DE2938127A1 - INTEGRATED METHOD FOR COMBATING IN WATER LIVING PESTS AND UNWANTED FLORA USING FLUORCHEMICAL SURFACE FILMS - Google Patents

Description

DR. BERG DiPL-ING. STAPF DlPL-ING. SCHWABE DF .. DR. SANDVAlP.

PATENTANWÄLTE PO Box 860245 8000 Munich £ 86 »J O 0» £ #

Attorney's file: 30 386

CIBA-GEIGY AG
Basel

Integrated method of controlling aquatic pests and unwanted flora using fluorochemicals Surface films

f (019) 911272 Teiejnmme: Binkkonten H> po-B »nV Munich 4410122850

9SI273 BERGSTAPFPATEKT Munich (BLZ 7OO2O01I) Swifl Code HYPO DE MM

»» «274 TELEX: Bayer Vereiiubuik Munich 453100 (BLZ 70Ο2ΟΓ7Ο)

"3310 05245 * 0 BERG d Postscheck Munich 65343-808 (BLZ 70010080)

030014/0807

Case 61-12043 / CGC 873 / +

USED INTEGRATED METHOD OF CONTROLLING SCALLOWS LIVING IN WATER AND UNWANTED FLORA OF FLUORCHEMICAL SURFACE FILMS

Effective means of combating mosquitoes are e.g. petroleum oils, which because of their suffocating effects of the oil film have larvae and pupa killing effectiveness, and surfactants that act on larvae and pupae, because they reduce the surface tension of watery surfaces and thereby the mortality of mosquitoes cause them to interfere with their ability to stay on the surface to breathe. Furthermore, one sets also use monomolecular phospholipid layers, e.g. lecithin, or hydrocarbon-based agents to treat mosquito larvae and choke dolls.

Unfortunately, the methods mentioned above generally have certain "inherent disadvantages". For example, petroleum oils are relatively toxic and are usually produced in much larger quantities per unit area applied as a hydrocarbon based surface scavenger. Conventional surface capture agents are less toxic »but generally do not reduce the surface tension of the water below 25 dyn / cm and have insufficient spreading pressure. In addition, many such funds result from their water solubility does not have a tough, permanent film. Since conventional surfactants are water-soluble »they have to are often used in intolerable amounts.

The present invention relates to a method

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~ v

for mosquito control, where you hit the surface of mosquito larvae-infested water, an effective amount of a permanent, rapidly spreading surface film from a liquid composition which

(1) about 0.1 to 95 parts by weight of a fluorochemical compound having a density higher than water, higher Spreading pressure as 50 dynes / cm at one concentration of less than 10 mg / square meter of water surface and a water solubility lower than 0.01% by weight 6,

(2) about 99.9 to 5 parts by weight of a diluent in which the fluorochemical compound is at least 0.1% by weight is soluble and that is at least 0.0196 water soluble, as well as optionally

(3) up to 90 parts by weight based on the weight of this fluorochemical compound and diluent, a biocide such as an insecticide, algaecide, molluscicide, herbicide or mixtures thereof, with the proviso that the resulting composition reduces the surface tension of the water to below 29 dynes / cm humiliated, contains.

The invention furthermore relates to the liquid composition for carrying out the according to the invention Mosquito control method. When an effective amount of biocide is present, the resulting composition Use to combat insects, algae, mollusks, weeds and the like living in water.

Another object of the present invention is the biocide containing components (1), (2) and (3) Composition for use in combating aquatic flora, fauna, or both together.

The mosquito control compositions according to the invention particularly preferably contain (1) 0.1 to 95 parts by weight of a fluorochemical compound with a density higher than water, of the formula

030014/0807

where η and r each 1 or 2 and m 0 or 1, a straight-chain or branched perfluoroalkyl group with 4 to 20 »preferably 6 to 12» carbon atoms or such perfluoroalkyl substituted by perfluoroalkoxy with 2 to 6 carbon atoms or this alkyl is not exclusively by fluorine substituted ', but also contains at most one chlorine or hydrogen atom for every two carbon atoms, T is a covalent bond or a bridging group with the functionality (n + r) to link a maximum of 2 R _f chains and 2 Z groups, where T represents -R ₃ - or -R, (XR ^ -), in which R, and R ^ are, independently of one another, straight-chain or branched, saturated or unsaturated, optionally halogen-substituted alkylene or arylene groups with up to 12 carbon atoms, -X- a Thio, oxy or imino function, where the nitrogen atom in this imino group is secondary or tertiary, and ρ is 1 to 4 and Z is one or two neutral or polar groups denotes which are independently and preferably the groups -CONR ₁ R ₂ * -OH, -CN, -CONR ₁ COR ₂ , -SO ₂ NR-R ₂ , -O ₃ CR ₁ and -CO ₂ R ₁ , where R , and R _{2 are} independently hateful or straight-chain or branched _{alkyl with 1 to 12 carbon atoms, optionally monosubstituted or polysubstituted by -OH, -COCH 3} or -CONH (CH ₃ ), and in the event that R _{f is} 6 or more, especially 10 or more. Contains carbon atoms, anionic or cationic strongly polar groups of the formulas -CO ₂ H, -SO ₃ H, -PO (OH) ₂ , -OSO ₃ H, -S ₃ O ₃ Na or quaternary ammonium, provided that the resulting fluorochemical The compound is less than 0.0196 water-soluble and has a spreading pressure greater than 50 dynes / cm at a concentration of less than 10 mg / m water surface,
(2) 99.9 to 5 parts by weight of a diluent, in

030014/0807

ORIGINAL INSPECTED

which the fluorochemical compound contains at least 0.1% by weight is soluble and which is at least 0.01% water-soluble and optionally

(3) up to 90 parts by weight based on the weight of (1) and (2) of a biocide.

As stated above, the R ^ group can be perfluoroalkyl with 4 to 20 carbon atoms in the broader sense, however, it is preferably perfluoroalkyl of 5 to 14 or 6 to 12 carbon atoms.

The fluorochemical compound has a covalently bonded end group -T _1n Z _x , * which as such is not critical. However, the overall solubility and physical properties, as determined by the interrelationship of the Rf, T and Z proportions, are important in determining the effectiveness of the spreading agent. In general, it is necessary that the combination of the fluorinated radical with the end group is balanced so that the water solubility at 25 ⁰ C is minimal, ie below 0.01 wt .-%, and that the fluorocarbon / diluent composition has a low melting point, preferably at room temperature is liquid, and very particularly preferably remains liquid ^{at 0 ° C.} The relatively simple aid of using mixtures of telomeric Rf groups helps to achieve such low melting eutectic liquids. The use of a diluent for the fluorochemical compound also helps to maintain the fluidity of the composition at low temperatures.

Suitable diluents are solvents in which the fluorochemical compound is at least 0.1% soluble, which are environmentally friendly, have a low toxicity to vertebrates, have a high flash point, a melting point ^ O ⁰ C and a density below 1.0, easily accessible and are completely miscible with water or at least 0.01% soluble in water.

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Such compositions form an extremely mobile film under use conditions.

Appropriately lowers the resulting composition the surface tension of the water to below 29 dyn / cm. As a result, the wetting of the internal leads hydrophobic structure of the trachea of mosquito pupae and larvae to block with fluid and to Respiratory problems, causing them to drown.

If there is also a conventional biocide in the composition, it can be used to to release the agent into the aquatic environment.

There is also a use of the inventive A composition containing an effective amount of the biocide for controlling aquatic pests and unwanted flora into consideration, either concurrently with mosquito control as integrated Control method or in the absence of mosquito pupae and larvae.

Suitable biocides include insecticides, fungicides, algaecides, molluscicides, herbicides and the like Mixtures.

Insecticides suitable for use in the present invention include, for example, chlorine-containing ones Compounds into consideration, such as the commercial products (trademarks): DDT (dichlorodiphenyltrichloroethane), Lindane (hexachlorocyclohexane), aldrin (hexachlorhexahydrodlmethanonaphthalin, Dieldrin (1,2,3 ^, 10,10-HeXaChIOr-6,7-epoxy-1 »4,4a, 5,6,7,8,8a-oc tahydro-endo, exo-1,4,5 * 8-dimethanonaphthalene), Methoxychlor (1,1,1-trichloro-2,2-bis- (4-methoxyphenyl) -ethane), Heptachlor (1,4,5,6,7,8,8-heptachlor-3a, 4,7,7a-tetrahydro-4,7-methanoindene) or toxaphene (chlorinated camphene). Organic phosphoric acid esters and thiophosphoric acid esters are also used as insecticides in question, such as methyl parathion (p-Nltrophenyl-dimethylthiophosphoric acid ester), Ethyl parathion (p-nitrophenyl diethylthiophosphoric acid ester, malathion

030014/0807

(OιO-dimethyl-S-1,2-dicarbäthoxyäthyl-dithiophosphat) or diazinon (0,0-diethyl-0- [2-isopropyl-6-methylpyrimidinyl- (5 ^ -thiophosphoric acid ester) and also (1,2-dibromo-2,2-dichloroethyl) dimethyl phosphate, pyrethrins, Piperonyl butoxide, chlorpyrifos (0,0-diethy1-0-3 »5,6-trichloro-2-pyridyl-phosphorothioate) and penthione (0,0-dimethyl-O-A-methylthio-m-tolyl phosphorothioate).

Examples of suitable molluscicides are metaldehyde (polymeric acetaldehyde), N-methylcarbamic acid-A-dimethylamino-3,5-xylyl ester, Bismuth methoxyhydroxybenzoate, chlordane and clonitralide.

Suitable algaecides are, for example, diisobutylphenoxyethoxyethyl-dimethyl-benzylammonium chloride and copper salts and complexes such as copper nitrate, copper gluconate and copper-triethanolamine complexes.

Examples of suitable herbicides for use in water are urea derivatives such as 3- (3 »A-dichlorophenyl) -1, 1-dimethylurea (Diuron), l-butyl-3- (3, A-dichlorophenyl) -l-methylurea (Neburon), 1,1-dimethyl-3-phenylurea (Fenuron), 3- (A-chlorophenyl) -1, dimethylurea (Monuron) or 6,7-dihydro-dipyrido- (1 »2-a: 2, 1-oc] -pyrazidinium bromide (Diquat). The names in brackets are trademarks.

Prior art spreading agents have generally been useless when they have a greater density than possessed water as they would sink. Unexpectedly, this applies to those used according to the invention Compositions are not allowed, which can have a much higher density than water and still usable are. This is because the fluorochemical type capture agents have such high spreading speeds that the agent spreads before the local surface thickness exceeds the limit at which the force of gravity Makes droplets coalesce and sink. Once the agent reaches a useful molecular thickness has spread, strong surface tension forces act

030014/0807

as a protective skin that can carry the tight catchment device and prevents it from sinking in spite of its density.

It is particularly useful to lower solutions of the fluorochemical agent in a diluent To apply density, which has a finite solubility in water. This allows the application of a Dissolving the spreading agent at a density lower than water, the solution floating and acting as a reservoir serves for further fluorochemical agent as required, but eventually dissolves and does not have a surface film leaves behind.

A particularly suitable class of liquid diluents includes those normally liquid aliphatic Compounds containing at least one polar group in their molecule and mixtures thereof Links. Any polar groups present are, for example, hydroxyl, ether, ester, Keto, keto alcohol, keto ether, keto ester or Ether alcohol groups. Special classes of such compounds are the ether and ester derivatives of alkylene glycols and alcohols and ketones.

While the ether and ester derivatives of alkylene glycols or their mixtures are normally without If another liquid diluent is added, it may be advantageous to use one or more lower to add aliphatic alcohols with at most 3 carbon atoms in their molecule as an additional liquid diluent material when a fluorochemical agent lower solubility, e.g. with a high telomer content, is used.

The addition of such lower aliphatic alcohols cannot be ruled out if ether and ester derivatives of alkylene glycols and alcohols, ketones or mixtures thereof are to be used. Generally the liquid diluents can be added to achieve optimal pour points. The liquid cons

0300U / 0807

dünnungsmaterial should be able to prevent at -29 ⁰ C, the solidification of the entire liquid batch at 0 ° or even.

The liquid diluent also serves to reduce the density of the perfluorinated component. It can be miscible with water or only sparingly soluble to help the active ingredient become uniform to spread and not to collect and set down locally.

The components to be mixed should preferably be selected in such a way that the resulting Composition of the fluorochemical active ingredient easily into a largely water-insoluble film of monomolecular Thick spreads.

Among the ether and ether which can be used as diluents in the compositions according to the invention Ester derivatives of alkylene glycols are preferred those represented by one of the following general formulas can be represented:

(D R ¹ (OR ") OH
η (2) R ¹ (OR ") OR ¹
η (3) R ¹ COOR " (A) R ¹ COO (R "- (5) R ¹ COOR " (6) R * COO (R "- -OH —0—) R ¹
η —OOCR · —0 -) - R ¹¹ OOCR '
η

wherein R ^{1 is in} each case, independently of one another, alkyl with 4 to 20 carbon atoms, R "is alkylene with 2 or 3 carbon atoms and η 1 or 2. Those in which R ^{1 has} 4 to 10 carbon atoms are particularly preferred, which means that one Monoalkyl ethers of ethylene or propylene glycol in which the alkyl group has 4 to 10 carbon atoms is used. Mixtures of ethers of this type can of course also be used.

030014/0807

Examples are the monobutyl and monohexyl ethers of ethylene, propylene and diethylene glycol. links this class can be prepared using methods well known in the art. The monobutyl or isobutyl ethers of ethylene or propylene glycol are particularly preferred as solvents.

An important class of compositions according to the invention are those which, in addition to the fluorochemical Compound a monobutyl ether of ethylene or propylene glycol, isomeric hexanols or methyl amyl ketone included as a diluent.

Particularly suitable mixture in which t ^he fluorochemical compound in an amount below 50 wt .-% of the composition and this then has a density of about 0.95 g / cnr has.

Furthermore, the reservoir effect makes one special colored foam blanket makes the barrier more visible and can be used to deter waterfowl from landing.

It should be emphasized that the active permanent spreading agent is the insoluble, monomolecular one Layer-forming fluorochemical compound is. It is necessary to choose solvents carefully, so as not to reduce the performance. Preferred spreading agents are neutral and use a wide variety of solvents and materials compatible.

The present fluorochemical compounds are readily available derivatives. They can hold a mixture of fluorinated end groups of C ^ to ^C 2o FQ ^F 4l ~ ^ervt or a specific, resulting from the Simons cell technology have chain length. Although they can have different functionalities, the most effective capture agents are neutral and still contain strongly polar functions and particularly preferably those that can be made soluble by hydrogen bonds. Strongly acidic or basic, corrosive, extremely volatile

0300U / 0807

or otherwise unstable fluorochemical derivatives are not recommended for purposes of this invention.

Perfluorinated components can also be released from a solid carrier material. For example the solid carrier materials can be water-soluble, so that the liquid with the Dissolution of the carrier in the water is released. However, the carrier materials can also be insoluble in water, the liquid slowly leaching from the carrier when applied to oil contaminated water. The liquid collecting means mixed with the carrier material may only consist of one or two fluorochemical agents, but there may also be one or two like besides. liquid diluents defined above contain.

Polymers are preferred for both the water-soluble and the water-insoluble carrier materials. Naturally occurring substances are suitable as such, including e.g. polysaccharides and gums, as well as man-made substances, including e.g. carboxymethyl cellulose, carboxyvinyl polymers, Carbopol polyamides, Polyurethanes, polyvinylpyrrolidone, polyesters of polycarboxylic acids, polyolefin oxides, polyacrylates and methacrylates, polyvinyl ethers and polyvinyl alcohols. For example, you can mix the liquid agent with water and then with the polymer thicken or gel into a composition which is a relatively thin liquid if the liquid agent Should disperse quickly during application, or can be a thick paste if slower dispersion of the liquid agent is desired. The composition can of course also be an intermediate one State.

If the liquid agent is incorporated into a water-soluble polymer, the resulting mixture becomes preferably dried in the desired shape.

03001 A / 0807

Such mixtures can be applied as a paint on solid bodies that are to float on the water. You can also apply them to tapes, which you then attached to solid bodies intended to float on the water.

The spreading agent compositions according to the invention can be applied, for example, by spraying, pouring out, injecting or brushing. Man can also encapsulate them in desired amounts in a water-soluble envelope or bag. Here can a number of such capsules with different release rates over a period of time use.

Furthermore, one can use a porous solid with the spreading agent composition as such or diluted Soak condition. Suitable porous materials include soft materials, e.g. dew, sponge, Tissue, cloth and paper as well as hard materials, e.g. wood, porous plastics and porous stone. Finely divided Solids such as vermiculite or various clays can also be used to soak up the compositions or to thicken if they are already present as pastes. Such materials can then be broken down into different Deform large and shape. If necessary or desired one can use finely divided material for the purpose Fill into the bag at varying release speeds. Furthermore, the spreading agents can be converted into a polymer Substrate are sucked in, from which they are released with diffusion-determined speed, e.g. Hydrogels.

Finally, the spreading agent can be used as a foam. You can turn it into a proteinaceous one Incorporate foaming composition of particular stability, which then acts as a drainage source and as a marker serves for where the surface scavenger is applied became. Conventional surfactant foams are also

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if applicable.

The packaging and conveyor system for the present funds are not of paramount importance for their successful use and should not be restricted in any way.

Preferred fluorochemical compounds for use in the present invention are those of the formula

(7) R _f TZ,

(8) \ Z

: '- z, (9) R _f -T · _or

R Z

do) \ "^ κ / \

wherein R- are each perfluoroalkyl with 4 to 20, preferably 6 to 12, carbon atoms or perfluoroalkoxy perfluoroalkyl with a total of 4 to 20, preferably 4 to 12, carbon atoms;

T q straight-chain or branched alkylene with 1 to 10 carbon atoms, alkenylene with 2 to 10 carbon atoms, arylene with 6 to 10 carbon atoms or -X- interrupted alkylene with 2 to 10 carbon atoms, where X is oxy, thio or imino with hydrogen or lower alkyl Imino nitrogen and where this alkylene, alkenylene, arylene or interrupted alkylene is optionally halogen-substituted, or T is a direct bond and Z is independently -CONR ₁ R ₂ , -OH, -CN, -SO ₂ NR ₁ R ₂ , -OOCR ₁ or -COOR ₄ , where R ₁ and R _{2 are} independently hydrogen or optionally mono- or polysubstituted alkyl having 1 to 12 carbon atoms, R _{4 being} alkyl having 1-12 carbon atoms, substituted with one or more

030014/0807

-OH, -COCH ₃ or -CONHCH ₃ groups; T ^{1 represents} alkanetriyl with 1 to 10 carbon atoms, alkenetriyl with 2 to 10 carbon atoms or alkanetriyl with 2 to 10 carbon atoms interrupted by -X-, where X is oxy, thio or imino with hydrogen- or lower alkyl-substituted imino nitrogen and this alkanetriyl, alkenentriyl and interrupted alkanetriyl is optionally substituted by halogen such as fluorine, chlorine or bromine; and

T "Alkantetrayl with 1 to 10 carbon atoms, Alkentetrayl with 2 to 10 carbon atoms or by -X- interrupted alkane tetrayl with 2 to 10 carbon atoms represents, wherein X has the meaning given above; provided that the water solubility of the fluorochemical Compound is less than 0.01 wt%.

Those compounds in which -X- is oxy or mercapto are particularly preferred.

Conveniently one should use the fluorochemical compound select from those that have an effective spreading pressure greater than 50 dynes / cm at a concentration less than 10 mg per square meter.

Suitable fluorochemical compounds are known from German Offenlegungsschrift No. 2,856,616. Such fluorochemical compounds which either undiluted (column 2) or as a 75% solution in butyl cellosolve (column 3 of the table below) have a maximum film pressure, _max » ^of less than 50 dynes / cm, are particularly useful for carrying out the method according to the invention .

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Tabel
STRUCTURE

2λ

C ₇ F ₁₅ CH = CHCH ₂ OCH CK OH

C ₀ F ₁ , CH CH ₀ SCH = CHCH ₀ OH ox / 22 2

R CH CH SCH CH CH OH

R _f CH ₂ CH ₂ SCH ₂ CH ₂ OCH ₂ CH ₂ OH

L = liquid level 1 level 2

S = more solid
State ¹¹ max
(un IT
Max
(75% thin) Solution) L. 55 52 S. 1 52 S. 36 55 L. 56 52 S. 53 57

CH ₂ CH ₉ OH

(CFJ ₀ CFOCF ₀ CF ₀ CH-CH ₀ SCHCh OH 3 2 ZZZZ 2

51

^C 8 ^F 17 ^CH 2 ^CH 2 ^SCH 2 ^CH 2 ^OCH 2 ^CH 2 ^OH

CF, .CH-CH ₀ SCH ₀ CH-O (CH ₀ ), OH O LI ZZ ZZ <- *

R _x CH-CH-S (CH ₀ CH-CO-CH ₀ CH ₀ OH) -Caigomer t ZZ ZZZZZ η

CF, -CH.CH _o SCH.CH _o C0NHC (CH-) _o CH_COCH-O 13 ZZZZ j Z Z j

C ₀ F ₁ .CH-CH ₀ SCH.CH _o CONHC (CH.) _ CH _o C00CH-R CH CH SCH CH CONHC (CH) CH ₂ COCH R CH CH ₂ SCH CHOHCh ₂ OCH ₂ CK OCK R CH CH ₂ SCH ₂ CHOKCh ₀ (OCH ₂ CtI ₀ ) ₃ OCH ₃

^C 8 ^F 17 ^CH 2 ^CH 2 ^SCH ' ^{CH (CH} 3 ^{) CO} 2 ^CH 2 ^CH 2 ^OH C ₀ F ₁ -CH ₀ CH ₀ SCH ₀ CH (CH ₀ ) CO ₀ CH ₀ CHCHCh,

CF CONHCH CH OH
R CH ₂ CH ₂ SCH CH COXHC (CH) CH ₂ COCH R ^ CH ₀ CH ₀ SCH ₀ CK, CONHC (CH ₃ ) _? CK COCK ^ CK (CK) CO.CH ₀ CHOHCH

L. 57 54 S. 51 57 S. 49 57 S. 52 52 L. 50 48 S. 53 57 L-S 49 57 L. 58 L. 56 57 L. 49 50 S. 50 L. 58 57 L. 48 53 S. 51 59 S. 55 58 S. 53 46 L. 50.0 54.5 L. 50.0 50.0 L-S 54.0 54.5

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STRUCTURE

R ^ CH CH SCH CH (CH) C0 CH ₀ CHOHCH, χ 2 2 ·. 322

^R f ^CH 2 ^CH 2 ^SCH 2 ^CH 2 ^CO 2 ^CH 2 ^CH 2 ^OH R ^ CH CH SCH CH CO ₂ CH CH OH

R CH CH SCH CH OCH CH CH OH

^R f ^CH 2 ^CH 2 ^SCH 2 ^CH 2 ^OCH 2 ^CH 2 ^CH 2 ° ^H R ^ CH CH SCH CH CO CH CHOHCH

CH (CH

L = liquid stage 1 stage

S = fixed ff DD

max max

Condition (un- (75% ige

thin) solution)

L-S

CH (CH

₂ ] ₂ - (EG) _k ^{Ί a}

(EG) L L S

53.5 54.5 56.0 54.0 52.5 55.5 56.0 56.0 56.5 55.5 56.0 ² 51.0 57.5 51.5 57.5 57.0 58.0 55.5 56.0 53.0 5I ₁ O 53.0 50.5 48.0

CH CO CH CKOHCH C "F CH CH SCH CH CO CH CH OCH

^C 8 ^F 17 ^CH 2 ^CH 2 ^SCH 2 ^CH 2 ^CO 2 ^CH 2 ^CHCH 2 ^CH 2 ^CH 2 ° ^C 8 ^F l7 ^CH 2 ^CH 2 ^SCH 2 ^CH 2 ^CO 2 ^(CH 2 ^CH 2 ^O) 2 ^C 2 ^H 5 R * "CH CH SCH CH ₀ OCH CH OH

R ^ CH CH SCK- ¹ I.

CH ₀ O (CH _n CH O) H 2 2 2 n LL

L-S S

53.5 53.5

49.0 51.0 52 53 56 50 48 58

a. R _f = C ₆ , C ₈ , C ₁₀ - 79, 15,

b. R _f = C _6, C _8, C _10, C _{12 to} 39, 33, 16, 9

c. R _f = C _6, C _8, C _10, C _{12 to} 51, 35, 10, 2

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1 Derived from (a) tetraethylene, (b) triethylene glycol

2 measured value unstable

According to the invention, the following further Fluorochemicals in suitable solvents (such as 5-methyl-2-octanone, propylene glycol isobutyl ether, Methyl amyl ketone, diisobutyl ketone, .4-methoxy-4-methyl-2-pentanone, Use isooctanol, diethylene glycol monobutyl ether or ethylene glycol monobutyl ether):

₈ C ₇ F CON (C ₂ H ₅ ) CH ₂ CH ₂ OH

^CF ₃ VlO ^SO 2 ^{N (C} 2 ^H 5 ^{) CH} 2 ^CH 2 ^OH C ₃ F ₇ O (C ₃ F ₆ O) ₂ CF ₉ CON (CH ₃ ) C ₃ H ₆ OH

C ₈ F ₁₇ SO ₂ N (C ₄ H ₉ ) CH ₂ CH ₂ CH ₂ OH

^C 8 ^F 17 ^SO 2 ^{N (C} 2 ^H 5 ⁾ «^ W *

^R f ^CH 2 ^CH 2 ^SO 2 ^{N (C} 2 ^H 5 ^{) CH} 2 ^CH 2 ° ^H

R _r OC, H, SO-N (C-H_) CH, CH OH f 6 4 2 Id Ii

C, "F, _ft OC _c H, CON (CH.) CH.CONH 10 19 6 4 3 2 I.

EXAMPLE

A mixed fluorochemical compound of the formula R ^ CH ₂ CH ₂ SCH ₂ CH ₂ COOCH ₂ COOCH ₂ CHOHCh ,, where R _{f is} a mixture of CgF ^, - (51%), CgF, ^ - (35%), C is added _{10 is} F ₂₁ - (10%) and C ₁₂ F ₂ C ₅ - (2%), in an amount of 80 parts by weight to butylcellosolve in an amount of 20 parts by weight. At a concentration of less than 10 mg per square meter, the composition has a spreading coefficient of about 51.5 dynes per centimeter. This solution is mixed with one part by weight of 0,0-diethyl-O- [2-isopropyl-6-methylpyrimidinyl-

030014/0807

5! -Thiophosphoric acid ester (Diazinon - trademark), which dissolves in it. The resulting composition spreads rapidly on water to form a film thereon, thereby releasing the insecticide into the aquatic environment.

Instead of this fluorochemical compound one can use the other fluorochemicals mentioned above in the table insert.

If the above-mentioned mixture is mixed with one part by weight of piperonyl butoxide, malathion (trademark), Copper citrate or Diquat (trade mark) instead of Diazinon (trade mark) gives analogous results. In addition, the above-mentioned compositions, with or without a biocide, have a mosquito larva killing effect on.

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Claims (16)

Expectations 1. Method of mosquito control, characterized in that one is on the surface of a mosquito larvae contaminated water, an effective amount of a permanent, rapidly spreading surface film from a a liquid composition which (1) about 0.1 to 95 parts by weight of a fluorochemical compound with a higher density than water, a higher spreading pressure than 50 dynes / cm at one concentration of less than 10 mg / square meter of water surface and a water solubility lower than 0.01% by weight, (2) about 99 »9 to 5 parts by weight of a diluent, in which the fluorochemical compound is at least 0.1% by weight soluble and at least 0.01% is water soluble, as well as optionally (3) up to 90 parts by weight of a biocide based on the weight of this fluorochemical compound and des Diluent, with the proviso that the resulting composition reduces the surface tension of the water to below 29 dyn / cm humiliated, contains. 2. Method according to claim 1, characterized in that the liquid composition (1) 0.1 to 95 parts by weight of a fluorochemical compound having a density higher than water, of the formula <Wm ^Z r
where η and r each 1 or 2 and m 0 or 1, R _{f is} a straight-chain or branched perfluoroalkyl group with 4 to 20 carbon atoms or such perfluoroalkyl substituted by perfluoroalkoxy with 2 to 6 carbon atoms ^ or this alkyl is not exclusively substituted by fluorine, but also contains at most one chlorine or hydrogen atom for every two carbon atoms, T a covalent bond or a bridging group with the functionality (n + r) for linking at most 2 R ^ chains and 030014/0807 2 Z groups, where T is -R ₃ - or -R ₃ (XR ₄ -) where R ₃ and R _{4 are} independently straight-chain or branched, saturated or unsaturated, optionally halogen-substituted alkylene or arylene groups with up to 12 carbon atoms , -X- a thio, oxy or imino function, where the nitrogen atom in this imino group is secondary or tertiary, and ρ is 1 to 4 and Z is one or two neutral or polar groups, which are independently and preferably the groups -CONR ₁ R ₃ , -OH, -CN, -CONR ₁ COR ₂ -SO ₂ NR ₁ R ₂ , -O ₂ CR ₁ and -CO ₂ R ₁ , where R ₁ and R _{2 are} independently hydrogen or straight-chain or branched, alkyl having 1 to 12 carbon atoms, optionally monosubstituted or polysubstituted by -OH, -COCH ₃ or -CONH (CH ₃ ), and in the case that R _{f contains} 6 or more, in particular 10 or more, carbon atoms, anionic or cationic strongly polar ones Groups are provided that the results The fluorochemical compound is less than 0.01% water-soluble and has a spreading pressure greater than 50 dynes / cm at a concentration 2
has a tration of less than 10 mg / m water surface, (2) 99.9 to 5 parts by weight of a diluent, in which the fluorochemical compound is at least 0.1% by weight soluble and that is at least 0.0196 water soluble is, as well as where applicable (3) up to 90 parts by weight of a biocide based on the weight of (1) and (2). 3. Method according to claim 2, characterized in that an ether or ester derivative is used as the diluent an alcohol or alkylene glycol, a ketone or a mixture thereof is present. 4. The method according to claim 3, characterized in that a compound of the following is used as the diluent Formulas 0300U / 0807 R. (or ..) _0H Rt _(0R ") _0R , R'COOR "OH R ¹ COO (R "0 ~) R ¹ R'COOR "OOCR · R ¹ COO (R "0-) -R ¹¹ OOCR ¹ wherein the R 'each independently of one another for an alkyl radical having 4 to 20 carbon atoms, R "for one Alkylene radical with 2 or 3 carbon atoms and η stand for 1 or 2, is present. 5. The method according to claim 4, characterized in that a monoalkyl ether of Ethylene or propylene glycol, in which the alkyl group Has 4 to 10 carbon atoms is present. 6. Method according to claim 4, characterized in that a monobutyl ether of ethylene is used as the diluent or propylene glycol, an isomeric hexanol, or methyl amyl ketone is present. 7. The method according to claim 1, characterized in that the biocide is an insecticide, fungicide, algaecide, Molluscicide, herbicide or a mixture thereof is present. 8. Liquid composition for mosquito control, characterized in that it contains the compounds (1), (2) and optionally (3) according to claim 1 contains. 9. Biocidal composition for use in combating aquatic flora, fauna, or both together; characterized in that they (1) about 0.1 to 95 parts by weight of a fluorochemical agent having a density higher than water, higher Spreading pressure than 50 dynes / cm at a concentration of less than 10 mg / square meter of water surface and a water solubility lower than 0.01% by weight, (2) about 99 »9 to 5 parts by weight of a diluent 030014/0807 s in which the fluorochemical compound is at least 0.1% soluble and at least 0.01% soluble in water is, as well (3) an effective amount of a biocide, provided that the resulting composition the surface tension of the water is reduced to below 29 dynes / cm. 10. Composition according to claim 9 »characterized in that that they (1) 0.1 to 95 parts by weight of a fluorochemical compound having a density higher than water, of the formula ( ^R f> n ^T m ^Z r
where η and r are each 1 or 2 and m is 0 or 1, R ^ is a straight-chain or branched perfluoroalkyl group with 4 to 20 carbon atoms or perfLvoralkyl substituted by perfluoroalkoxy with 2 to 6 carbon atoms ^ or this alkyl is not exclusively substituted by fluorine, but also contains at most one chlorine or hydrogen atom for every two carbon atoms, T is a covalent bond or a bridging group with the functionality (n + r) for linking at most 2 R ^ chains and 2 Z groups, where T is -R-, - or -R, (XR ^ -) where R, and R ^ independently of one another «erarikettiqe _or branched, cresaturated or unsaturated, optionally halogen-substituted alkylene or arylene groups with up to 12 carbon atoms, -X- are a thio, oxy - Or imino function, where the nitrogen atom in this imino group is secondary or tertiary, and ρ ι is up to 4 and Z is one or two neutral or polar groups which are independent gig from each other and preferably the groups -CONR ₁ R ₂ , -OH, -CN, -CONR ₁ COR-, -SO ₉ NR ₁ R ₉ , -O ₉ CR, and -CO ₁ R ₁ , where R-, and R ^ independently of one another hydrogen or straight-chain or branched, optionally mono- _{or polysubstituted by -OH, -COCH 3} or -CONH (CH ₃ ) alkyl having 1 to 12 carbons 0300U / 0807 are material atoms, and in the case that R _{f contains} 6 or more, in particular 10 or more, carbon atoms, but are also anionic or cationic groups with strongly polar functions, provided that the resulting fluorochemical compound is less than 0.01% water-soluble and has a spreading pressure greater than 50 dynes / cm at a concentration of less than 10 mg / m water surface, (2) 99.9 to 5 parts by weight of a diluent, in which the fluorochemical compound is at least 0.1 wt -% is soluble and which is soluble in water to at least 0.01%, and optionally. (3) up to 90 parts by weight of a biocide based on the weight of (1) and (2). 11. Composition according to claim 10, characterized in that that they are an ether derivative of an alcohol or glycol or a ketone or a diluent Contains mixture thereof. 12. The composition according to claim 11, characterized in that it is a compound as a diluent of the following formulas R '(OR ") OH R ¹ (OR ") OR ¹ R ¹ COOR "OH R ¹ COO (R "0 ~) R ' R ¹ COOR "OOCR ¹ R ¹ COO (R "0—) -R ¹¹ OOCR ' wherein the R 'are each independently of one another for an alkyl radical having 4 to 20 carbon atoms, R "for one Alkylene radical with 2 or 3 carbon atoms and η for 1 0300U / 0807 or 2 stand, contains. 13. Composition according to claim 12, characterized in that a monoalkyl ether is used as the diluent of ethylene or propylene glycol, in which the alkyl group A has up to 10 carbon atoms, is present. 14. Composition according to claim 12, characterized in that that as a diluent a monobutyl ether of ethylene or propylene glycol, an isomeric hexanol or methyl amyl ketone is present. 15. Composition according to claim 9 »characterized in that the biocide is an insecticide, fungicide, algaecide, Molluscicide, herbicide or a mixture thereof is present, 16. Method for combating aquatic flora, fauna or both together, characterized in that one applying a composition according to any one of claims 9 to 15 to a body of water. 030014/0807