding cation as counter ion counterionsl gegenions.Suitable cationic example is alkali metal cation such as Na ⁺Or K ⁺, alkaline-earth metal ions such as Ca ²⁺And Mg ²⁺, also have ammonium ion such as NH in addition ₄ ⁺, tetraalkyl ammonium ion such as tetramethyl-ammonium, tetraethyl ammonium and TBuA also have protonated primary, second month in a season and tertiary amine in addition, particularly have 1,2 or 3 and are selected from C ₁-C ₂₀Those of the group of alkyl and ethoxy, for example the list of 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, the N-dimethylethanolamine.

Preferably containing at least one sulfonic ethylenically unsaturated monomer is defined monomer among the formula II, more preferably acrylamido-2-methyl propane sulfonic acid and sodium salt thereof.

Other suitable comonomers are monomers of following formula (I):

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 is as phenyl or naphthyl; Perhaps C ₇-C ₁₉, preferred C ₇-C ₁₂Aralkyl is 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 ₅That alkoxy substituent, described substituting group can be straight chain or side chain, perhaps 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 for example is phenyl, p-methylphenyl, benzyl, to hydroxybenzyl, p-hydroxybenzene, p-methoxyphenyl, to methoxy-benzyl or cyclohexyl.

Index n in the formula (I) is 0-100, preferred 1-100, the integer of preferred especially 1-25, particularly 1-10.If n is the number greater than 1, so the radicals R 2 of each repetitive each have identical implication, perhaps independent of one another, if suitable random distribution is H or CH in each case ₃In this case, preferably the radicals R 2 of about 50-100% is H, and the radicals R 2 of about 0-50% is CH ₃In the preferred embodiment of the present invention, under n was situation greater than 1 number, all groups all had identical implication.The preferred especially H of R2 this moment.

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 ₃₀The organic 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, hexadecane acid, n-heptadecane acid and n-octadecane acid and isomer thereof.Vinyl acetate most preferably.

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 also is statistical copolymer or the block-wise copolymers by oxirane, expoxy propane or epoxy butane preparation, as polyethylene glycol-propane diols block copolymer.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 the N-dialkyl group replaces.Described polymer can be made of following material:

● 60wt% at least, the preferred vinyl pyrrolidone of 70wt% at least;

● 1-30wt%, preferred 5-22wt% has a C ₈-C ₃₀N-alkyl or the N of the acrylic or methacrylic acid of alkyl, the acid amides that the N-dialkyl group replaces; And

● 0.5-10wt%, PAA or the Sodium methacrylate of preferred 2-8wt%.

These copolymers can have 5-60, preferred 10-35, and the K value of preferred especially 12-30, described K value are to be to record under 1% the condition according to Fikentscher method concentration in 0.1mol NaCl solution.This polymer is can be in accordance with known methods synthetic by radical polymerization, for example as described in the WO2007/017452.

In another preferred embodiment, described polymer contains the C of vinyl pyrrolidone, acrylic or methacrylic acid with polymerized form ₈-C ₂₀Arrcostab and randomly contains the combination of the mineral salt of at least one sulfonic ethylenically unsaturated monomer and acrylic or methacrylic acid.Preferably, described polymer contains the C of vinyl pyrrolidone, acrylic or methacrylic acid with polymerized form ₈-C ₂₀Arrcostab, contain the mineral salt of at least one sulfonic ethylenically unsaturated monomer and acrylic or methacrylic acid.The same C that preferably contains vinyl pyrrolidone and acrylic or methacrylic acid in addition ₈-C ₂₀The copolymer of Arrcostab.

The C that contains vinyl pyrrolidone and acrylic or methacrylic acid at described copolymer ₈-C ₂₀Under the situation of Arrcostab, described copolymer preferably contains:

● 60-99wt%, preferred 70-95wt%, the vinyl pyrrolidone of preferred especially 75-90wt%, and

● 1-40wt%, preferred 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, preferred 10-35, and the K value of preferred especially 12-30, described K value are to be to record under 1% the condition according to Fikentscher method concentration in 0.1mol NaCl solution.This polymer is can be in accordance with known methods synthetic by radical polymerization, for example as described in the WO2007/017452.Described polymer can be statistical copolymer, block copolymer or graft copolymer.Preferred statistical copolymer and graft copolymer.

The C that contains vinyl pyrrolidone, acrylic or methacrylic acid at described copolymer ₈-C ₂₀Arrcostab, contain under the situation of mineral salt of at least one sulfonic ethylenically unsaturated monomer and acrylic or methacrylic acid, following composition is preferred:

● 60wt% at least, the preferred vinyl pyrrolidone of 70wt% at least,

● 1-30wt%, the C of the acrylic or methacrylic acid of preferred 5-22wt% ₈-C ₂₀Arrcostab, and

● 0.5-10wt%, preferred 1-8wt% contain at least one sulfonic ethylenically unsaturated monomer and

The mineral salt of acrylic or methacrylic acid; Wherein the summation of monomer is 100wt%.

These copolymers have with GPC method well known by persons skilled in the art and are measured as 10,000-100, and 000g/mol is preferred 10,000-75, and 000g/mol, preferred especially 10,000-50, the weight average molecular weight of 000g/mol.This polymer is can be in accordance with known methods synthetic by radical polymerization, for example as described in the WO2006/111327.

In another preferred embodiment, described polymer contains the monomer of vinyl pyrrolidone and formula (I) with polymerized form, and wherein residue R1 to R3 and n are as hereinbefore defined:

Formula (I)

Described polymer can be made of following material:

● 10-99.5wt%, the vinyl pyrrolidone of preferred 50-99wt%, particularly 90-98wt%, and

● 0.5-90wt%, the monomer of the formula (I) of preferred 1-50wt%, particularly 2-10wt%; Wherein the summation of monomer is 100wt%.

These copolymers can have and are at least 7, preferred 15-50, and the K value of preferred especially 25-45, described K value are to be to record under 1% the condition according to Fikentscher method concentration in 0.1mol NaCl solution.This polymer is can be in accordance with known methods synthetic by radical polymerization, for example as described in the 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 of following material:

● 20wt% at least, the caprolactam of preferred 20-80wt%,

● 5wt% at least, the aliphatic C of preferred 19-50wt% ₁-C ₃₀The organic acid vinyl esters, and

● 1wt% at least, the polyether polyols of preferred 1-61wt%; Wherein the summation of monomer is 100wt%.

These copolymers can have 50,000-500, and 000g/mol is preferred 100,000-250, the weight average molecular weight of 000g/mol.This polymer is can be in accordance with known methods synthetic by radical polymerization, for example as described in the WO2007/051743.

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, preferred 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 of following material:

● 90wt% at the most, preferred (methyl) alkyl acrylate of 50wt%, particularly 10-50wt% at the most, and

● 10wt% at least, 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, the preferred 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, preferred 5-50, and the K value of preferred especially 10-35, described K value are to be to record under 1% the condition according to Fikentscher method concentration in 0.1mol NaCl solution.This polymer can be synthetic by radical polymerization in accordance with known methods.

In the coating of described inert particle, there is at least a agriculturally active ingredients.Randomly, among the described inert particle or on or on described coating, for example in the surface pore of described inert particle, can exist identical or other active components.Based among the particle of the present invention or on the total amount of active component, preferred 80wt% at least, more preferably 90wt% at least, particularly 98wt% at least especially are present in the coating of described particle for all active components.

Within intended scope of the present invention, optional one or more compounds from following group of term " at least a agriculturally active ingredients " expression: 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 the above-mentioned classification.Preferably, adopt fluorine worm nitrile (fipronil) or contain the mixture of fluorine worm nitrile.

The example of suitable insecticide is organic (sulfo-) phosphate, 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 inhibitor 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 such 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 usually:

The inert particle of 70-99.3wt%,

The polymer of 0.1-10wt%,

The 0.1-10wt% dispersant,

The agriculturally active ingredients of 0.1-10wt%,

Gross weight based on the inert particle of 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%,

The 1-7wt% dispersant,

The agriculturally active ingredients of 0.3-3wt%,

Gross weight based on the inert particle of described coating.

The preparation method of particle of the present invention comprises the steps:

(1) water is handled at least a polymer, at least a agriculturally active ingredients and at least a dispersant,

(2) waterborne compositions that obtains with step (1) is handled inert particle, and

(3) composition of drying steps (2).

In step (1), can handle described polymer, active component and surfactant system separately or with various order waters.Preferably, step (1) comprises the steps:

(1a) water is handled at least a polymer and at least a dispersant,

(1b) water is handled at least a agriculturally active ingredients and optional at least a dispersant, and

(1c) step (1a) and waterborne compositions (1b) are mixed.

In preferred embodiment, step (1a) is included in before water handles, at first with at least a polymer and at least a dispersant.Step (1a) and (1b) in the dispersant that adds can be similar and different.

Described compound can be in solution, emulsion, suspension or the suspended emulsion.In preferred embodiment, when step (1) finished, described polymer and dispersant are with very big degree, and be preferably soluble in water fully.Another preferred embodiment in, when step (1) finished, described active component was suspended in the water with at least a 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 on the 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 preferred embodiment, preferably by hybrid mode, with the waterborne compositions of step (1) described inert particle is handled.Preferred mixing can add in the uncoated inert particle by the waterborne compositions with step (1) to be finished.Preferred steps (2) is at ambient temperature, more preferably carries out under 15-25 ℃.In preferred embodiment, step (2) is in the heat input less than the 6000kJ/kg coated polymer, is more preferably less than the heat input of 3000kJ/kg, most preferably is to carry out under the situation that does not have the heat input.

In step (3), adopt known method, for example apply heat, vacuum and/or air or nitrogen stream, with the composition dries of step (2).For example, described composition in being provided, is handled by the porous urn of controlled drying medium.Usually, adopt 30-180 ℃, preferred 35-90 ℃ temperature.

Comprise at least a dispersant among the inert particle that applies and their preparation method.Dispersant is surface active cpd, and it helps thin solids are dispersed in the liquid by reducing the surface tension between component.Usually, described dispersant comprises at least a ion, nonionic or ion and non-ionic dispersing agent.Preferably, described dispersant comprises at least a ion dispersant.

Suitable dispersant is lignin sulfonic acid, naphthalene sulfonic acids, phenolsulfonic acid, the 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, the condensation product of sulfonated naphthalene and naphthalene derivatives and formaldehyde in addition, 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 pure and mild 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 dispersing agent contains lignosulfonates, preferably is made up of lignosulfonates.

Can add formulation aid at described preparation method's any time point.Term " formulation aid " refers to be suitable for preparing the auxiliary agent of agricultural chemicals within intended scope of the present invention, as other solvents and/or preservative and/or defoamer and/or antifreezing agent, and optional colorant and/or adhesive and/or gelling agent and/or thickener.

The example of appropriate solvent is water, aromatic solvent is (as the Solvesso product, dimethylbenzene), alkane (mineral oil fractions for example, 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, the 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 preservatives is as 1,2-benzisothiazole-3-ketone and/or 2-methyl-2H-isothiazole-3-ketone or Sodium Benzoate or benzoic acid.

Thickener (that is, can give described preparaton with flow behavior-have high viscosity when namely leaving standstill of 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, and it contains the inert particle of coating of the present invention or the inert particle that prepared according to the methods of the invention applies.Described agrochemical formulation can prepare in the following way: mix with described particle and formulation aid (as mentioned listed formulation aid) or with other agrochemical formulations.Preferably, described auxiliary agent is solid.These solids can be powdery or be graininess as preferred.Preferably, described agrochemical formulation is made up of the inert particle of coating of the present invention.

All embodiments of above-mentioned application all are 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 with 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.Usually, the 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 seeds of the plant of various cultivations or weeds and these plants, described plant or weeds such as wheat, rye, barley, oat, paddy rice, corn, dogstail, banana, cotton, soybean, coffee, sugarcane, liane, fruit and ornamental plants, and vegetables such 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 wherein agricultural chemicals is the agricultural chemicals that can give the plant health effect.

The present invention also comprises a kind of method of controlling undesired plant growth, and described method comprises that the agrochemical formulation of the present invention that makes herbicidally effective amount acts on plant, their growing environment or the seed of described plant.Usually, the veteran can select suitable agriculturally active ingredients with control undesired plant growth, for example weed killer herbicide.Therefore, preparaton of the present invention is suitable for controlling in the useful plant, the common noxious plant in crops or the perennial crops particularly, described crops such as oat, barley, millet, corn, paddy rice, wheat, sugarcane, cotton, rape, flax, lentil, sugar beet, tobacco, sunflower and soybean.Especially, crops are rice crop.The growth of control undesired plants should be understood to refer to eliminate weeds.Weeds should be understood to refer to that with its wideest implication all are grown in those plants in the place of not expecting their growths.

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 foliage applying, for example the mode by dusting; Perhaps described mixture is applied on seed, rice shoot or the plant.

Another embodiment of the invention comprises to be handled soil, before with described plant seeding (for example, mode by soil pouring) or afterwards or before or after described plant emerges, for example by dusting mode or other modes described mixture is imposed on soil.

According to the variant that soil is used, another theme of the present invention is a kind of by applying, and particularly is applied to the mode in the drilling machine, the method that soil is handled.

According to the variant that soil is used, another theme of the present invention is to handle for ditch dug with a plow, and it comprises solid or liquid adjustments be applied to broadcasts in the seed-bearing exposed ditch dug with a plow, perhaps seed and preparaton is applied in the exposed ditch dug with a plow simultaneously.

In preferred embodiment, the granular preparaton of agricultural chemicals is used for antagonism rice grub and disease.This normally finishes in the following way: described granular preparaton is added in the aqueous medium of paddy growth, typically be in adding paddy field water either or the raising rice seedlings case.

The present invention is described further with the embodiment by hereinafter, but be not subjected to the restriction of these embodiment.

EmbodimentAbbreviation

The ai active component

AMPS 4-acrylamido-2-methyl isophthalic acid-propane sulfonic acid

DMAc N, the N-dimethylacetylamide

The GPC gel permeation chromatography

H hour

The ha hectare

The LA lauryl acrylate

The MAA methacrylic acid

The MMA methyl methacrylate

NaOH sodium hydroxide

The PAA polyacrylic acid

PEG6000 polyethylene glycol, molecular weight are 6000g/mol

The PMMA polymethyl methacrylate

POEA acrylic acid phenoxy group ethyl ester

The PVA polyvinyl alcohol

T-BPPiv crosses the neopentanoic acid tert-butyl ester

The VAc vinyl acetate

The VCap caprolactam

The 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, and it contains polyether polyols sulphate, sodium lignin sulfonate, formaldehyde-sodium naphthalene sulfonate 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 with nitrogen, and be heated to temperature in 85 ℃ the reactor.Begin to add charging 1-3 then.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 with mixture back polymerization 2 hours again.Ethanol is removed in distillation, and reactant mixture is carried out steaming.Obtain molecular weight Mn=7,300g/mol, Mw=22, the polymer of 000g/mol (adopt GPC,, measure in DMAc as standard specimen with PMMA).

Polymer b)

Vinyl pyrrolidone/lauryl acrylate copolymer (90/10wt%)

(350g isopropyl alcohol, 10g VP) sucks with nitrogen with initial charge, and is heated to 80 ℃ the interior temperature of reactor.Begin to add charging 1-3 then.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-BPPiv75wt%, 100g isopropyl alcohol).Then with mixture back polymerization 2 hours again.Isopropyl alcohol is removed in distillation, and reactant mixture is carried out steaming.After the distillation, polymer solution is diluted with 200g water.Obtaining the k value is 14, molecular weight Mn=4,400g/mol, Mw=7, the polymer of 600g/mol (adopting GPC, is standard specimen with PMMA, measures in HFIP).

Polymer c)

Vinyl pyrrolidone/acrylic acid phenoxy group ethyl ester copolymer (96/4wt%)

With initial charge (420g water, 0.4g Wako V50,420g ethanol, 1.6g POEA 34.4gVP) sucks with nitrogen, and is heated to temperature in 75 ℃ the reactor.Begin to add charging 1 and 2 then.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 with mixture back polymerization 2 hours again.Ethanol is removed in distillation then, and reactant mixture is carried out steaming.Obtaining the k value is 31, molecular weight Mn=10,400g/mol, Mw=27, the polymer of 600g/mol (adopting GPC, is standard specimen with PMMA, measures in HFIP).

Polymer d)

Methyl methacrylate/methacrylic acid copolymer (25/75wt%)

Initial charge (333.33g isopropyl alcohol, 58.33g charging 1) is sucked with nitrogen, and be heated to temperature in 75 ℃ the reactor.Begin to add charging 1 and 2 then.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).With polymerization behind the mixture 1 hour, add 25gNaOH (40wt%) then then.Isopropyl alcohol is removed in distillation, and reactant mixture is carried out steaming.Obtaining the k value is 18, molecular weight Mn=12,300g/mol, Mw=62, the polymer of 000g/mol (adopting GPC, is standard specimen with PAA, and (pH7) measures in water).

Polymer e)

Vinyl pyrrolidone/lauryl acrylate/4-acrylamido-2-methyl isophthalic acid-propane sulfonic acid sodium/PAA (76/20/2/2wt%)

(250g isopropyl alcohol, 25g VP, 25g LA) sucks with nitrogen with initial charge, and is heated to 75 ℃ the interior temperature of reactor.Then, in 3h, add charging 1 (350g isopropyl alcohol, 165g VP, 25g LA), charging 2 (222g water, 28g AMPS sodium salt, pH are 7) and charging 3 (27g water, 13g PAA).In 4.5h, add charging 4 (47.5g water, 2.5g

V50).After the back polymerization of 1h, add charging 5 (10g water, 0.65g Wako V50), carry out the back polymerization of 2h then.Isopropyl alcohol is removed in distillation then, and reactant mixture is carried out steaming.Obtaining the k value is 22, molecular weight Mn=9,700g/mol, Mw=31, the polymer of 300g/mol (adopting GPC, is standard specimen with PMMA, measures in DMAc).

Polymer f)

PEG6000/ vinyl acetate/caprolactam graft copolymer (13/30/57wt%)

Initial charge (50g butyl acetate, 130g PEG6000,1g charging 3) is sucked with nitrogen, and be heated to temperature in 77 ℃ the reactor.Begin to add charging 1-3 then.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-BPPiv75wt%, 117.25g butyl acetate).With mixture back polymerization 4 hours again, add the 500ml butyl acetate then.Volatile compound is removed in distillation, and reactant mixture is carried out steaming.Obtain molecular weight Mn=44,000g/mol, Mw=140, the polymer of 000g/mol (adopting GPC, is standard specimen with PMMA, measures) in HFIP.

The preparation of embodiment 2A-particle (according to method of the present invention)

Be prepared as follows coating suspension: be that each polymer of 0.5g and the dispersant 1 (sodium lignin sulfonate) of 1.35g are dissolved in the 5.75g water with consumption.In polymer solution, add slurry, described slurry by the 0.5g fluorine worm nitrile in 1.0g water and 0.17g dispersant 2 (

5082) form.

(diameter is 1.2mm by added 5g above-mentioned coating solution to be in the 100mL flask 47.5g particle under stirring at room in 5 minutes, length is 1.5-3mm) on, the 47.5g particle is applied, and described particle is made of the synthetic precipitated silica of 94wt% clay, 2.0wt% polyvinyl alcohol and 4.0wt%.

With the wet granular that obtains under 60 ℃ in baking oven dry 10 minutes.In an identical manner remaining above-mentioned coating suspension is joined in the dried granules, and following dry 60 minutes at 60 ℃ in baking oven again.

The particle of the coating that acquisition is made of polymer, 2.7wt% dispersant 1,1wt% fluorine worm nitrile and the 0.3wt% dispersant 2 of the synthetic precipitated silica of 89.3wt% clay, 1.9wt%PVA, 3.8wt%, 1wt% (wt% be based on initial substance calculate).

Embodiment 2B-does not contain the preparation (Comparative Examples does not adopt method of the present invention) of the particle of polymer

The particle that does not contain polymer in contrast according to the step preparation of embodiment 2A.Adopt identical particle and compound, and adopted identical concentration.Obtained the particle that the surfactant by the synthetic precipitated silica of 90.3wt% clay, 1.9wt%PVA, 3.8wt%, 2.7wt% dispersant, 1wt% fluorine worm nitrile and 0.3wt% constitutes (wt% be based on initial substance calculate).

Embodiment 2C – commodity particle (Comparative Examples 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 the comparative example.Described particle is to be made of the grains of sand that are coated with 1wt% fluorine worm nitrile based on gross weight.

The rate of release of embodiment 3-fluorine worm nitrile

In order to determine the fluorine worm nitrile rate of release of described particle, at room temperature the 100mg particle is put into the beaker that 300mL water is housed.Adopt HPLC to measure the concentration of fluorine worm nitrile after 6 hours.The result can be referring to table 1.

Table 1

Particle	Rate of release [mg/l]
		Commodity particle (embodiment 2C, Comparative Examples)	0.07
Do not contain polymer (embodiment 2B, Comparative Examples)	0.83
		Use polymer a) to apply (embodiment 2A)	1.21
Use polymer b) coating (embodiment 2A)	1.16

The result of table 1 shows that by means of coating of the present invention, the rate of release of particle can improve.

The rate of release of fluorine worm nitrile when embodiment 4 – change the content of dispersant

In order to determine the influence of dispersant, under the change dispersant, measured rate of release.In order to carry out these tests, according to the described method of embodiment 2A, adopt polymer c) as polymer, and the content of change dispersant 1 (lignosulfonates), prepared particle.The result can be referring to table 2.As embodiment 2A calculated, the percetage by weight of lignosulfonates was based on the particle of 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
		The coating of (2.7 Comparative Examples does not contain polymer c))	0.72

The result of table 2 shows that the rate of release of fluorine worm nitrile increases along with the increase of dispersant.Rate of release when not containing polymer is littler than dispersant/combination of polymers.This shows that polymer and dispersant have synergistic effect.

The picked-up of embodiment 5-fluorine worm nitrile

In order to determine the amount of the fluorine worm nitrile that plant absorbs, particle is added in the rice, and sowing.The consumption of fluorine worm nitrile is 100 grams/hectare, and this is corresponding to 10kg particle/hectare.After sowing 18 days, the harvesting paddy rice is with the vegetable material homogenizing, with the fluorine worm nitrile content in GC (adopting N-P to detect) and the GC/MS mensuration vegetable material.The result can be referring to table 3.

Table 3

Particle	Fluorine worm nitrile intake (ppm)
		Commodity particle (embodiment 2C, Comparative Examples)	7.0
Do not contain polymer (embodiment 2B, Comparative Examples)	9.7
		Use polymer a) to apply (embodiment 2A)	11.1
Use polymer b) coating (embodiment 2A)	12.7
		Use polymer c) coating (embodiment 2A)	11.0
Use polymer d) coating (embodiment 2A)	10.6
		Use polymer e) coating (embodiment 2A)	10.1

The result of table 3 shows that when applying particle of the present invention, the amount of taking in the fluorine worm nitrile in the plant obviously raises.

The prevention and control of embodiment 6-insect

In order to determine the improvement of insect prevention and control effect, described particle is added into the rice plant that is in transplanting stage (being transplanted to the basin from raising box).The consumption of fluorine worm nitrile is 100 grams/hectare, corresponding to 10kg particle/hectare.

After transplanting 33 days, the water brown plant-hopper is infected described rice plant.After infecting 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 Examples)	33.3
Do not contain polymer (embodiment 2B, Comparative Examples)	50.0
		Use polymer a) to apply (embodiment 2A)	66.7
Use polymer c) coating (embodiment 2A)	86.7

The result of table 4 clearlys show that when adopting the particle of coating of the present invention, insect prevention and control effect has improved.

Claims

1. the inert particle of Tu Fuing, its coating contains at least a polymer, at least a agriculturally active ingredients and at least a dispersant, and wherein said polymer contains with polymerized form:

A) vinyl lactam and

F) monomer of formula (I):

Formula (I)

Wherein

R1 and R2 are H or CH independently ₃,

N is the integer of 1-100.

2. particle as claimed in claim 1, wherein said polymer contains with polymerized form:

A) vinyl pyrrolidone and

F) monomer of formula (I):

Formula (I)

Wherein

R1 and R2 are H or CH independently ₃,

R3 is C ₆-C ₁₀Aryl or C ₇-C ₁₂Aralkyl, it can be by identical or different C ₁-C ₉Alkyl and/or C ₁-C ₅Alkoxy substituent replaces,

N is the integer of 1-10.

3. particle as claimed in claim 1 or 2, wherein among the described inert particle or on or on described coating, exist identical or other active components.

4. as each described particle among the claim 1-3, wherein said dispersant comprises lignosulfonates.

5. as each described particle among the claim 1-4, wherein said inert particle has the density higher than water.

6. as each described particle among the claim 1-5, wherein at least a agriculturally active ingredients is fluorine worm nitrile.

7. a method for preparing each described particle among the claim 1-6 comprises the steps:

(2) handle inert particle with the waterborne compositions of step (1), and

(3) composition of drying steps (2).

8. method as claimed in claim 7, wherein step (2) is carried out under the heat input not having.

9. agrochemical formulation, it contains the inert particle of each described coating among the claim 1-6 or according to the inert particle of the coating of claim 7 or 8 described methods preparations.

10. method of resisting insect and/or plant pathogenic fungi, described method comprise with 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 1-6 of the plant, seed or the soil that infect and effective dose in each described particle or contact according to particle or the described agrochemical formulation of claim 9 that claim 7 or 8 described methods prepare.

11. a method of controlling undesired plant growth, described method comprise each described particle among the claim 1-6 that makes herbicidally effective amount or act on plant, their growing environment or the seed of described plant according to particle or the described agrochemical formulation of claim 9 of claim 7 or 8 described methods preparations.

12. as claim 10 or 11 described methods, wherein said plant is paddy rice.