Patent Application
20070066489
The present invention relates to new, oil-based suspension concentrates of agrochemical active compounds, a process for the preparation of these formulations, and their use for the application of the active compounds contained.
Numerous anhydrous suspension concentrates of agrochemical active compounds have already been disclosed. Thus, EP-A 789,999 describes formulations of this type which, in addition to active compound and oil, contain a mixture of various surfactants—among them also those which serve as penetration promoters—and a hydrophobized alumo-layer silicate as a thickening agent. The stability of these preparations is good. It is disadvantageous, however, that a thickening agent is compulsorily present, because the preparation is more complicated on account of this. Moreover, the thickening agent in each case absorbs some of the amount of penetration promoter added, which is therefore not available for its real function.
Furthermore, U.S. Pat. No. 6,165,940 already discloses non-aqueous suspension concentrates in which, apart from agrochemical active compound, penetration promoter and surfactant or surfactant mixture, an organic solvent is present, suitable solvents of this type also being paraffin oil or vegetable oil esters. The biological activity and the stability of the spray liquors which can be prepared from these formulations by diluting with water, however, is not always adequate.
This invention relates to new oil-based suspension concentrates that consist of
It has furthermore been found that the oil-based suspension concentrates according to the invention can be prepared by mixing
Finally, it has been found that the oil-based suspension concentrates according to the invention are very highly suitable for the application of the agrochemical active compounds contained to plants and/or their habitat.
It is to be indicated as extremely surprising that the oil-based suspension concentrates according to the invention have a very good stability, although they contain no thickening agent. It is also unexpected that they exhibit a markedly better biological activity than the previously known formulations having the most similar composition. Otherwise, the oil-based suspension concentrates according to the invention, with respect to their activity, surprisingly also excel analogous preparations which, in addition to the other components, contain either only penetration promoter or only vegetable oil. Such a synergistic effect could not be foreseen on the basis of the prior art described above.
The oil-based suspension concentrates according to the invention are also distinguished by a number of advantages. Thus their preparation is less complicated than the preparation of corresponding formulations in which thickening agents are present. It is furthermore advantageous that on diluting the concentrates according to the invention with water neither a significant formation of cream nor a troublesome formation of flocks occurs, which is frequently the case with corresponding previously known preparations. Finally, the formulations according to the invention favor the biological activity of the active components contained, so that in comparison to conventional preparations either a higher activity is achieved or less active compound is necessary.
Solid, agrochemical active compounds are to be understood in the present composition as meaning all substances customary for plant treatment, whose melting point is above 20° C. Fungicides, bactericides, insecticides, acaricides, nematicides, molluscicides, herbicides, plant growth regulators, plant nutrients and repellents may preferably be mentioned.
Examples of fungicides that may be mentioned are 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2′,6′-dibromo-2-methyl-4′-tri-fluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide; (E)-2-methoximino-N-methyl-2-(2-phenoxyphenyl)-acetamide; 8-hydroxyquinoline sulphate; methyl (E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate; methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]-acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polysulphide, captafol, captan, carbendazim, carboxin, quino-methionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram, carpropamide, dichlorophen, diclobutrazole, dichlofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fthalide, fuberidazole, furalaxyl, furmecyclox, fenhexamide, guazatine, hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodion, isoprothiolan, iprovalicarb, kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxine, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxine, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB), quinoxyfen, sulphur and sulphur preparations, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichiamide, tricyclazole, tridemorph, triflumizole, triforin, triticonazole, trifloxystrobin, validamycin A, vinclozolin, zineb, ziram, and 2-[2-(1-chloro-cyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione.
Examples of bactericides that may be mentioned are bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinon, furancarboxylic acid, oxytetracycline, probenazole, strepto-mycin, tecloftalam, and copper sulphate and other copper preparations.
Examples of insecticides, acaricides, and nematicides that may be mentioned are abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, 4-bromo-2-(4-chlorphenyl)-1-(ethoxymethyl)-5-(tri-fluoromethyl)-1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxine, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chloretoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-ethaneimidamide, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazin, deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflu-benzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton, emamectin, esfen valerate, ethiofencarb, ethion, ethofenprox, etho-prophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, feno-thiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, nitenpyram, omethoate, oxamyl, oxydemethon M, oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate, phosalon, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenophos, promecarb, propaphos, propoxur, prothiophos, prothoate, pymetrozine, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, salithion, sebufos, silafluofen, sulfotep, sulprofos, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiacloprid, thiafenox, thiamethoxam, thiodicarb, thiofanox, thiomethon, thionazine, thuringiensin, tralomethrin, transfluthrin, triarathen, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, and zetamethrin.
Examples of molluscicides that may be mentioned are metaldehyde and methiocarb.
Examples of herbicides that may be mentioned are anilides, such as, for example, diflufenican and propanil; arylcarboxylic acids, such as, for example, dichlorpicolinic acid, dicamba, and picloram; aryloxyalkanoic acids, such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP, and triclopyr; aryloxy-phenoxy-alkanoic acid esters, such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl, and quizalofop-ethyl; azinones, such as, for example, chloridazon and norflurazon; carbamates, such as, for example, chlorpropham, desmedipham, phenmedipham, and propham; chloroacetanilides, such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor, and propachlor; dinitroanilines, such as, for example, oryzalin, pendimethalin, and trifluralin; diphenyl ethers, such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen, and oxyfluorfen; ureas, such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron, and methabenzthiazuron; hydroxylamines, such as, for example, alloxydim, clethodim, cycloxydim, sethoxydim, and tralkoxy-dim; imidazolinones, such as, for example, imazethapyr, imazamethabenz, imazapyr, and imazaquin; nitriles, such as, for example, bromoxynil, dichlobenil, and ioxynil; oxyacetamides, such as, for example, mefenacet; sulphonylureas, such as, for example, amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron, and tribenuron-methyl; thiocarbamates, such as, for example, butylate, cycloate, diallate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb, and triallate; triazines, such as, for example, atrazine, cyanazine, simazine, simetryne, terbutryne, and terbutylazine; triazinones, such as, for example, hexazinon, metamitron, and metribuzin; others, such as, for example, aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluoro-chloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate, and tridiphane. In addition, 4-amino-N-(1,1-dimethylethyl)-4,5-dihydro-3-(1-methylethyl)-5-oxo-1H-1,2,4-triazole-1-carboxamide and 2-((((4,5-dihdydro-4-methyl-5-oxo-3-propoxy-1H -1,2,4-triazol-1-yl)carbonyl)amino)sulfonyl) methyl benzoate may be mentioned.
Examples of plant growth regulators that may be mentioned are chlorocholine chloride and ethephon.
Examples of plant nutrients that may be mentioned are customary inorganic or organic fertilizers for supplying plants with macro- and/or micronutrients.
Examples of repellents that may be mentioned are diethyl-tolylamide, ethylhexanediol, and buto-pyronoxyl.
Suitable penetration promoters in the present composition are all those substances that are customarily employed in order to improve the penetration of agrochemical active compounds into plants. Alkanol alkoxylates of the formula
R—O-(-AO)mH (I)
in which
A particularly preferred group of penetration promoters are alkanol alkoxylates of the formula
R—O-(-EO—)n—H (Ia)
in which
A further particularly preferred group of penetration promoters are alkanol alkoxylates of the formula
R—O-(-EO—)p—(—PO—)q—H (Ib)
in which
A further particularly preferred group of penetration promoters are alkanol alkoxylates of the formula
R—O—(—PO—)r-(EO—)s—H (Ic)
in which
A further particularly preferred group of penetration promoters are alkanol alkoxylates of the formula
CH3—(CH2)t—CH2—O—(—CH2—CH2—O—)u—H (Id)
in which
In the formulas indicated beforehand R preferably represents butyl, i-butyl, n-pentyl, i-pentyl, neopentyl, n-hexyl, i-hexyl, n-octyl, i-octyl, 2-ethyl-hexyl, nonyl, i-nonyl, decyl, n-dodecyl, i-dodecyl, lauryl, myristyl, i-tridecyl, trimethyl-nonyl, palmityl, stearyl, or eicosyl.
An example of an alkanol alkoxylate of the formula (Ib) which may be mentioned is 2-ethyl-hexyl alkoxylate of formula (Ib-1)
in which
An example of an alkanol alkoxylate of the formula (Ic) which may be mentioned is 2-ethyl-hexyl alkoxylate of formula (Ic-1)
in which
Particularly preferred alkanol alkoxylates of the formula (Id) are compounds of this formula in which
The above formulas give a general definition of the alkanol alkoxylates. These substances are mixtures of substances of the type indicated having different chain lengths. For the indices, therefore, average values are calculated that can also differ from integers.
By way of example, an alkanol alkoxylate of the formula (Id) may be mentioned, in which
The alkanol alkoxylates of the formulas indicated are known or can be prepared by known methods (cf. WO 98/35,553, WO 00/35 278, and EP-A 681,865).
Possible vegetable oils are all oils that can customarily be employed in agrochemical agents and can be obtained from plants. By way of example, sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, maize germ oil, cottonseed oil, and soya bean oil may be mentioned.
The oil-based suspension concentrates according to the invention contain at least one non-ionic surfactant or dispersing aid and/or at least one anionic surfactant or dispersing aid.
Suitable non-ionic surfactants or dispersing aids are all substances of this type that can customarily be employed in agrochemical agents. Preferably, polyethylene oxide-polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and/or propylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinyl-pyrrolidone, and copolymers of (meth)acrylic acid and (meth)-acrylic acid esters, alkyl ethoxylates and alkylaryl ethoxylates, which can be optionally phosphated and optionally neutralized with bases (where sorbitol ethoxylates may be mentioned by way of example), and polyoxyalkylenamine derivatives may be mentioned.
Possible anionic surfactants are all substances of this type that can customarily be employed in agrochemical agents. Alkali metal and alkaline earth metal salts of alkylsulphonic acids or alkylarylsulphonic acids are preferred.
A further preferred group of anionic surfactants or dispersing aids are salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of naphthalenesulphonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulphonic acid, phenol-sulphonic acid and formaldehyde, and salts of lignosulphonic acid, which are not very soluble in vegetable oil.
Suitable additives that can be contained in the formulations according to the invention are emulsifiers, antifoam agents, preservatives, antioxidants, colorants, and inert filling materials.
Preferred emulsifiers are ethoxylated nonylphenols, reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethoxylated arylalkylphenols, ethoxylated and propoxylated arylalkylphenols, and sulphated or phosphated arylalkyl ethoxylates or -ethoxy-propoxylates, where sorbitan derivatives, such as polyethylene oxide-sorbitan fatty acid esters and sorbitan fatty acid esters, may be mentioned by way of example.
Suitable antifoam substances are all substances that can customarily be employed in agrochemical agents for this purpose. Silicone oils and magnesium stearate are preferred.
Possible preservatives are all substances that can customarily be employed in agrochemical agents for this purpose. Examples that may be mentioned are Preventol® (Bayer AG) and Proxel®.
Suitable antioxidants are all substances that can customarily be employed in agrochemical agents for this purpose. Butylhydroxytoluene is preferred.
Possible colorants are all substances that can customarily be employed in agrochemical agents for this purpose. Titanium dioxide, carbon black, zinc oxide, blue pigments, and Permanent Red FGR may be mentioned by way of example.
Suitable inert filling materials are all substances that can customarily be employed in agrochemical agents for this purpose and that do not function as thickening agents. Inorganic particles, such as carbonates, silicates, and oxides and organic substances, such as urea-formaldehyde condensates, are preferred. Kaolin, rutile, silica (“highly disperse silicic acid”), silica gels, and natural and synthetic silicates, as well as talc, may be mentioned by way of example.
The content of the individual components can be varied within a wide range in the oil-based suspension concentrates according to the invention. Thus, the concentrations of
The oil-based suspension concentrates according to the invention are prepared by mixing the components with one another in the ratios desired in each case. The sequence in which the constituents are blended with one another is arbitrary. Expediently, the solid components are employed in finely ground state. However, it is also possible firstly to subject the suspension resulting after the blending of the constituents to a coarse grinding and then to a fine grinding so that the average particle size is below 20 μm. Suspension concentrates are preferred in which the solid particles have an average particle size of between 1 and 10 μm.
The temperatures can be varied within a certain range when carrying out the process according to the invention. The process is in general carried out at temperatures between 10° C. and 60° C., preferably between 15° C. and 40° C.
For carrying out the process according to the invention, customary mixing and grinding equipment that is employed for the preparation of agrochemical formulations is suitable.
The oil-based suspension concentrates according to the invention are formulations that remain stable even after relatively long storage at elevated temperatures or in the cold, since no crystal growth is observed. They can be converted into homogeneous spray liquids by dilution with water. These spray liquids are used according to customary methods, i.e., for example, by spraying, watering, or injecting.
The application rate of the oil-based suspension concentrates according to the invention can be varied within a relatively wide range and depends on the particular agrochemical active compounds and on their content in the formulations.
With the aid of the oil-based suspension concentrates according to the invention, agrochemical active compounds can be applied to plants and/or their habitat in a particularly advantageous manner. The agrochemical active compounds contained in this case display a better biological activity than on application in the form of the corresponding conventional formulations.
The invention is illustrated by the following examples.
For the preparation of a suspension concentrate
in which
EO represents —CH2—CH2—O—,
PO represents
and
the numbers 8 and 6 are average values, and 176.8 g of sunflower oil.
After addition is complete, the mixture is stirred at room temperature for a further 10 minutes. The homogeneous suspension resulting in the course of this is firstly subjected to a coarse grinding and then to a fine grinding so that a suspension is obtained in which 90% of the solid particles have a particle size of below 6 μm.
For the preparation of a suspension concentrate
After addition is complete, the mixture is stirred at room temperature for a further 10 minutes. The homogeneous suspension resulting in the course of this is firstly subjected to a coarse grinding and then to a fine grinding so that a suspension is obtained in which 90% of the solid particles have a particle size of below 6 μm.
For the preparation of a suspension concentrate
After addition is complete, the mixture is stirred at room temperature for a further 10 minutes. The homogeneous suspension resulting in the course of this is firstly subjected to a coarse grinding and then to a fine grinding so that a suspension is obtained in which 90% of the solid particles have a particle size of below 6 μm.
For the preparation of a suspension concentrate
After addition is complete, the mixture is stirred at room temperature for a further 10 minutes. The homogeneous suspension resulting in the course of this is firstly subjected to a coarse grinding and then to a fine grinding so that a suspension is obtained in which 90% of the solids particles have a particle size of below 6 μm.
For the preparation of a suspension concentrate
After addition is complete, the mixture is stirred at room temperature for a further 10 minutes. The homogeneous suspension resulting in the course of this is firstly subjected to a coarse grinding and then to a fine grinding so that a suspension is obtained in which 90% of the solid particles have a particle size of below 6 μm.
For the preparation of a suspension concentrate
After addition is complete, the mixture is stirred at room temperature for a further 10 minutes. The homogeneous suspension resulting in the course of this is firstly subjected to a coarse grinding and then to a fine grinding so that a suspension is obtained in which 90% of the solid particles have a particle size of below 6 μm.
For the preparation of a suspension concentrate
After addition is complete, the mixture is stirred at room temperature for a further 10 minutes. The homogeneous suspension resulting in the course of this is firstly subjected to a coarse grinding and then to a fine grinding so that a suspension is obtained in which 90% of the solid particles have a particle size of below 6 μm.
For the preparation of a suspension concentrate
After addition is complete, the mixture is stirred at room temperature for a further 10 minutes. The homogeneous suspension resulting in the course of this is firstly subjected to a coarse grinding and then to a fine grinding so that a suspension is obtained in which 90% of the solid particles have a particle size of below 6 μm.
For the preparation of a suspension concentrate
After addition is complete, the mixture is stirred at room temperature for a further 10 minutes. The homogeneous suspension resulting in the course of this is firstly subjected to a coarse grinding and then to a fine grinding so that a suspension is obtained in which 90% of the solid particles have a particle size of below 6 μm.
Stability Test
For the determination of the stability, 100 g in each case of a suspension concentrate of the composition described in Example 2 are stored for a number of weeks at
−10° C.,
room temperature,
+30° C.,
+40° C.
+54° C.
alternating temperatures (6 hours at −15° C., then 6 hours at +30° C.).
The experimental results are compiled in the following tables.
*Sediment volume = volume of the sediment phase in relation to the total volume of the sample.
**The average particle size which 90% of the solid particles in the oil phase have was measured.
*Sediment volume = volume of the sediment phase in relation to the total volume of the sample.
**The average particle size which 90% of the solid particles in the oil phase have was measured.
*Sediment volume = volume of the sediment phase in relation to the total volume of the sample.
**The average particle size which 90% of the solid particles in the oil phase have was measured.
*Sediment volume = volume of the sediment phase in relation to the total volume of the sample.
**The average particle size which 90% of the solid particles in the oil phase have was measured.
*Sediment volume = volume of the sediment phase in relation to the total volume of the sample.
**The average particle size which 90% of the solid particles in the oil phase have was measured.
*Sediment volume = volume of the sediment phase in relation to the total volume of the sample.
**The average particle size which 90% of the solid particles in the oil phase have was measured.
Penetration Test
In this test, the penetration of active compounds through enzymatically isolated cuticles of apple tree leaves was measured.
Leaves were used which were cut off in the fully developed state of apple trees of the variety Golden Delicious. The cuticles were isolated by
After this, only the leaf cuticles of the tops of the leaves that were free from stomata and hairs were used further. They were washed a number of times alternately with water and a buffer solution of pH 7. The clean cuticles obtained were finally mounted on small Teflon plates and smoothed out and dried using a gentle jet of air.
In the next step, the cuticle membranes thus obtained were placed into diffusion cells (=transport chambers) of stainless steel for membrane transport investigations. For this, using tweezers the cuticles were placed centrally on the edges of the diffusion cells coated with silicone grease and sealed using a likewise greased ring. The arrangement had been chosen such that the morphological outer side of the cuticles was directed outwards, i.e. to the air, while the original inner side was facing the interior of the diffusion cell. The diffusion cells were filled with water or with a mixture of water and solvent.
For determination of the penetration, 9 μl in each case of a spray liquor of the composition mentioned below was applied to the outer side of a cuticle.
Spray liquor A
in 1 liter of water.
Spray liquor B
in 1 liter of water.
Spray liquor C
in 1 liter of water.
Spray liquor D
in 1 liter of water
(prepared from commercially available suspension concentrate by diluting with water). CIPAC water was in each case used in the spray liquors.
After the application of the spray liquors, the water was allowed to evaporate in each case, then the chambers were in each case turned and placed in thermostatted baths, a saturated aqueous calcium nitrate 4-hydrate solution in each case being located under the outer side of the cuticles. The resultant penetration took place at a relative humidity of 56% and a set temperature of 25° C. Samples were removed at regular intervals using a syringe and investigated by means of HPLC for the content of penetrated active compound.
The experimental results can be seen from the following table. The numbers stated are average values of 8 measurements.
| Number | Date | Country | Kind |
|---|---|---|---|
| 101 29 855.2 | Jun 2001 | DE | national |
This application is a continuation-in-part of U.S. application Ser. No. 10/480,945, filed Dec. 16, 2003, which was filed under 35 U.S.C. 371 as a national stage application of PCT/EP02/06323, filed Jun. 10, 2002, which was published in German as International Patent Publication WO 03/000053 on Jan. 3, 2003, which is entitled to the right of priority of German Patent Application 101 29 855.2, filed Jun. 21, 2001.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10480945 | Dec 2003 | US |
| Child | 11500827 | Aug 2006 | US |
