WO2009095139A2 - Silica dispersion - Google Patents

Silica dispersion Download PDF

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Publication number
WO2009095139A2
WO2009095139A2 PCT/EP2008/068339 EP2008068339W WO2009095139A2 WO 2009095139 A2 WO2009095139 A2 WO 2009095139A2 EP 2008068339 W EP2008068339 W EP 2008068339W WO 2009095139 A2 WO2009095139 A2 WO 2009095139A2
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WO
WIPO (PCT)
Prior art keywords
insecticides
dispersion
acaricides
weight
methyl
Prior art date
Application number
PCT/EP2008/068339
Other languages
French (fr)
Other versions
WO2009095139A3 (en
Inventor
Jochen Scheffler
Wolfgang Lortz
Gabriele Perlet
Original Assignee
Evonik Degussa Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Degussa Gmbh filed Critical Evonik Degussa Gmbh
Priority to EP08871855A priority Critical patent/EP2285741A2/en
Priority to JP2010544606A priority patent/JP2011514312A/en
Publication of WO2009095139A2 publication Critical patent/WO2009095139A2/en
Publication of WO2009095139A3 publication Critical patent/WO2009095139A3/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14Colloidal silica, e.g. dispersions, gels, sols
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds

Definitions

  • the invention relates to a silica dispersion, to a process for the preparation thereof and to the use thereof.
  • Pulverulent hydrophobic silica is used to combat sucking insects, the application taking place by means of dusting (DE 38 35 592) .
  • aqueous dispersions likewise described in DE 38 35 592, which consist of a hydrophobic silica and water, do not exhibit satisfactory stability.
  • US 5 830 512 describes a dispersion in which satisfactory stability is achieved by addition of hydrophilic substances, such as, for example, silicas. However, the active hydrophobic component is through this diluted by a hydrophilic substance. Furthermore, only a very low stability of the dispersion, from hours to a few days, is achieved.
  • hydrophilic substances such as, for example, silicas.
  • EP 1 250 048 describes stabilizing the dispersion of hydrophobic silicon dioxide through gelling additives, such as xanthan gum, sodium alginates or neutralized carboxyvinyl polymers, mixtures of these additives also being possible.
  • a distinct structural viscosity is exhibited when applying by spraying: during the spraying process, the viscosity of the dispersion is relatively low at the shear forces acting on it. After the dispersion drops impact the surface to be coated, the visocity again increases strongly, in order to avoid dripping/running off from in particular vertical surfaces .
  • Example 1 a density of only 0.6 g/ml is specified, i.e. that approximately 40% of the volume consists of air.
  • DE 10 2004 021 532 describes a dispersion which, in addition to water, comprises 0.5 to 20% by weight of hydrophobic silica, 0.01 to 10% by weight of a gelling or viscosity-increasing additive, 0.1 to 1% by weight of a preservative and 0 to 1% by weight of a surface-active agent .
  • This dispersion can be used as insecticide against insects and as acaricide against Arachnids, such as, e.g., mites.
  • the known dispersion has the disadvantage that it loses activity at high air humidity because, e.g., the mites then are not desiccated.
  • the known chemically active pesticides such as insecticides and in particular acaricides (pesticides for combating mites and ticks), are certainly highly active, even at high air humidities; unfortunately, relatively high residues of the pesticides can also be observed however, e.g. in uses in henhouses against the poultry red mite in the chicken and chicken eggs.
  • the object is accordingly to modify the silica dispersion so that the dispersion is active even at high air humidity, without resulting in major formation of organic pesticide residues .
  • a subject-matter of the invention is a dispersion comprising, in addition to water, from 0.5 to 20% by weight of hydrophobic silica, 0.01 to 10% by weight of a gelling or viscosity-increasing additive, 0.1 to 1% by weight of a preservative and 0 to 1% by weight of a surface-active agent, which is characterized in that it comprises, as additional component, at least one pesticide and/or acaracide .
  • the use of the dispersion according to the invention with markedly reduced organic pesticide concentration can furthermore result in a considerable reduction in the residue formation, e.g. with uses in henhouses against the poultry red mite in the chicken and in the egg.
  • the dispersion according to the invention comprises an active pesticide component with a damaging or lethal effect, it is also possible to combat harmful organisms which are resistant to desiccation, be it through a considerably denser surface than with mites or through the sheer size of the harmful organism, in which the surface to volume ratio is markedly smaller in comparison with the relatively small mites. Desiccation accordingly cannot be achieved or cannot be quickly achieved.
  • active substance groups can in particular be used as insecticides or acaricides, some exhibiting both insecticidal and acaricidal properties.
  • EMPC ethiofencarb fenethacarb fenobucarb isoprocarb methiocarb metolcarb mexacarbate promacyl promecarb propoxur trimethacarb XMC xylylcarb • diamide insecticides chlorantraniliprole flubendiamide
  • fluorine insecticides sulfluramid • formamidine insecticides amitraz chlordimeform formetanate formparanate • insect growth regulators o chitin synthesis inhibitors bistrifluron buprofezin chlorfluazuron cyromazine diflubenzuron flucycloxuron flufenoxuron hexaflumuron lufenuron novaluron noviflumuron penfluron teflubenzuron triflumuron o juvenile hormone mimics epofenonane fenoxycarb hydroprene kinoprene methoprene pyriproxyfen triprene o juvenile hormones juvenile hormone I juvenile hormone II juvenile hormone III o moulting hormone agonists chromafenozide halofenozide methoxyfenozide tebufenozide o moulting hormones ⁇ -ecdysone ecdysterone o
  • organochlorine insecticides bromo-DDT camphechlor DDT pp '-DDT ethyl-DDD HCH gamma-HCH lindane methoxychlor pentachlorophenol TDE o cyclodiene insecticides aldrin bromocyclen chlorbicyclen chlordan chlordecone dieldrin dilor endosulfan endrin
  • organophosphorus insecticides o organophosphate insecticides bromfenvinfos chlorfenvinphos crotoxyphos dichlorvos dicrotophos dimethylvinphos fospirate heptenophos methocrotophos mevinphos monocrotophos naled naftalofos phosphamidon propaphos TEPP tetrachlorvinphos organothiophosphate insecticides dioxabenzofos fosmethilan phenthoate ⁇ aliphatic organothiophosphate insecticides acethion amiton cadusafos chlorethoxyfos chlormephos demephion demephion-0 demephion-S demeton demeton-0 demeton-S demeton-methyl demeton-0-methyl demeton-S-methyl demeton-S-methylsulphon disulfoton ethion ethoprophos
  • IPSP isothioate malathion methacrifos oxydemeton-methyl oxydeprofos oxydisulfoton phorate sulfotep terbufos thiometon ⁇ aliphatic amide organothiophosphate insecticides amidithion cyanthoate dimethoate ethoate-methyl formothion mecarbam omethoate prothoate sophamide vamidothion
  • pyrethroid insecticides o pyrethroid ester insecticides acrinathrin allethrin bioallethrin barthrin bifenthrin bioethanomethrin cyclethrin cycloprothrin cyfluthrin beta-cyfluthrin cyhalothrin gamma-cyhalothrin lambda-cyhalothrin cypermethrin alpha-cypermethrin beta-cypermethrin theta-cypermethrin zeta-cypermethrin cyphenothrin deltamethrin dimefluthrin dimethrin empenthrin fenfluthrin fenpirithrin fenpropathrin fenvalerate esfenvalerate flucythrinate fluvalinate tau-fluvalinate furethrin imiprothrin metoflu
  • antibiotic insecticides allosamidin thuringiensin o macrocyclic lactone insecticides ⁇ avermectin insecticides abamectin doramectin emamectin eprinomectin ivermectin selamectin
  • organotin acaricides azocyclotin cyhexatin fenbutatin oxide
  • antibiotic acaricides nikkomycins thuringiensin o macrocyclic lactone acaricides tetranactin ⁇ avermectin acaricides abamectin doramectin eprinomectin ivermectin selamectin
  • the proportion of water can be from 68 to 99.4% by weight.
  • the specific density of the dispersion can be greater than 0.6 g/ml, preferably from 0.7 to 1.02 g/ml .
  • Use may be made, as hydrophobic silica, of a pyrogenically prepared hydrophobized silica. It can exhibit a BET surface of 20 to 600 m 2 /g.
  • the gelling or viscosity-increasing additive can be a biopolymer, such as, for example, xanthan gum, sodium alginate, locust bean flour, pectin, agar, carrageenans, alginates and/or neutralized carboxyvinyl polymers, or mixtures of these substances.
  • Use may be made, as preservatives, of preservatives approved for foods.
  • These can be: sorbic acid, sodium sorbate, potassium sorbate, calcium sorbate, benzoic acid, sodium benzoate, potassium benzoate, calcium benzoate, PHB ethyl ester, PHB ethyl ester sodium salt, PHB propyl ester, PHB propyl ester sodium salt, PHB methyl ester, PHB methyl ester sodium salt, sulphur dioxide, sodium sulphite, sodium hydrogensulphite, sodium disulphite, potassium disulphite, calcium disulphite, calcium hydrogensulphite, biphenyl, ortho-phenylphenol, sodium ortho-phenylphenolate, thiabendazole, nisin, natamycin, formic acid, sodium formate, calcium formate, hexamethylenetetramine, dimethyl dicarbonate, propionic acid, sodium propionate, calcium propionate, or potassium propionate
  • nitrates nitrites
  • carbon dioxide nitrites
  • chlorine nitrites
  • Use may be made, as surface-active agents, of ionic, nonionic and anionic surfactants.
  • An additional subject-matter of the invention is a process for the preparation of the dispersion according to the invention, which is characterized in that the individual components are dispersed, successively or together, in the water and, in this connection, the individual components are deaerated before and/or during the addition or the dispersion is deaerated during the individual dispersing stages. Residual dispersed air still present can finally be removed by further mixing under vacuum.
  • the deaerating can be carried out by means of application of vacuum.
  • a stable and active dispersion can be achieved which does not comprise extensive amounts of air.
  • This deaerated dispersion can be obtained by the dispersing of previously deaerated hydrophobic SiC>2.
  • a subsequent deaerating of the dispersions is admittedly possible technically but can only be achieved with great effort due to the increased viscosity of the homogeneous phase water (gelling agent as additive) .
  • At least the largest possible portion of the air which can be dispersed can be removed by deaeration measures before or during the dispersing.
  • any dispersing process is suitable which either makes possible prior deaerating of the powder to be dispersed or prevents air from being dispersed during the dispersing.
  • One embodiment of the deaerating and dispersing is the use of a vacuum dissolver.
  • water and the gelling additive to be briefly predispersed, for the entire amount of hydrophobic SiC>2 to be then added without stirring to the surface of the solution, for the mixture to be evacuated and only then for dispersing of the hydrophobic SiC>2 to be begun.
  • a PSI Mix® from Netzsch can also manage this deaerating of the powder.
  • deaerating units such as the Netzsch DA-VS vacuum deaerator from Netzsch, a vacuum thin-film rotation method.
  • the dispersion according to the invention can be used, for example, as pesticide or acaricide against house dust mite: Dermatophagoides pteronyssinus poultry red mite: Dermanyssus gallinae red flour beetle: Tribolium castaneum granary weevil: Sitophilus granarius

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Plant Pathology (AREA)
  • Environmental Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Silicon Compounds (AREA)

Abstract

Dispersion comprising, in addition to water, from 0.5 to 20% by weight of hydrophobic silica, 0.01 to 10% by weight of a gelling or viscosity-increasing additive, 0.1 to 1% by weight of a preservative and 0 to 1% by weight of a surface-active agent, which comprises, as additional component, at least one insecticide and/or acaricide. It is prepared by dispersing the individual components, successively or together, in the water and, in this connection, deaerating the individual components before and/or during the addition or deaerating the dispersion during the individual dispersing stages. The dispersion can be used as insecticide or acaricide.

Description

Silica dispersion
The invention relates to a silica dispersion, to a process for the preparation thereof and to the use thereof.
Pulverulent hydrophobic silica is used to combat sucking insects, the application taking place by means of dusting (DE 38 35 592) .
Disadvantageously, dust development is such that this method of insect control finds little acceptance.
The aqueous dispersions likewise described in DE 38 35 592, which consist of a hydrophobic silica and water, do not exhibit satisfactory stability.
US 5 830 512 describes a dispersion in which satisfactory stability is achieved by addition of hydrophilic substances, such as, for example, silicas. However, the active hydrophobic component is through this diluted by a hydrophilic substance. Furthermore, only a very low stability of the dispersion, from hours to a few days, is achieved.
EP 1 250 048 describes stabilizing the dispersion of hydrophobic silicon dioxide through gelling additives, such as xanthan gum, sodium alginates or neutralized carboxyvinyl polymers, mixtures of these additives also being possible.
These gelling additives bring about, by interaction with the hydrophobic SiC>2 particles and the incorporated air, a marked structural viscosity.
A distinct structural viscosity is exhibited when applying by spraying: during the spraying process, the viscosity of the dispersion is relatively low at the shear forces acting on it. After the dispersion drops impact the surface to be coated, the visocity again increases strongly, in order to avoid dripping/running off from in particular vertical surfaces .
According to EP 1 250 048, in the preparation of the dispersion, in addition to the hydrophobic SiC>2 particles to be dispersed, large amounts of air are incorporated.
With the known dispersion processes, this cannot be avoided without the use of wetting surfactants and antifoaming agents. Thus, in Example 1, a density of only 0.6 g/ml is specified, i.e. that approximately 40% of the volume consists of air.
In order to achieve a satisfactory activity, a minimum weight has to be applied to the surfaces to be sprayed. If, per spraying operation, only approximately 60% of the volume of the spraying appliances can be used, this represents a significant reduction in the effectiveness.
Disadvantageously, the transportation, packaging and waste disposal costs of the required packaging are higher by this proportion .
In addition, during storage, an approximately 40% larger storage space has to be taken into account.
Furthermore, with an air-comprising dispersion, it is not possible to achieve a homogeneous bubble-free coverage of surfaces to be treated.
DE 10 2004 021 532 describes a dispersion which, in addition to water, comprises 0.5 to 20% by weight of hydrophobic silica, 0.01 to 10% by weight of a gelling or viscosity-increasing additive, 0.1 to 1% by weight of a preservative and 0 to 1% by weight of a surface-active agent .
This dispersion can be used as insecticide against insects and as acaricide against Arachnids, such as, e.g., mites. The term "pesticide", from Latin pestis = epidemic, caedere = to kill, is a term for chemical substances which kill or expel troublesome or damaging organisms or restrict their germination, growth or reproduction, also including insecticides and acaricides.
The known dispersion has the disadvantage that it loses activity at high air humidity because, e.g., the mites then are not desiccated.
The known chemically active pesticides, such as insecticides and in particular acaricides (pesticides for combating mites and ticks), are certainly highly active, even at high air humidities; unfortunately, relatively high residues of the pesticides can also be observed however, e.g. in uses in henhouses against the poultry red mite in the chicken and chicken eggs.
The object is accordingly to modify the silica dispersion so that the dispersion is active even at high air humidity, without resulting in major formation of organic pesticide residues .
This object is achieved through the subject-matter of the invention.
A subject-matter of the invention is a dispersion comprising, in addition to water, from 0.5 to 20% by weight of hydrophobic silica, 0.01 to 10% by weight of a gelling or viscosity-increasing additive, 0.1 to 1% by weight of a preservative and 0 to 1% by weight of a surface-active agent, which is characterized in that it comprises, as additional component, at least one pesticide and/or acaracide .
An essential protective function of the surface of the insects, such as, for example, of the mites, is removed or weakened by the defatting or dewaxing action of the hydrophobic silica. Consequently, organic pesticide active substances can more easily and more quickly penetrate into the insect, in order to develop their action therein even at high air humidities. Since the protecting fatty or waxy layer has now been removed, the damaging or lethal action of the organic pesticide active substances can already be achieved with considerably lower concentrations.
The use of the dispersion according to the invention with markedly reduced organic pesticide concentration can furthermore result in a considerable reduction in the residue formation, e.g. with uses in henhouses against the poultry red mite in the chicken and in the egg.
Since the dispersion according to the invention comprises an active pesticide component with a damaging or lethal effect, it is also possible to combat harmful organisms which are resistant to desiccation, be it through a considerably denser surface than with mites or through the sheer size of the harmful organism, in which the surface to volume ratio is markedly smaller in comparison with the relatively small mites. Desiccation accordingly cannot be achieved or cannot be quickly achieved.
The following active substance groups can in particular be used as insecticides or acaricides, some exhibiting both insecticidal and acaricidal properties.
Organic insecticides
• botanical insecticides anabasine azadirachtin d-limonene nicotine pyrethrins cinerins cinerin I cinerin II jasmolin I jasmolin II pyrethrin I pyrethrin II rotenone ryania sabadilla carbamate insecticides bendiocarb carbaryl o benzofuranyl methylcarbamate insecticides benfuracarb carbofuran carbosulfan decarbofuran furathiocarb o dimethylcarbamate insecticides dimetan dimetilan hyquincarb pirimicarb o oxime carbamate insecticides alanycarb aldicarb aldoxycarb butocarboxim butoxycarboxim methomyl nitrilacarb oxamyl tazimcarb thiocarboxime thiodicarb thiofanox o phenyl methylcarbamate insecticides allyxycarb aminocarb bufencarb butacarb carbanolate cloethocarb dicresyl dioxacarb
EMPC ethiofencarb fenethacarb fenobucarb isoprocarb methiocarb metolcarb mexacarbate promacyl promecarb propoxur trimethacarb XMC xylylcarb • diamide insecticides chlorantraniliprole flubendiamide
• dinitrophenol insecticides dinex dinoprop dinosam DNOC
• fluorine insecticides sulfluramid • formamidine insecticides amitraz chlordimeform formetanate formparanate • insect growth regulators o chitin synthesis inhibitors bistrifluron buprofezin chlorfluazuron cyromazine diflubenzuron flucycloxuron flufenoxuron hexaflumuron lufenuron novaluron noviflumuron penfluron teflubenzuron triflumuron o juvenile hormone mimics epofenonane fenoxycarb hydroprene kinoprene methoprene pyriproxyfen triprene o juvenile hormones juvenile hormone I juvenile hormone II juvenile hormone III o moulting hormone agonists chromafenozide halofenozide methoxyfenozide tebufenozide o moulting hormones α-ecdysone ecdysterone o moulting inhibitors diofenolan o precocenes precocene I precocene II precocene III o unclassified insect growth regulators dicyclanil • nereistoxin analogue insecticides bensultap cartap thiocyclam thiosultap • nicotinoid insecticides flonicamid o nitroguanidine insecticides clothianidin dinotefuran imidacloprid thiamethoxam o nitromethylene insecticides nitenpyram nithiazine o pyridylmethylamine insecticides acetamiprid imidacloprid nitenpyram thiacloprid
• organochlorine insecticides bromo-DDT camphechlor DDT pp '-DDT ethyl-DDD HCH gamma-HCH lindane methoxychlor pentachlorophenol TDE o cyclodiene insecticides aldrin bromocyclen chlorbicyclen chlordan chlordecone dieldrin dilor endosulfan endrin
HEOD heptachlor
HHDN isobenzan isodrin kelevan mirex
• organophosphorus insecticides o organophosphate insecticides bromfenvinfos chlorfenvinphos crotoxyphos dichlorvos dicrotophos dimethylvinphos fospirate heptenophos methocrotophos mevinphos monocrotophos naled naftalofos phosphamidon propaphos TEPP tetrachlorvinphos organothiophosphate insecticides dioxabenzofos fosmethilan phenthoate ■ aliphatic organothiophosphate insecticides acethion amiton cadusafos chlorethoxyfos chlormephos demephion demephion-0 demephion-S demeton demeton-0 demeton-S demeton-methyl demeton-0-methyl demeton-S-methyl demeton-S-methylsulphon disulfoton ethion ethoprophos
IPSP isothioate malathion methacrifos oxydemeton-methyl oxydeprofos oxydisulfoton phorate sulfotep terbufos thiometon ■ aliphatic amide organothiophosphate insecticides amidithion cyanthoate dimethoate ethoate-methyl formothion mecarbam omethoate prothoate sophamide vamidothion
5 ■ oxime organothiophosphate insecticides chlorphoxim phoxim phoxim-methyl
■ heterocyclic organothiophosphate 10 insecticides azamethiphos coumaphos coumithoate dioxathion 15 endothion menazon morphothion phosalone pyraclofos 20 pyridaphenthion quinothion
■ benzothiopyran organothiophosphate insecticides dithicrofos 25 thicrofos
■ benzotriazine organothiophosphate insecticides azinphos-ethyl azinphos-methyl
30 ■ isoindole organothiophosphate insecticides dialifos phosmet
■ isoxazole organothiophosphate 35 insecticides isoxathion zolaprofos
■ pyrazolopyrimidine organothiophosphate insecticides
40 chlorprazophos pyrazophos
■ pyridine organothiophosphate insecticides chlorpyrifos chlorpyrifos-methyl
■ pyrimidine organothiophosphate insecticides
5 butathiofos diazinon etrimfos lirimfos pirimiphos-ethyl
10 pirimiphos-methyl primidophos pyrimitate tebupirimfos
■ quinoxaline organothiophosphate 15 insecticides quinalphos quinalphos-methyl
■ thiadiazole organothiophosphate insecticides
20 athidathion lythidathion methidathion prothidathion triazole organothiophosphate 25 insecticides isazofos triazophos
■ phenyl organothiophosphate insecticides azothoate 30 bromophos bromophos-ethyl carbophenothion chlorthiophos cyanophos 35 cythioate dicapthon dichlofenthion etaphos famphur 40 fenchlorphos fenitrothion fensulfothion fenthion fenthion-ethyl 45 heterophos jodfenphos mesulfenfos parathion parathion-methyl phenkapton phosnichlor profenofos prothiofos sulprofos temephos trichlormetaphos-3 trifenofos o phosphonate insecticides butonate trichlorfon o phosphonothioate insecticides mecarphon
■ phenyl ethylphosphonothioate insecticides fonofos trichloronat
■ phenyl phenylphosphonothioate insecticides cyanofenphos
EPN leptophos o phosphoramidate insecticides crufornate fenamiphos fosthietan mephosfolan phosfolan pirimetaphos o phosphoramidothioate insecticides acephate isocarbophos isofenphos methamidophos propetamphos o phosphorodiamide insecticides dimefox mazidox mipafox schradan diazine insecticides indoxacarb
• oxadiazolone insecticides metoxadiazone
• phthalimide insecticides dialifos phosmet tetramethrin
• pyrazole insecticides chlorantraniliprole dimetilan tebufenpyrad tolfenpyrad o phenylpyrazole insecticides acetoprole ethiprole fipronil pyraclofos pyrafluprole pyriprole vaniliprole
• pyrethroid insecticides o pyrethroid ester insecticides acrinathrin allethrin bioallethrin barthrin bifenthrin bioethanomethrin cyclethrin cycloprothrin cyfluthrin beta-cyfluthrin cyhalothrin gamma-cyhalothrin lambda-cyhalothrin cypermethrin alpha-cypermethrin beta-cypermethrin theta-cypermethrin zeta-cypermethrin cyphenothrin deltamethrin dimefluthrin dimethrin empenthrin fenfluthrin fenpirithrin fenpropathrin fenvalerate esfenvalerate flucythrinate fluvalinate tau-fluvalinate furethrin imiprothrin metofluthrin permethrin biopermethrin transpermethrin phenothrin prallethrin profluthrin pyresmethrin resmethrin bioresmethrin cismethrin tefluthrin terallethrin tetramethrin tralomethrin transfluthrin o pyrethroid ether insecticides etofenprox flufenprox halfenprox protrifenbute silafluofen
• pyrimidinamine insecticides flufenerim pyrimidifen
• Pyrrole insecticides chlorfenapyr
• tetramic acid insecticides spirotetramat
• tetronic acid insecticides spiromesifen
• thiazole insecticides clothianidin thiamethoxam
• thiazolidine insecticides tazimcarb thiacloprid • thiourea insecticides diafenthiuron
• urea insecticides flucofuron sulcofuron see also chitin synthesis inhibitors
• antibiotic insecticides allosamidin thuringiensin o macrocyclic lactone insecticides ■ avermectin insecticides abamectin doramectin emamectin eprinomectin ivermectin selamectin
■ milbemycin insecticides lepimectin milbemectin milbemycin oxime moxidectin
■ spinosyn insecticides spinetoram spinosad
• unclassified insecticides closantel copper naphthenate crotamiton EXD fenazaflor fenoxacrim hydramethylnon isoprothiolane malonoben metaflumizone nifluridide pyridaben pyridalyl pyrifluquinazon rafoxanide triarathene triazamate
Organic acaricides
• bridged diphenyl acaricides azobenzene benzoximate benzyl benzoate bromopropylate chlorbenside chlorfenethol chlorfenson chlorfensulphide chlorobenzilate chloropropylate cyflumetofen
DDT dicofol diphenyl sulfone dofenapyn fenson fentrifanil fluorbenside proclonol tetradifon tetrasul
• carbamate acaricides benomyl carbanolate carbaryl carbofuran methiocarb metolcarb promacyl propoxur o oxime carbamate acaricides aldicarb butocarboxim oxamyl thiocarboxime thiofanox
• coarbazate acaricides bifenazate • dinitrophenol acaricides binapacryl dinex dinobuton dinocap dinocap-4 dinocap-6 dinocton dinopenton dinosulfon dinoterbon
DNOC
• formamidine acaricides amitraz chlordimeform chloromebuform formetanate formparanate
• mite growth regulators clofentezine cyromazine diflovidazin dofenapyn fluazuron flubenzimine flucycloxuron flufenoxuron hexythiazox
• organochlorine acaricides bromocyclen camphechlor DDT dienochlor endosulfan lindane • organophosphorus acaricides o organophosphate acaricides chlorfenvinphos crotoxyphos dichlorvos heptenophos mevinphos monocrotophos naled TEPP tetrachlorvinphos organothiophosphate acaricides amidithion amiton azinphos-ethyl azinphos-methyl azothoate benoxafos bromophos bromophos-ethyl carbophenothion chlorpyrifos chlorthiophos coumaphos cyanthoate demeton demeton-0 demeton-S demeton-methyl demeton-O-methyl demeton-S-methyl demeton-S-methylsulphon dialifos diazinon dimethoate dioxathion disulfoton endothion ethion ethoate-methyl formothion malathion mecarbam methacrifos omethoate oxydeprofos oxydisulfoton parathion phenkapton phorate phosalone phosmet phoxim pirimiphos-methyl prothidathion prothoate pyrimitate quinalphos quintiofos sophamide sulfotep thiometon triazophos trifenofos vamidothion o phosphonate acaricides trichlorfon o phosphoramidothioate acaricides isocarbophos methamidophos propetamphos o phosphorodiamide acaricides dimefox mipafox schradan
• organotin acaricides azocyclotin cyhexatin fenbutatin oxide
• phenylsulphamide acaricides dichlofluanid
• phthalimide acaricides dialifos phosmet
• pyrazole acaricides cyenopyrafen fenpyroximate tebufenpyrad o phenylpyrazole acaricides acetoprole fipronil vaniliprole • pyrethroid acaricides o pyrethroid ester acaricides acrinathrin bifenthrin cyhalothrin cypermethrin alpha-cypermethrin fenpropathrin fenvalerate flucythrinate flumethrin fluvalinate tau-fluvalinate permethrin o pyrethroid ether acaricides halfenprox
• pyrimidinamine acaricides pyrimidifen
• pyrrole acaricides chlorfenapyr
• quinoxaline acaricides chinomethionat thioquinox
• sulphite ester acaricides propargite
• tetronic acid acaricides spirodiclofen • tetrazine acaricides clofentezine diflovidazin
• thiazolidine acaricides flubenzimine hexythiazox
• thiocarbamate acaricides fenothiocarb
• thiourea acaricides chloromethiuron diafenthiuron
• antibiotic acaricides nikkomycins thuringiensin o macrocyclic lactone acaricides tetranactin ■ avermectin acaricides abamectin doramectin eprinomectin ivermectin selamectin
■ milbemycin acaricides milbemectin milbemycin oxime moxidectin
• unclassified acaricides acequinocyl amidoflumet arsenous oxide closantel crotamiton disulfiram etoxazole fenazaflor fenazaquin fluacrypyrim fluenetil mesulfen
MNAF nifluridide pyridaben sulfiram sulfluramid sulfur triarathene
The proportion of water can be from 68 to 99.4% by weight.
The specific density of the dispersion can be greater than 0.6 g/ml, preferably from 0.7 to 1.02 g/ml .
Use may be made, as hydrophobic silica, of a pyrogenically prepared hydrophobized silica. It can exhibit a BET surface of 20 to 600 m2/g.
The gelling or viscosity-increasing additive can be a biopolymer, such as, for example, xanthan gum, sodium alginate, locust bean flour, pectin, agar, carrageenans, alginates and/or neutralized carboxyvinyl polymers, or mixtures of these substances.
Use may be made, as preservatives, of preservatives approved for foods. These can be: sorbic acid, sodium sorbate, potassium sorbate, calcium sorbate, benzoic acid, sodium benzoate, potassium benzoate, calcium benzoate, PHB ethyl ester, PHB ethyl ester sodium salt, PHB propyl ester, PHB propyl ester sodium salt, PHB methyl ester, PHB methyl ester sodium salt, sulphur dioxide, sodium sulphite, sodium hydrogensulphite, sodium disulphite, potassium disulphite, calcium disulphite, calcium hydrogensulphite, biphenyl, ortho-phenylphenol, sodium ortho-phenylphenolate, thiabendazole, nisin, natamycin, formic acid, sodium formate, calcium formate, hexamethylenetetramine, dimethyl dicarbonate, propionic acid, sodium propionate, calcium propionate, or potassium propionate .
In addition, the following are approved: nitrates, nitrites, carbon dioxide, chlorine and chlorine dioxide .
Use may be made, as surface-active agents, of ionic, nonionic and anionic surfactants.
An additional subject-matter of the invention is a process for the preparation of the dispersion according to the invention, which is characterized in that the individual components are dispersed, successively or together, in the water and, in this connection, the individual components are deaerated before and/or during the addition or the dispersion is deaerated during the individual dispersing stages. Residual dispersed air still present can finally be removed by further mixing under vacuum.
In one embodiment of the invention, the deaerating can be carried out by means of application of vacuum.
Surprisingly, according to the invention, a stable and active dispersion can be achieved which does not comprise extensive amounts of air. This deaerated dispersion can be obtained by the dispersing of previously deaerated hydrophobic SiC>2. A subsequent deaerating of the dispersions is admittedly possible technically but can only be achieved with great effort due to the increased viscosity of the homogeneous phase water (gelling agent as additive) . At least the largest possible portion of the air which can be dispersed can be removed by deaeration measures before or during the dispersing.
In principle, any dispersing process is suitable which either makes possible prior deaerating of the powder to be dispersed or prevents air from being dispersed during the dispersing.
One embodiment of the deaerating and dispersing is the use of a vacuum dissolver. In this connection, it is possible for water and the gelling additive to be briefly predispersed, for the entire amount of hydrophobic SiC>2 to be then added without stirring to the surface of the solution, for the mixture to be evacuated and only then for dispersing of the hydrophobic SiC>2 to be begun.
A PSI Mix® from Netzsch can also manage this deaerating of the powder.
In order to remove residual microbubbles, use may be made of deaerating units, such as the Netzsch DA-VS vacuum deaerator from Netzsch, a vacuum thin-film rotation method.
The dispersion according to the invention can be used, for example, as pesticide or acaricide against house dust mite: Dermatophagoides pteronyssinus poultry red mite: Dermanyssus gallinae red flour beetle: Tribolium castaneum granary weevil: Sitophilus granarius
Indian meal moth: Plodia interpunctella greenbug: Schizaphis graminum

Claims

Patent claims
1. Dispersion comprising, in addition to water, from 0.5 to 20% by weight of hydrophobic silica, 0.01 to 10% by weight of a gelling or viscosity-increasing additive, 0.1 to 1% by weight of a preservative and 0 to 1% by weight of a surface-active agent, characterized in that it comprises, as additional component, at least one insecticide and/or acaricide.
2. Process for the preparation of the dispersion according to Claim 1, characterized in that the individual components are dispersed, successively or together, in the water, in which connection the individual components are deaerated before and/or during the addition or the dispersion is deaerated during the individual dispersing stages, and residual dispersed air still present is finally removed by further mixing under vacuum.
3. Process for combating insects, characterized in that a dispersion according to Claim 1 is used.
PCT/EP2008/068339 2008-01-30 2008-12-30 Silica dispersion WO2009095139A2 (en)

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Applications Claiming Priority (2)

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DE102008006683A DE102008006683A1 (en) 2008-01-30 2008-01-30 silica dispersion

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WO2009095139A3 WO2009095139A3 (en) 2009-11-19

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Cited By (1)

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WO2009095141A2 (en) * 2008-01-31 2009-08-06 Evonik Degussa Gmbh Silicon dioxide dispersion

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DE102010052152A1 (en) 2010-11-22 2012-05-24 Universität Hohenheim Apparatus and method for controlling avian parasites
JPWO2015105128A1 (en) * 2014-01-08 2017-03-23 アース製薬株式会社 Bed bug control agent, bed bug control composition, and bed bug control method

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GB1476633A (en) * 1973-10-03 1977-06-16 Unilever Ltd Dentifrice composition
DE3835592A1 (en) * 1988-10-19 1990-04-26 Degussa INSECTICIDES
AU2884692A (en) 1992-11-03 1994-05-24 Sil-Tech International Corporation Insect control compositions
JP4632614B2 (en) 1999-11-18 2011-02-16 ビーエイエスエフ ピーエルシー Insecticidal composition comprising aerated gel containing hydrophobic silica
AU781242B2 (en) * 2000-04-27 2005-05-12 Basf Plc Biocidal compositions comprising an aerated gel containing hydrophobic silica
DE102004021532A1 (en) * 2004-05-03 2005-12-08 Degussa Ag Dispersion with insecticidal activity

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009095141A2 (en) * 2008-01-31 2009-08-06 Evonik Degussa Gmbh Silicon dioxide dispersion
WO2009095141A3 (en) * 2008-01-31 2010-09-23 Evonik Degussa Gmbh Silicon dioxide dispersion

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JP2011514312A (en) 2011-05-06
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