DE2408370A1 - SOLID HYDROPHOBIC INSECTICIDAL PREPARATIONS - Google Patents

Description

Solid hydrophobic insecticidal preparation

The present invention relates to insecticidal preparations which, as the active ingredient, have one or more contain volatile insecticidal phosphoric acid esters and which because of their slow evaporation and increased action are particularly suitable for combating insects in closed rooms.

The volatile phosphoric acid esters are among the most effective insecticides, and among them is the best known the dimethyl-2,2-dichlorovinyl phosphate, which is under the Name DDVP is used worldwide in so-called "vaporizers", in which one is aware of the volatility of the substance to create an atmosphere that is permanently toxic to insects.

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Various solid preparations have been proposed, some of which are on the market, which contain a diluent for the phosphoric acid ester, which is intended to protect it against the moisture in the air and at the same time regulate its rate of evaporation. One of these preparations contains a macromolecular polymer as a carrier, such as z..B. Polyvinyl chloride; such a preparation, the melting temperature and viscosity of which in the molten state are very high, can only be processed by extrusion and requires complicated and expensive equipment; In addition, the rate of evaporation of the insecticidal phosphoric acid ester, which at the beginning of evaporation is fast enough to achieve a good effect, decreases considerably after 30 to 40 days. Furthermore, the utilization of the insecticidal phosphoric acid ester contained in the polymeric carrier is incomplete, since more than a third of the phosphoric acid ester is no longer released from the carrier during the evaporation.

Finally, such vaporizers with polymeric carriers show, before and during the evaporation, a strong, unavoidable, also known as "exudation" exudation of the active ingredient on the surface of the vaporizer, which is dangerous for the consumer and that of the regular evaporation

counteracts.

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Another type of vaporizer preparation uses sublimable substances as diluents and carriers.

These diluents, when sublime into the atmosphere, cause a strong odor of their own, which in general is undesirable, as is the case, for example, with naphthalene or para-dichlorobenzene, and / or they even spread an annoying, irritating odor, as happens when using benzoic acid. Furthermore show evaporators with sublimable substances as diluents poor stability during evaporation, as well as an unsatisfactory-sharing strength. When dropping on the solid preparation easily breaks into small pieces which endanger children and animals.

Another type of preparation used as a diluent heavy, higher fatty alcohols, which are opposite to the phosphoric acid esters are not necessarily chemically inert, but may react with them and more or less quickly decompose, giving these compositions stability is lacking. Such preparations also do not have sufficient strength or hardness.

A type of preparation similar to the latter uses FettsMuren as a diluent, but that too are not inert to the phosphoric acid esters; much more generally a transesterification reaction occurs, which means that these preparations are usually not very stable.

Finally, another type of preparation uses as a carrier heavy and non-volatile, saturated aliphatic hydrocarbons of high molecular weight, such as e.g. B. paraffin, together with an incorporation agent, which allows _} a sufficient amount of phosphoric acid ester to mix homogeneously with the paraffin to obtain a good long-acting evaporator in which the phosphoric acid ester is protected from the ambient humidity.

The strength of such known shaped solids can be increased by adding 0.1 to 15% by weight, based on the total weight the preparation, a thickener for the Liquefied paraffin, such as an aluminum mono-, di- or tristearate or a hydrophobic ammonium salt Dime thy ldialkylmontrnorillonits be increased.

Such preparations still lack sufficient firmness; also with these compositions is the efficiency, i.e. the proportion of the phosphorus actually used

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phosphoric acid ester is not particularly good, since about 60 to 65 % by weight of the initial amount of phosphoric acid ester is retained in the preparation after use of the evaporator.

Furthermore, with these preparations the initial release of the insecticide is still a multiple (e.g. a five or six times) of the release after one week of evaporation, so that the effect curve of the evaporator especially at the beginning of the Evaporation decreases quite steeply.

It has now been found that it is surprisingly possible to use a solid hydrophobic insecticidal preparation, which is free from the above-mentioned disadvantages and which has satisfactory strength obtained when a higher solid ketone is used as a carrier instead of solid hydrocarbons.

The present invention therefore relates to a solid, hydrophobic insecticidal preparation, characterized in that it is free of higher molecular weight hydrocarbons and the following Components contains:

40983 B / 1028

(A) as an insecticidal compound, 15 to 4-0 parts by weight of a Phosphorus Zstors, which has a vapor pressure at 20 ° C of at least 0.013 iribar and of the formula

R "R" ¹ R 0 0 CC

R ^1-0 . X

, wherein X or- an oxygen sulfur atom, R and R ^1, independently of one another, alkyl radicals having 1 to 4 carbon atoms, Y is a Halogenatora having an atomic number of at most 35, R "and R ^'1, independently of one another, a Wasserstoffaton, a Halogen atom has an atomic number of at most 35, a methyl group or an ethyl group and k is 1 or 2,

(B) as a carrier substance 10 to 50 parts by weight of a higher Ke.ton whose melting point is above 50 ° C

and whose vapor pressure at 110 ° C does not exceed 1.33 mbar,

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(C) 0.1 to 25 parts by weight of a stabilizing agent for the ester A,

(D) 0 to 30 parts by weight of a hydrophobic thickener,

(E) 0 to 75 parts by weight of an organic, volatile, die'Löslichkeit of the ester (A) in the carrier substance (B) • increase and preferably also the odor of the ester

(A) low-influencing medium whose vapor pressure to 6.66 mbar and at 100 ⁰ C of at least 1.33 mbar at 30 ° C is 0.066

the proportion of (D) and (E), based on the total weight of the preparation, being at least 4%.

The preparations according to the invention can also be used as further, non-essential components contain other substances different from components (A) to (E), such as insecticides, insect repellants, dyes, pigments, bactericidal agents, fungicidal agents, additional Diluents, dispersants and / or inert inorganic or organic fillers.

Such substances can be used in amounts of 0.5 to 30% by weight, based on the total weight of the preparation.

Of the esters, those of the general formula already mentioned (I), you can use, for example, the following phosphoric or thiophosphoric acid esters:

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Dimethyl-2,2-dichlorovinyl phosphate, Dimethyl-2-chlorovinyl phosphate, Diethyl 2,2-dichlorovinyl phosphate, diethyl 2-chlorovinyl phosphate, Dipropyl-2-chlorovinyl phosphate j Diisopropyl-2-chlorovinyl phosphate, Dibutyl-2-chlorovinyl phosphate, Diisobutyl-2-chlorovinyl phosphate, Dimethyl-2,2-dibromovinyl phosphate, Dimethyl-2-bromovinyl phosphate, Diethyl 2-bromovinyl phosphate, dimethyl 2-bromo-2-chlorovinyl phosphate, Diethyl 2-bromo-2-chlorovinyl phosphate, Methylethyl-2,2-dichlorovinyl phosphate, Dimethyl-1,2-dibromo-2,2-dichloroethyl-phosphate, Dimethy1-1-bromo-2,2,2-trichloroethyl-phosphate, Dimethyl 1,2,2,2-tetrabromoethyl phosphate, Dimethyl 1,2-dibromo-2,2-dichloropropyl phosphate, Dimethyl-2-chloro-l-methylvinyl-phosphate, Dimethyl-2-chloro-2-methylvinyl-phosphate, Dimethyl-2,2-dichloro-l-methylvinyl phosphate, Dimethyl 2-chloro-1-ethyl vinyl phosphate, Dirnethyl-2-chloro-2-ethyl vinyl phosphate,

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Dimethyl-2-chloro-1,2-dimethylvinyl-phosphate, Diethyl 2-chloro ~ 1-methyl vinyl phosphate, Dimethyl-2-chloro-vinyl-thionophosphate, Dimethyl 2-chloro-1-methyl vinyl thionophosphate, Dimethyl 2-chloro-2-methyl vinyl thionophosphate.

According to the invention, preferred among the esters mentioned are those in which the remainder

R "R" '

I I

-0 - C CY _{a group} _ ₀ _ _CH =

¹ KI

and X is an oxygen atom, i.e. the dialkyl-2,2-dichlorovinyl phosphate, to which the dimethyl-2,2-dichlorovinyl phosphate, which is available under the names DDVP and ÜICHLORVOS is known, counts.

The carrier (B) is advantageously made from higher ketones of the general formula

R ₁ CR ₂ (ID

selected where

(a) R, and R «, identical or different, each represent an alkyl or alkenyl group both of which together contain from 16 to 60 carbon atoms, or

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(b) RJ is a phenyl or a naphthyl radical which can be substituted by one or more chlorine, bromine, alkyl or acetyl groups and R _? an alkyl or alkenyl radical having 11 to 25 carbon atoms, or

• (c) R, and R-p together an alkylene or alkenylene group having at least 14 carbon atoms, preferably of 16 to 30 carbon atoms.

Under the term "higher ketone" are ketones which contain at least 14 carbon atoms understood.

The following ketones, for example, can be used as carrier (B):

- Di-alkyl and di-alkenyl ketones with at least S carbon atoms in each alkyl chain such as:

Heptadecan-9-one, nonadecan-10-one

Heneikosan-11-one Trikosan-12-one Heptakosan-14-one Hentriakontan-16-one Pentantriacontane-18-one

^C 9 ^H 19 " ^CO " ^C 9 ^H 19

^C 1O ^H 21 " ^CO " ^C 1O ^H 21

(Pelargon) (Caprinon)

C ₁₁ H ₂ --CO-C -, -. H ₂₃ (Lauron)

^C 13 ^H 27 ~ ^CO ~ ^C 13 ^H 27 O ^ Y ^ ston)

C ₁ ^ H ₃₁ -CO-C ₁ -H ₃₁ (palmiton)

C ₁₇ H ₃₅ -CO-C ₁₇ H ₃₁ - (stearon)

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Nonatriakontan-20-one C ₁₉ H ₃₉ -CO-C ₁₉ H ₃ (Arachidon)

Tritetrakontan-22-on C ₀ VHz ₀ -CO-C ₀₁ H ₇₀ (Behenon)

Zl 4j Zl M-j

Henpentakontan-26-one C ₀₅ H _5. , -CO-C ₀₅ H ₅ -, (Ceroton) Pentapentakontan-28-one C ₂₇ H ₅ C-CO-C ₂₇ H ₅₅ (Montanon)

Heneikosadien-l, 20-ll-one ^C 1O ^H 19 ~ ^CO ~ ^C 1O ^H 19

Pentatriakontadien-9,26-18-one C ₁ -JH ₀₀ -CO-Ct-TH ₀₀ , _.,,.

'17 33 17 33 (Oleon)

Pentatriakontatetraen-6,9,26,29-18-one C ^ ₃₁ -CO-C ₁₇ H ₃₁

(Lino1eon) Pentatriakontahexaen-3,6,9,26,29,32-18-one ^c i7 ^H 2q " ^C0 "" ^c 17 ^H 29

(Linolenone) or solid mixtures of these ketones.

Preferred in this class are the ketones which have at least 13 carbon atoms in each alkyl chain such as Myriston, Palmiton Arachidon and Behenon.

Particularly preferred are those ketones which have a melting point above 85 ° C, such as stearone (mp: 88.5 ⁰ C) and arachidonic.

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- 2-alkanones with a total of 19 carbon atoms, such as.:

Nonadecan-2-one CH ^ -CO-n-C, ^ H-r

Eikosan-2-one CH ^ -CO-nC, _Q H "

j Io ό /

Heneikosan-2-οη CH ₃ -CO-HC ₁₉ H ₃₉ Dokosan-2-one CH ₃ -CO-nC ^ H ^

Trikosan-2-one CH ₃ -CO-HC ₂₁ H ₄₃

Dokosan-2-on and Triko are preferred in this class. san-2-on.

- 3-alkanones with a total of at least 16 carbon atoms, such as.:

Eikosan-3-one C ₂ H ₅ -CO-HC ₁₇ H ₃₅

- alkyl phenyl ketones with at least 11 carbon atoms in the alkyl radical, such as:

Myristophenone C ₆ H ₅ -CO- (CH ₂ ) ₁₂ ~ ^CH 3

Palinitophenone C ₆ H ₅ -CO- (CH ₂ ). ,, - CH ₃

Stearophenone C ₆ H ₅ -CO- (CH ₂ ) ₁₆ "CH-

Arachidophenone C ₆ H ₅ -CO- (CH ₂ ) _Ig -CH ₃

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- alkyl naphthyl ketones with 1 to 4 carbon atoms in the alkyl radical, such as:

2-Acetylnaphthalene β-C ₁₀ H ₇ -CO-CH ₃ 1-Acetylnaphthalene Ot-C ₁₀ H ₇ -CO-CH ₃

6 - chlorinated and brominated alkylphenyl ketones with 1 to

4 carbon atoms in the alkyl chain, such as:

2,4-dichloroacetophenone C ₆ H ₃ Cl ₂ -CO-CH ₃ 4-chloropropiophenone C ₆ H-Cl-CO-C ₂ H ₅ 2,4-dibromoacetophenone C ₆ H ₃ Br ₂ -CO-CH ₃

- Monocycloaliphatic ketones with at least carbon atoms, such as: Cyclopentadecanone CH ₉ (CH ₉ )., --CO Cyclohexadecanone CH ₉ (CH ₂ ) - ,, - CO Cycloheptadecanone CH ₉ (CH ₉ ), ^ -

Gycloheptadecanone is preferred in this class

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Further, the present invention preparations "parts must be at least 0.1 to 25 parts by weight and preferably ₅ I O bis.10 wt. Of one or more stabilizing agent (G) against the decomposition of Phosphorsäureesters.

Such stabilizing agents are, in particular, acid-binding agents (proton acceptors), which are composed of phosphoric acid ester (A) bind the resulting acid, or anti-protonation agents, Many marriages prevent the protonation of the phosphoric acid ester.

As stabilizers "of the first group, for example epoxidized Compounds containing at least 1 gram equivalent of epoxy groups per kg of the compounds are preferred as defined in FR-PS 1 187 378, in particular epoxidized oils, e.g. epoxidized soybean oil,

or logenated epoxyalkanes / alkyl epoxystearates with 4 to 18 Carbon atoms in the alkyl chain, e.g. isooctyl epoxystearate, be used.

Isooctyl epoxystearate belongs to this group because of its good compatibility with higher ketones (B) and in particular particularly preferred with lauron and stearon.

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Amino compounds or nitrogen-containing heterocyclic compounds, as defined in FR-PS 1,379,851, also belong to this first group of stabilizers. The same group includes, for example, the salts of ethylenediaminotetraacetic acid, such as the disodium monocalcium salt of ethylenediarainotetraacetic acid (EDTA Na ₂ Ca) »or the salts of diethylenetriaminepentaacetic acid (DTPA), cyclohexanediaminotetraacetic acid (ethylenediaminotetraacetic acid (CDETRAEDTA), the triethyleneglycol-bis-aminotetraacetic acid (EGTA) and propylenedinitrilotetraacetic acid (MEDTA).

Anti-protonization stabilizers include Compounds containing an azo group and their metal complexes, as described in the Belgian patent 760,219; elemental sulfur according to Belgian patent 772 455; Connections of the divalent sulfur, according to the Belgian patent

and
font 772 457 / Benzodioxole, according to the Belgian

Patent 772,456.

An epoxy stabilizer is used, for example, in an amount from about 0 ^ 1 to 50% by weight, preferably from about 0.2 to 40% by weight Used; a non-heterocyclic amino compound

Or a nitrogenous hetero-

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cyclic compound is used, for example, in an amount of about 0.5 to 10% by weight; an azo compound is used, for example in an amount of about 0.1 to 5 parts by J _0, preferably from about 0.3 to 2 wt .-%; elemental sulfur and compounds of divalent sulfur are used, for example, in an amount of about 0.05 to 6% by weight; a benzodioxole is used in an amount of about 0.2 to 10% by weight, these proportions being based on the weight of the phosphoric acid ester (A).

However, mixtures of acid-binding stabilizers, in particular epoxidized stabilizers, are preferred as stabilizers Compounds such as alkyl epoxystearates with a stabilizer that protonates the phosphoric acid ester prevents, such as azo compounds, elemental sulfur, sulfur-containing compounds in particular those of divalent sulfur, benzodioxoles, or compounds containing amino groups.

A very particularly preferred stabilizing agent for the preparations according to the invention consists of a mixture of isooctylepoxystearate and disodium monocalcium salt of ethylenediaminotetraacetic acid im Weight ratio of about 10: 1, with the total amount of stabilizing agent from 20 up to about 50% by weight, based on the weight of the phosphoric acid ester.

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Particularly hard preparations obtained according to the invention when using a hydrophobic thickener (D).

The preparations obtained in this way cannot be crushed by hand, even if dropped on one they do not break hard ground.

With a block containing phosphoric acid insecticide, however, these benefits are extremely important as they are a Safe handling, e.g. also in households, and practically not dangerous for children and pets can be if they are installed in an appropriately designed holder.

The other constituents of the preparation according to the invention can be used as thickening agents (D) for gel formation suitable "metal soaps" (see Römpp Chemie Lexikon, 1958, column 2810).

fatty acid
Preferred are / aluminum, magnesium, calcium,

Strontium, barium, lithium and cobalt salts.

The fatty acid salts which cause gel formation in the context of the invention also include the lactates of the abovementioned Metals.

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Particularly suitable as thickeners (D) are, for example, aluminum mono- and tristearates, as well as aluminum and Calcium lactate, but especially aluminum distearate.

These fatty acid salts are mostly used in amounts of about 3 to 20% by weight, preferably from about 5 to 15% by weight, based on the total weight of the preparation.

Also, as the thickener (D) ammonium salts of Dimethyldialkylmontmorillonits having 14 to 18 carbon atoms - are used in the alkyl group, eg of that Dimeth3 ^T ldialkylinontmorillonits whose alkyl groups averaging 17 carbon hydrogen atoms

the / gs

included and / under the name Bentone 38 ^ (National

Lead Cy.) Is in trade. Such thickeners will be preferably used in amounts of about 6 to 8% by weight, based on the total weight of the preparation.

Thermoplastic polymers or copolymers with a molecular weight of over 1000, preferably above 5000 can be used as the thickening agent (D).

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These are e.g. cellulose derivatives, polymers, or Copolymers of vinyl, vinylidene, styrene, acrylic, methacrylic, alkenyl and polye ^^ l compounds, xd_e e.g. Cellulose esters (e.g. acetates, acetopropionates, butyrates, Phthalates, nitrates); Cellulose ethers (e.g. methyl, ethyl, benzyl ethers) as well as polymers and copolymers of vinyl esters (e.g. acetate, propionate, butyrate), vinyl ketals (e.g. formal, acetal, propional, butyral), vinyl chloride, vinyl pyrrolidones, lower olefins, especially mono- or diolefins (e.g. ethylene, propylene, butylene, isoprene, butadiene), styrenes, acrylic and methacrylic acid esters (e.g. the methyl and ethyl esters) and AUyl esters (e.g. phthalate, isophthalate, Maleate, cyanurate).

The following compounds can also be used: Macromolecular Epoxy resins less than 1 gram equivalent an- epoxy groups per kg of resin, preferably those formed by condensation of an epoxy compound with a polyphenol obtained; Polyester resins made by reacting a polybasic acid with a polyhydric alcohol obtained; Polyurethanes obtained by condensation of a polyisocyanate with a polyhydric alcohol will; and coumarone-indene resins.

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Preferred in this class are the copolymers of Yj acetate and ethylene and especially those with a vinyl acetate content of 25-30% by weight, based on the total weight of the polymer j, for example those under the name Elvax ^ (Dupont de Nemours) im Products in trade.

Such high molecular weight thickeners are mostly used in amounts of about 5 to 30 wt .-%, preferably of about 6 to 15 wt .-%, based on the total weight of the Preparation used. For example, Elvax 250 ^ is preferably used in an amount of 7 to 12% by weight.

The preparations according to the invention can preferably be about

5 to 40% by weight, based on the weight of the preparation, of volatile organic agent (E) which influences the odor of the composition, the vapor pressure of which at 30 ^° C. is in the range from 0.006 to 6.66 mbar, preferably 0.013 to 1 .33 mbar and that has a vapor pressure of

1.33 mbar at temperatures below 100 ⁰ C, preferably below 80 ⁰ C.

having.

Such volatile agents (E) fall into two different categories:

(a) to natural essences or their hydrocarbon, alcohol, phenol, ether, aldehyde, ketone and ester components,

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(b) to synthetic, aromatic hydrocarbons different from (a) or aliphatic, cycloaliphatic and aromatic, ethers, aldehydes, ketals, ketones and esters, which are artificial or synthetic chemical fragrance components are.

In general, therefore, means (E) are natural essences, uniformly defined fragrances of natural origin, uniform defined artificial fragrances, synthetic organic fragrances or mixtures of one or more of these Fabrics.

1) Examples of natural essences are the essential oils, such as anisole, aspic oil, lemon oil, citronella oil, eucalyptus oil, geranium oil, lavender oil, lemon grass oil, mandarin oil, peppermint oil, orange oil, petitgrain oil, pine oil, vetiver oil. Rosemary oil, Kopalö'l, Tepentinöl, pine needle oil, cedar oil, thuja oil, Zypressenö'l, juniper berry oil, Tuberoseöl, iris oil, violet blossom oil, ginger oil, cardamom oil, pepper oil, Betelöl, Myricinb'l, hop oil, sandalwood _it neroli, basil oil, bergamot oil, bitter Pomeranzenschalzenöl , Caraway oil, cumin seed oil, fennel oil,

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Clove oil, marjoram oil, myrtle oil, patchouli oil, quendel oil, Thyme oil, camphor oil, cinnamon oil, rosewood oil, laurel oil, Rose oil, bitter almond oil, acacia oil, star anise oil, jasmine oil.

Extractable from natural essences materials can be used such as:

2) Hydrocarbons, such as: cymene, ocyraene, phellandrene, Terpinen, Terpinolen, Bornylen, Camphan, Isocamphan, Camphene, Caran, Caren, Fenchan, Fenchen, Menthadiene, menthane, menthene, pinane, pinene, myrcene, Thuyan, Thuyen, Verbenen, Cedren, Sabinen, SyI-vestren and Norcamphen;

3) Alcohols, such as: Rhodinol, Citronellol, GeranioL, -Linalool, Nerol, terpineol, citronellol, menthol, borneol, isoborneol, fenchyl alcohol, menthanediol, Piperitol, carol, myrtle oil and verbenol;

4) Phenols, such as: Anol, Chavicol, Charvacrol, Thymol, Safrole and estragole;

5) ethers extractable from natural essences, such as e.g .: anethole, eugenol, eucalyptol, safrole, geranyl alkyl ethers and phenyl alkyl ethers;

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2,08370

6) Aldehydes, such as: Citronellal, Geranial, Santalal, Anisaldehyde, cinnamaldehyde, vanillin, phellandral, isocyclocitral and cuminaldehyde;

7) Ketones, such as: Anisketone, Menthon, Ionon, Iron, Fenchone, camphor, carvone, pulegon, carvenon, isopulegon, piperiton, verbenone and thuyon;

8) Esters of the alcohols indicated above, such as, for example: geranyl acetate, linalyl acetate, eugenyl acetate, bornyl acetate, isobornyl acetate, linalyl propionate, citronellyl acetate and menthyl acetate;

As examples of synthetic or artificial fragrance components, you can use for example:

9) aromatic hydrocarbons such as: diphenylmethane, Diphenylethane and diphenyl;

10) aliphatic ethers, such as, for example: 3,6-dioxa-octanol, 3 ', 6 ^f -dioxadecanol;

aromatic ethers, such as: methoxy-1-naphthalene, 2-methoxy-naphthalene and diphenyl 'ät ago (DPA);

11) aliphatic aldehydes such as: nonanal, decanal and undecanal;

aromatic aldehydes, V7ie e.g .: phenylacetaldehyde; 409838/1028

12) Acetals from the above-mentioned aldehydes and above-mentioned alcohols such as, for example, glycol acetal of 2,4-dimethyl-tetrahydrobenzaldehyde, dimethylacetal of phenylacetaldehyde, "pentranol-diethyl-acetal" (DRAGOCO), resedy acetal (DRAGOCO) ;

13) aliphatic ketones whose melting point is below 50 °

and their vapor pressure at 110 ° C. is more than 1.33 mbar, such as, for example, methyl hexyl ketone, methyl nonyl ketone, methyl heptenone; cycloaliphatic ketones, such as, for example: "Musk-Keton" (NITINE INC.);
aromatic ketones, such as, for example: benzophenone;

14) aliphatic, cycloaliphatic and aromatic esters, such as esters of alkanols and alkenols, cycloalkyl alcohols or phenylalkyl alcohols and lower fatty acids and esters of lower fatty alcohols and pelargonic acid, Caprinspire, lauric acid, benzoic acid, cumin

acid, phenylacetic acid, cinnamic acid, salicylic acid, anisic acid or methoxycinnamic acid; e.g. 6-methyl-5-hepten-2-ylacetate, Methyl laurate, methyl caprate, dimethyl fumarate, diallyl fumarate, n-hexyl acetate, 2-hexenyl acetate, dimethyl succinate, Dimethyl maleate, diethyl succinate, diethyl maleate and cyclohexanol.

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Preferred in the preparations according to the invention are e.g .:

Pine oil, turpentine oil, spruce needle oil, sandalwood oil, fennel oil, camphor oil; d-limonene, camphene, cedar;

Diinethyl succinate, diethyl succinate, dimethyl maleate, dimethylraaleate, Bornyl acetate, isobornyl acetate, linalyl acetate, linalyl propionate, geranyl acetate, citronellyl acetate,

Menthyl acetate, n-hexyl acetate, 2-hexenyl acetate;

Isoc3 ^r clocitral, citral, phenylacetaldehyde dimethylacetal;

Menthol, linalool, cinnamon alcohol, as well as o-, m- and p-cresol ;

Camphor, fenchone; Diphenylmethane, diphenyloxide, diphenyl.

The preferred volatile agents (E) have a vapor pressure at 30 ° C between 0.013 mbar and 0.66 mbar, and usually a pleasant odor that does not irritate the mucous membranes.

Diphenyl ether, whose vapor pressure, Odor and compatibility in the preparations according to the invention is very satisfactory.

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Preparations according to the invention which diphenyl ether contain in weight ratios of about 1: 1 to the phosphoric acid ester, show for a long time, E.g. 3 to 4 months, a very good, regular release of the phosphoric acid ester, as well as an almost complete release of the existing active ingredient.

If the preparations according to the invention have a volatile, contain the odor of the composition influencing agent (E), this is preferably in Amounts from 0.1 to 3 parts by weight and optimally in amounts from 0.5 to 1 part by weight (U) per part by weight Phosphoric acid ester present in the preparation.

The amount of volatile agent (E), which in the invention Preparations used is preferably dimensioned so that they are in the same Period evaporates like the phosphoric acid ester, so that the consumer can easily take it to the then occurring " Change in the smell of the preparation notices that the phosphoric acid ester release and thus the insecticidal Effect has fallen below the effective limit.

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Among the up to E different from the components A additives, the total amount thereof is preferably 30 parts by weight of 7 _3, based not exceed on the total weight of the preparation are additional insecticides and / or insect repellent agent preferably in an amount of etvja 0.5 to 30 weight .-% and optimally from about 2 to 15 wt. X ₅ based on the total weight of the preparation in the latter.

As additional insecticides one can e.g. 1,2,3,4,5,6 »Hexa ~ chlorocyclohexane (and in particular its 7-isomer, known under the name "Lindane"), 1,4-dichlorobenzene, Use naphthalene, bromonaphthalene, dichloronaphthalene and aldrin.

As insect repellants, for example, the following can be used:

Almond acid alkyl esters such as commercial a'urehexyl ester and mandelic acid isobutyl ester; Isoborneol morpholine acetate, dimethyl carbamate, diethyl phthalate, lower alkyl tartrates such as diisopropyl tartrate, 2-ethyl-l, 3-hexanediol, 2-cyclohexylcyclohexanol, 2-phenylcyclohexanol, dimethylhexahydrophthalate, Diethyl hexahydrophthalate, pentane l, 5-diyl dipropionate, ß-tetralol, 1,2,3,6-tetrahydrophthalimide,

with
Amylbutoxyacetamide and / lower alkyl radicals K, K - disubstituted

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te formamides and acetamides, such as dimethylformamide, diethy! formamide, dimethylacetamide, diethylacetamide, Dipropylacetamide and dibutylformamide.

As additives useful dispersants are those having a low HLB value, preferably propylendiammoniumdioleat N-octadecyl between 1.5 and 6, such as salts of higher fatty acids and higher fatty amines, such as N-Hexadec3 ^r l-propylendiammoniumdioleat, and N-

as

Octadeeenyl-propylenediammonium dioleate / non-ionic surfactants such as "block copolymers", which are ethylene oxide-propylene oxide copolymers.

Additional diluents are particularly non-pesticidal Phosphoric acid esters, such as methyl, ethyl, butyl, octyl, decyl, dodecyl, phenyl, cresyl and Diphenyl triester of phosphoric acid suitable.

Inorganic fillers are mainly pyrogenic silicon dioxides with preferably spherical particles, whose mean diameter is in the range of 5 to 50, preferably 5 to 20 millimicrons, natural fossil and non-fossil silicon dioxides, artificial precipitated silicon dioxides, inert metal oxides, water-

409838/1028

free calcium sulfate, brick, pumice stone i / e-n- · - ·· Kulite, kaolin, dried clay, calcium carbonates Pyrophyllite, dolomite, glass fibers, gypsum and talc can be used.

Wood flour, cellulose and starch, for example, can be used as organic fillers.

The preparations according to the invention can take the form of a Have plate, a hollow cylinder, a granulate or a molded decorative article. You can also form a coating on an inert substrate. The preparations according to the invention preferably have in the form of granules.

Such granules are placed in a casing which is suitable for the Active substance vapors is permeable, packaged and the like preserved evaporator hung in a room. The granules advantageously have an average Diameter from 0.5 to 3 mm, preferably from 1 to 2.5 mm.

Before use, the preparations according to the invention are in an impermeable to the volatile substances Case, e.g. in a metal can or in a

either

Packing made of a / outside or preferably 'inside metallized Plastic wrap kept.

The preparations according to the invention can be prepared by simply mixing the constituents at one temperature

40 9 8 38/1028

240837Q

between 50 ° C and 200 ° C obtained v / earth, where-im In general, a temperature below 100 ° C is sufficient and the optimum temperature is that at which the constituents are miscible in the chosen proportions and this temperature preferably allows it to enable a liquid state by melting or dissolving normally solid components.

If the preparations according to the invention Contain thickeners, their production may take longer and one of the following procedural measures make necessary:

1) Uniform heating with constant stirring of the ketone (B) and the thickeners, dispersants and Stabilizers and stirring until a homogeneous liquid mass is obtained, the temperature of which is between 50 and is 200 ° C;

2) If necessary, addition of the volatile organic agent (E) in the liquid state and homogenization;

3) addition of the phosphoric acid ester and subsequent homogenization;

4) Conversion into forms which are cooled to 40/50 ° C "; or

1) Uniform heating to a temperature of 50/150 ° C with constant stirring of the mixture containing the phosphoric acid ester and optionally the thickener contains, with 10 to 20% by weight of an 409838/1028

240837Ö ³¹ "

Ketone (B) is the intended amount until a homogeneous melt is obtained;

2) adding the remainder of the molten ketone that is the contains other additional substances and homogenization by stirring;

3) Conversion of the mass into the forms, as already mentioned above ·

Prepared in this way, the preparations according to the invention are solid at room temperatures and have a very good dimensional stability.

The preparations can be in any form as shaped articles, for example such as it is described in French patent 1,562,932.

They have clear advantages over the preparations known up to now; so is the release of the volatile active ingredients, i.e. components (A) and (E) _; much more constant and generally higher and still more even than with the evaporators known up to now. Even

409833/1028

is the yield of active ingredient at the end of the period of action much more complete than with the previously known vaporizers.

The advantages of the preparations according to the invention are illustrated in the following studies and examples: where the numbers represent parts by weight.

example 1

Two rows of four solid blocks each are made, those described in the following under I-A and I-B Preparations exist.

I-A I-B

DDVP 25 .25

Stearon - 40

Paraffin 60-62 ⁰ C AO -.

Diphenyl ether 20 20

Aluminum distearate 4 - 4

Isooctyiepoxystearate 10 10

EDTA Na ₂₃ Ca 1 1

£ 09833/10

These blocks are made in the following way:

The paraffin (preparation 1-A) or the stearon (preparation 1-B) are brought to a temperature of 95 ° C. with constant stirring. Once the mixture has melted is, one adds aluminum distearate, heats the mixture with constant stirring further with a temperature increase of 1 ° C per minute up to one Temperature of 100-110 ° C. The mixture then obtained is quickly cooled. If the mix is a

When the temperature has reached 95 ° C, the

there
remaining components / to ^ and after homogenization, the molten mass is poured into stainless steel molds suitable for the formation of hollow cylinders.

As soon as the temperature of the mass in the molds in contact with the ambient air has dropped to about 20 ° C, remove the hollow cylindrical blocks from the molds.

The dimensions of the blocks thus obtained are as follows

Height of the cylinder: 10 cm, outer diameter: 4.5 cm Diameter of the cavity: 2.0 cm

Each block weighs 100 + Ig. "

S. ■■

4098 3 8/1028

Comparison search

Four blocks of each row were hung in a ventilated room, the temperature to 22 - held for 2 ° C _u w and RDE in which the relative humidity was 65-5.

The four suspended blocks were at regular time intervals weighed.

The biological effectiveness was determined by the following test method tested: one piece of each preparation the one surface

of 10 cm was exposed immediately after production and after a period of 15, 30, 60 and 99 days, each in a 40-liter chamber, into which 50 polyvalent-resistant flies were inserted after 30 minutes. Temperature: 23 ° C. ReI. Humidity: 60 %. Each attempt was carried out in duplicate.

After 1, 2, 3, 4, 6, 7 and 8 hours, the number of insects that had fallen was counted and the result was given as a percentage (KD 7 ") of the flies that had fallen in each count.

The results obtained are summarized in the following tables:

409838/102 8

8201/868607

Table I. Evaporation rate

I - A
Days of imposition 1 day 7 days 15 days 30 days • 9 days * I - B
Days of imposition 1 day 8 days 15 days 30 days I. 90 days* Total weight loss
of a block 0.39Og _- 1.56g 2.77g 4.58g 9.70g 0.680g 3.76g 6.37g 9.57g 15.23g ϊ
i
t
H Average,
daily evaporation
rate of DDVP + DPA ** 390mg 155mg 174mg 116mg 54mg 680mg 437mg 374mg 169mg 67mg I.
Yield after 90
Days * (based on
Initial amount of the DDVP) 23% 36.6%

* End of effectiveness ** Diphenyl ether

O CO CO <] O

Table II Biological effectiveness

1 day I. 30 days - A 99 days 1 day I - B. 60 days I. 99 days Duration of imposition - ^ 60 days 30 days Effective time
^ (Hour 0 0 2 3 7th 0 Percent fly in
Supine position
KD% after 1 hour 41 1 8th 9 10 53 19th 0 2 hours 85 8th 8th 15th 65 91 0 0 3 " 94 25th 14th 21 97 95 63 67 4 " 98 50 22nd 51 0 99 92 83 5 " 0 70 44 86 0 0 0 94 6. " 0 80 92 0 0 0 0 0 7 " 0 0 99 0
I. 0 0 0 0 8th "
1 0 0

2 ^ 08370

Table III

Hardness properties

Penetration after.
ASTM 1321-61T 'I - A I - B 0.66 mm 0.60 mm

409838/1028

Example 2

First 529.9 kg of stearon are introduced into a mixer equipped with a FIUge! Stirrer and melted. ^{The temperature of the melt is kept at 125-14O 0} C with constant stirring at a speed of 400 rpm, and 60 kg of aluminum distearate are added. Stirring is continued until the mass has swelled completely, which is the case after 10 to 15 minutes. Then 150 kg of isooctyl epoxystearate and 10 kg of disodium calcium salt of ethylenediaminetetraacetic acid (EDTA) and 0.1 kg of a yellow, solvent-soluble azo dye such as Irgacetgelb 3 GLG (Color Index Solvent yellow 48) are added while the temperature of the melt is increased to 90 ⁰ C. At this temperature, the melt are 250 kg DDVP added and stirred, and after the temperature has dropped to 72-75 ⁰ C, the liquid mass is still well in a granulator known construction, for example in the German in the Offenlegv.ngsschrift 1,542,093 given, operating with ultrasound device described and granulated therein. For granulation in this device, an ultrasonic frequency of 7500 oscillations per second is used. If the diameter of the nozzle opening is 0.1 mm and the liquid pressure used is 0.4-0.5 bar, granules with an average particle size of 0.6 mm are obtained.

409838/1028

Example, 3

Example 2 is repeated, but the following amounts of the constituent parts are used:
329.9 kg of stearon

60 "aluminum distearate

200 "diphenyl ether, which is composed of the swollen melt with

150 "isooctyl poxystearate,
10 "disodium calcium EDTA salt and 0.1" Irgacetgelb 3 GLG (CI. Solvent yellow 48) were added

will; finally 250 "DDVP.
Example 4

Example 2 is repeated with the following amounts of the ingredients:

559.9 kg of stearon

30 "aluminum distearate 150 " isooctyl epoxystearate 10 '"disodium calcium EDTA salt

0.1 "Irgacetgalb 3 GLG (CI. Solvent yellow 48). Example 5

There are granules of the following composition as in the example 2 manufactured:

DDVP 25

Stearon -. 53

Aluminum distearate 6

409838/1028

Isooctylepoxystearate ± q OZf) Q ^ If)

EDTA Ka ₂ Ca: ι.

100 g of these granules are packed in a fabric made of polyamide fibers.

An evaporator obtained in this way was hung in a ventilated room, the temperature of which is kept at 22 + 2 ° C and in which the relative humidity is 65 + 5%.

Such a vaporizer was made at regular time intervals weighed. -

The biological effectiveness was also tested using the test method given in Example 1.

The results obtained are summarized in the following tables.

Table IV Vapor fungi sr ate

after 2
Weeks after 4
Weeks after 6 -
Weeks after 8
Weeks Total weight loss of
100 g granules 3.5 g 6.8 g 9.3 g 11.7 g Average daily
Evaporation * 0.25 g 0.236g O ₅ 178g 0.172 g

409838/1028

Table V Biological effectiveness

Duration of imposition
Effective time in
Minutes 7 days 30 days 60 days - 40 Percent fly in
Supine position 72 after 15 minutes 13th 10 88 30 " 33 25th 100 45 " 62 45 - 60 " 80 76 - 75 " 90 88 - 90 " 95 94 105 " 97 97 120 " 100 100

409838/1028

These results show that the preparations according to the invention allow evaporator bodies to be produced which have the following advantages over the compositions known hitherto demonstrate:

a) a higher delivery of DDVP if it is sufficiently uniform Evaporation during the entire service life,

b) a better yield of DDVP

c) greater hardness or strength.

d) an equally high biological effectiveness during the entire service life ..

The following examples illustrate the invention Preparations which as in Example 1 as a block oder'wie in example 2 can be shaped as granules: in the tables below, the quantities indicated Parts by weight.

4098 38/102

Examples 6 to 13

6th 7th 8th 9 10 11 12th 13th DDVP 25th 25th 25th 25th 25th 25th 25th 25th Stearon 38 38 38 - - - - - Lauron - - - 38 38 38 38 38 Diphenyl ether - - 20th - - - - Diphenylmethane 20th - - - 20th - - - Bornyl acetate - 20th - - - 20th - - Citronellyl acetate - - 20th - - - 20th - Diphenyl - - - - - - - 20th Aluminum distearate 6th 6th 6th 6th 6th 6th 6th 6th Isooctyl epoxystearate 10 10 10 10 10 10 10 10 EDTA Na ₂ approx 1 1 1 1 1 1 EDTA 1 1

409838/1028

Examples ] Λ to 21

- - DDYP 14th 25th 15th 16 17th 18th 19th 20th 21 Stearon 37 25th 25th 25th 25th 25th 25th 25th Lauron - 37 37 - - - - - Diphenyl ether - - - 37 37 37 37 37 Dipheny! Methane 20th - 20th - - - - Bornyl acetate - - - - 20th - - - Citronellyl acetate - 20th - - - 20th - - Diphenyl - - 20th - - - 20th - Elvax 250 ^ 7th - - - - - - 20th Isooctyl epoxystearate 10 7th 7th 7th 7th 7th 7th 7th EDTA Na ₂ Ca ^ 1 10 10 10 10 10 10 10 1 1 1 1 1 1 1

(1) copolymer of vinyl acetate / ethylene with 27 to 29% by weight of vinyl acetate, manufactured by DOW CHEMICAL CO.

(2) Dimethyldialkylmontmorillonitammoniumsalz in which each of the two alkyl groups having an average of 17 carbon atoms, supplied by ABBEY Chemical Ltd., London, England.

(3) disodium monocalcium salt of ethylenedianlntetraacetic acid.

409838/1028

Examples 22 to 29.

22nd 23 24 25th 26th 27 28 29 DDVP 25th 25th 25th 25th 25th 25th 25th 25th Stearon 35 35 35 Lauron - - - 35 35 35 35 35 Diphenyl ether - - - 20th - - - - Diphenylmethane 20th - - - 20th - - - Bornyl acetate - 20th - - - 20th - - Citronellyl acetate - - 20th - - - 20th - Diphenyl - - - - - - - 20th Bentone 38 ^ 9 9 9 9 9 9 9 9 Isooctylepoxys tearat 10 10 10 10 10 10 10 10 EDTA Na ₂ approx 1 1 1 1 1 1 1 1

409838/1028

Examples 30 to 37

30th 31 32 33 34 35 36 37 DDVP 25th 25th 25th 25th 25th 25th 25th 25th Stearon 57 57 55 - 44 44 44 44 Lauron - - - 44 - - - - Diphenyl ether - - 20th 20th - - - Dipheny! Methane - - - - - 20th - - Bornyl acetate - - - - - - 20th - Citronellyl acetate - - - - - - - 20th Aluminum distearate 7th - - - - - - - Elvax 250 ^ ' - 7th - - - - - - Bentone 38 ^ ^ - - 9 - - - - - Isooct3 ⁷ lepoxys tearat 10 10 10 10 10 10 10 10 EDTA Na ₂ Ca ^ 1 1 r-l
i 1 r-l 1 1 1

With pie le 38 to 4.5

38 39 40 41 42 A3 44 45 DDVP 25th 25th 25th 25th 25th 25th 25th -
25th Myriston 38 - - - - - - - Palmiton - 38 - - ■ - - - - Arachidon - - 38 - - - - - Behenon - - - 38 - - - - Oleon - - - - 38 - - - Linoloa- - - - - - 38 - - Heneicosan-2-one - - - - - - 38 - Docosan-2-one - - - - - - - 38 Diphenyl ether 20th 20th 20th 20th 20th 20th 20th 20th Aluminum dis t earat 6th 6th 6th 6th 6th 6th 6th 6th Isooctyl epoxystearate 10 10 10 10 10 10 10 10 EDTA Na ₂ Ca ( ³ ) 1 1 1 1 1 1 1
i 1

40 983 8/1078

Examples 46 to 53

I. DDYP 46 47 48 49 50 51 52 53 Eikosan ~ 3-one 25th 25th 25th 25th 25th 25th 25th 25th Cyclopentadecanone 38 - - - 57 - - - Cycloheptadecanone - 35 - - - 57 - - Aluminum distearate - - 37 37 - 57 55 Bentone 38 ⁽² >
Elvax 250 6th - - - 7th _ - _ Diphenyl ether - 9 - - - - - 9 Dipheny! Methane - - 7th 7th - - 7th - Bornyl acetate 20th - - - - - - - Citronellyl acetate - 20th - - - - - - Isooctylepoxys tearat - - 20th - - - - - EDTA Na ₂ Ca ( ³ ) - - - 20th - - - - 10 10 10 10 10 10 10 10 1 1 1 1 1 1 1 1

409838/1028

Examples 54 to 61

54 55 56 57 58 59 60 61 DDVP 25th 25th 25th 25th 25th 25th 25th 25th Stearon 42 42 42 42 42 42 42 42 Pine oil 15th - - - - - - Turpentine oil - 15th - - - - - - Spruce needle - 15th - - - - - Sandwood oil - - - 15th - - - - Fennel oil - - - - 15th - - Camphor'dl - - - - - 15th - - d-limonene - - - - - - 15th - Camphene - - - - - - 15th Alurainium distearate 7th 7th 7th 7th 7th 7th 7th 7th Isooctylepoxys t earat 10 10 10 10
1 10
1 10 10 10 EDTA Na ₂ Ca ^ ³⁾ r-i 1 1 1 1 1 1 .1

409838/1028

62 to 69

62 63 \ 7th 64 65 66 67 68 69 DDVP 25th 25th 10 25th 25th 25th 25th 25th 25th Stearon 42 42 r-l 42 42 42 42 42 42 Cedren 15th - - - _ - Benzyl acetate - 15th - - - - - - 2-hexenyl acetate - - 15th - - - - - n-hexyl acetate - - 15th - - - - Phen3 ^T lacetaldehyde - dimethyl acetal - - - - 15th - - - menthol - - - - - 15th - - Terpineol - - - - - - 15th - Cinnamon alcohol - - - - - - 15th Aluminum distearate 7th 7th 7th 7th 7th 7th 7th Isooctyl epoxystearate 10 10 10 10 10 10 10 EDTA Well _? Approx t-l I-I 1 1 1 r-l 1

409838/1028

Examples 70 to 77_

r
70 71 72 73 74 75 76
I. 77 DDVP 25th 25th 25th 25th 25th 25th 25th 25th Lauron 42 42 42 42 42 42 42 42 o.m.p. cresol 15th - - - - - - - - Camphor - 15th - - - - - - Fenchon - - 15th - - - - Citronellol - - - 15th - - - - Geraniol - - - - 15th - - - Ment hylac e tat - - - - - 15th - - Terpinoles - - - - - 15th - Borneol - - - - - - - 15th Aluminum dispenser 7th 7th 7th 7th 7th 7th 7th 7th Isooctyl epoxystearate 10 10 10 10 10 10 10 10 (3)
EDTA NA ₂ approx 1 1 1 EDTA 1 1 1 I-t 1

409838/1028

Examples 79 to 86

79 - 1 80 - 1 81 4th - 1 82 83 84 85 - 1 86 4th - DDVP 15th 40 15th 40 40 40 20th j
15th - Lauron 60 - - - - - - - 1
0.1
—.—. , J Stearon - 20th 80 - - - - 79.9 Stearophenon - - - 10 - - - 2-acetylnaphthalene - - - - 10 - - - 4-chloropropiophe-
non - - - - - 10 - - Diphenyl ethers 20th 20th - 40 40 40 72 Aluminum dis tearat 4th 9 6th 6th 6th 7th Isooctyl-9, 10-epo-
xystearate 3 3 3 EDTA Ka ₂ Ca (3)
yellow azo dye 1 1 1

409838/1028

Examples 87 to 90

87 6th 88 - 3 - 89 1 90 0.1 25th 11 25th 25th 25th DDVP 38 - - - - Stearon - - 38 38 38 Lauron 20th - - Diphenyl ethers - 28 -. 20th Diphenylmethane 6th 6th 6th Aluminum disuearate 10 10.9 Isooctyl 9,10-epoxystearate - - epoxidized soybean oil Epichlorohydrin

409838/1028

Claims (64)

Claims 1. Hydrophobic insecticidal preparation, characterized in that it is made of higher molecular weight hydrocarbons is free and contains the following components: (A) as an insecticidal compound 15 to 40 parts by weight of a phosphorus-containing ester which has a vapor pressure at 20 ° C of at least 0.013 mbar and of the formula R "R ¹ " RO '0 C- -C ^f k-1 R ^f where X is an oxygen or sulfur atom, R and R ', independently of one another, are alkyl radicals with 1 to 4 carbon atoms, Y is a halogen atom with an atomic number of at most 35, R "and R" ¹ , independently of one another, are a hydrogen atom, a halogen atom with an atomic number of not more than 35, denote a methyl group or an ethyl group and k is 1 or 2, (B) as a carrier substance 10 to 80 parts by weight of a higher ketones with a melting point above 50 ° C 409838/1028 and its vapor pressure at 110 ° C at most 1.33 ntbcV is, ■ - (C) 0.1 to 25 parts by weight of a stabilizing agent for the ester A, (D) 0 to 30 parts by weight of a hydrophobic thickener. (E) 0 to 75 parts by weight of an organic, volatile agent which increases the solubility of the ester (Λ) in the carrier substance (B) and preferably also has a beneficial effect on the odor of the ester (A), whose steam pressure ■ at 30 ° C 0.066 to .6.66 uibar and at 100 ⁰ C is at least 1.33 mbar the proportion of (D) and (E), based on the total weight of the preparation, being at least 4 "L. 2. Preparation according to claim 1, characterized in that it is a ketone of the formula as component (B) R ₁ CR ₉ (II) contains where (a) R and R ₂ each represent an alkyl or alkenyl group mean, where both together 16 to 60 carbon atoms included, or 409838/10? » (b) R is a phenyl or a naphthyl radical, which 28370 by one or more chlorine atoms, bromine atoms, alkyl groups and / or acetyl groups may be substituted, and R ^ is an alkyl or alkenyl radical having 11 to 25 carbon atouien mean, or (c) R and Ry together represent an alkylene or alkenylene group with at least 14 carbon atoms, represent. 3. Preparation according to claim 2, characterized in that it is a di-alkyl or di-alkenyl ketone as component (B) with at least S carbon atoms in the alkyl chain contains. 4. Preparation according to claim 2, characterized in that it is a 2-alkanone with a total of as component (B) Contains at least 19 carbon atoms. 5. Preparation according to claim 2, characterized in that it is a 3 ~ alkanone with a total of as component (B) Contains at least 16 carbon atoms. 6. Preparation according to claim 2, characterized in that that it contains as component (B) an alkylphenyl ketone with at least 11 carbon atoms in the alkyl radical. 409838/1028 7. Preparation according to claim 2, characterized in that it is an alkyl naphthyl ketone with 1 to as component (B) Contains 4 carbon atoms in the alkyl radical. - "■ - 8. Preparation according to claim 2, characterized in that it has a monocycloaliphatic ketone as component (B) contains at least 15 carbon atoms. 9. Preparation according to claim 2, characterized in that that they are chlorinated and / or brominated as component (B) Contains alkyl phenyl ketone with 1 to 4 carbon atoms in the alkyl radical. 10. Preparation according to one of claims 1 to 9, characterized in that that as component (B) pelargon, caprinone, lauron, myriston, palmiton, stearon, arachidon, behenon, oleon, Iiinolon, Linolenon, Nonadecan-2-one, Eikosan-2-one, Heneikosan-2-one, Dokosan-2-one, Trikosan-2-one, Eikosan-3-one, Cyclopentadecanone, Contains cyclohexadecanone or cycloheptadecanone. 11. Preparation according to one of claims 1 to 10, characterized in that that they as component (B) myristophenone, palmitophenone, stearophenone, arachidophenone, 3,4-dichloroacetophenone, 4-chloropropiophenone, Contains 2,4-dibromoacetophenone or 4-butoxyacetophenone. 409838/1028 12, preparation according to any one of claims 1 to 11, characterized in that it is 2-acetylnaphthalene as component (B) or contains 1-acetylnaphthalene. 13- Preparation according to one of claims 1 to 12, characterized in that it is used as a stabilizing agent (C) an epoxy compound, a non-heterocyclic amino compound, nitrogen-containing heterocyclic compound, benzodioxole compound, azo compound, optionally in the form of a metal complex, a compound of divalent sulfur or contains molecular sulfur or a mixture of such stabilizing agents. 14. Preparation according to one of claims 1 to 13, characterized in that it is 0.1 to 50 as component (C) Weight%, based on the weight of the phosphoric acid ester, one Contains epoxidized oil. 15. Preparation according to claim 14, characterized in that it is an epoxidized gel, epoxidized soybean oil, halogenated Epoxyalkane and / or alkyl epoxystearate with 4 to 18 carbon atoms and preferably contains 8 carbon atoms in the alkyl chain. 16. Preparation according to one of claims 1 to 15, characterized in that it is 0.5 to 10 as component (C) 409838 / 102B % By weight, based on the weight of the phosphoric acid ester (A) of a non-heterocyclic amino compound or nitrogen-containing compound contains heterocyclic compound. 17. Preparation according to one of claims 1 to 16, characterized in that it as component (C) 0.1 to 5 Gew.7o, based on the weight of the phosphorus ^y ureesters (A) an azo compound or a metal complex ?; an azo verb. 18. Preparation according to one of claims 1 to 17, characterized characterized in that they are as component (c) 0.05 to 6% by weight, based on the weight of the phosphoric acid ester (A) contains elemental sulfur or compounds of divalent sulfur. 19. Preparation according to one of claims 1 to 18, characterized in that it as component (G) 0.2 to 10 wt.%, based on the weight of the phosphoric acid ester (A), a benzodioxole, contains. 20. Preparation according to one of claims 1 to 19, characterized in that it is used as component (C) 2 to 6 % By weight, based on the weight of the phosphoric acid ester (A), of an amino acid salt. 409838/1078 2sQ8370 21. Preparation according to claim 20, characterized in that the amino acid salt, the disodium and
Calcium salt. which is ethylenediaminetetraacetic acid. 22. Preparation according to one of claims 1 to 21, characterized in that the stabilizing agent
(C) consists of a mixture of acid-binding stabilizers and stabilizers which act against the protonization of the phosphoric acid ester. 23. Preparation according to claim 22, characterized in that the stabilizing agent (C) consists of a mixture of isooctyl epoxystearate with disodium monocalcium salt of ethylenediaminotetraacetic acid in weight ratios of about 10: 1. 24. Preparation according to one of claims 1 to 23, characterized in that it as component (D) at least contains a salt of a higher fatty acid. 25. Preparation according to claim 24, characterized in that component (D) is an aluminum, magnesium, calcium, Strontium, barium, lithium or cobalt salt of a higher fatty acid. 409838/1028 26. Preparation according to claims 24 and 25, characterized in that that they there · .. fatty acid salt in an amount of 3 to 20% by weight, based on the total weight of the preparation, contains. 27. Preparation according to one -ier claims 24 to 26, characterized in 'that they al ^ fatty acid salt 3 to 15 wt. J ₀ of an aluminum mono-, di- ur.d / or -tristearates and / or an aluminum or Calciumltctäts contains. 28. Preparation according to one of claims 1 to 27, characterized in that it as component (D) at least an ammonium salt of dimethyldialkylmontmorillonite with 14 bis Contains 18 carbon atoms in the alkyl group. 29. Preparation according to claim 28, characterized in that it is based on 6 to 8% by weight as component (D) based on the total weight of the preparation, a dimethylalkylraontmorillonite Contains in an amount of 6 to 8% by weight. 30. Preparation according to claim 29, characterized in that the alkyl group of dimethyldialkylmoiitmorillonite contains an average of 17 carbon atoms. 40 983 8/102 8 31. Preparation according to one of claims 1 to 30, characterized in that it as component (D) at least a thermoplastic polymer or copolymer whose molecular weight is over 1000 contains. 32. Preparation according to claim 31, characterized in that it is a thermoplastic polymer cellulose ester, Cellulose ethers, polymers or copolymers of vinyl esters, Vinyl ketals, vinyl chloride, vinyl pyrrolidones, lower olefins, styrenes, acrylic or methacrylic acid esters and / or allyl esters or epoxy resins less than 1 gram equivalent Epoxy groups per kg resin or polyester resins or polyurethanes or Contains coumarone-indene resins or mixtures of such thermoplastics. 33. Preparation according to claim 32, characterized in that it contains the thermoplastic polymer in an amount of 5 to 30% by weight, based on the total weight of the preparation. 34. Preparation according to one of claims 31 to 33, characterized in that it consists of a copolymer as component (D) Contains vinyl acetate and ethylene with a content of 25 to 30% by weight, based on the total weight of the copolymer, of vinyl acetate. 4 (Γ9 838/102 8 35. Preparation according to one of claims 1 to 34, characterized in that it is used as component (E) 5 to 40 Weight%, based on the total weight of the preparation, one volatile substance which affects the odor of the ester (A). 36.. Preparation according to Claim 35, characterized in that it contains natural essences and / or theirs as component (E) Hydrocarbon, alcohol, phenol, ether, aldehyde, ketone and ester components of the same, synthetic, of the components mentioned various aromatic hydrocarbons, aliphatic, cycloaliphatic, aromatic ethers, Contains aldehydes, ketals, ketones and / or esters. 37. Preparation according to claim 36, characterized in that it contains as component (E) anisole, aspic oil, lemon oil, citronella oil, Eucalyptus oil, geranium oil, lavender oil, lavandin oil, lemongrass oil, Mandarin oil, peppermint oil, orange oil, petitgrain oil, pine oil, Vetiver oil, rosemary oil, copal oil, turpentine oil, spruce needle oil, cedar oil, thuja oil, cypress oil, juniper berry oil, tuberos oil, Iris oil, violet flower oil, ginger oil, cardamom oil, pepper oil, Betel oil, myricin oil, hop oil, sandalwood oil, bitter orange flower oil, Basil oil, bergamot oil, bitter bitter orange peel oil, rock oil, cumin seed oil, fennel oil, clove oil, marjoram oil, Myrtle oil, patchouli oil, mullet oil, thyme oil, camphor oil, cinnamon oil, rosewood oil, laurel oil, rose oil, bitter almond oil, acacia oil, stemanis oil or jasmine oil or mixtures of such oils. 409838/1028 38. Preparation according to one of claims 35 and 36, characterized in that it is used as component (E) cymene, Ocymen, Phellandren, Terpinen, Terpinolen, Bornylen, Camphan, Isocamphane, Camphene, Caran, Caren, Fenchan. Fenchen, Menthadiene, menthane, menthene, pinene, myrcene, thuyan, tiurya, Verbenen, Cedren, Sabinen, Sylvestrcn or Norcamphen or mixtures of such compounds contains. 39. Preparation according to one or more of claims 35 to 38, characterized in that it is used as component (E) Rhodinol, Citronellol, Geraniol, Linalool, Nerol, Terpineol Menthol, borneol, isoborneol, fenchyl alcohol, menthandiol, piperitol, carol, myrtle or verbenol or Contains mixtures of such compounds. 40. Preparation according to one or more of claims 35 to 39, characterized in that it is used as component (E) Anol, Chavicol, Charvacrol, Thymol, Safrol. Or Estragole or mixtures of such compounds. 41. Preparation according to one or more of claims 35 to 40, characterized in that it is used as component (E) Anethole, eugenol, eucalyptol, safrole, geranyl alkyl ethers or phenylalkyl ethers or mixtures of such compounds. 40983B / 1028 2,08370 42. Preparation .according to one or more of the claims 35 to 41, characterized in that it contains citronellal, geranial, santalal, anisaldehyde, cinnamaldehyde, Contains vanillin, phellandral, isocyclocitral or cuminaldehyde or mixtures thereof. 43. Preparation according to one or more of the claims 35 to 42, characterized in that they contain anisketone, menthone, ionone, iron, fenchone, camphor, carvone, Pulegon, Carvenon, Isopulegon, Piperiton, Verbenon or Thuyon or mixtures of such compounds. 44. Preparation according to one or more of claims 35 to 43, characterized in that it is used as component (E) Geranyl acetate, linalyl acetate, eugenyl acetate, bornyl acetate, isobornyl acetate, Contains linalyl propionate, citronellyl acetate or menthyl acetate or mixtures of such compounds. 45. Preparation according to one or more of claims 35 to 44, characterized in that it is used as component (E) Diphenymethane, diphenylethane or diphenyl or mixtures contains such compounds. 46. Preparation according to one or more of the claims 35 to 45 j characterized in that it is used as component (E) Methoxy-1-naphthalene, methoxy-2-naphthalene, or diphenyl ether or mixtures of such compounds. 47. Preparation according to one or more of the claims 35 to 46, characterized in that they are used as component (E) nonanal, decanal, undecanal or phenylacetaldehyde or mixtures contains such compounds. 48. Preparation according to one or more of claims 35 to 47, characterized in that they are glycol acetal as component (E) des 2,4-dimethyl-tetrahydroberizaldehyde, dimethyl acetal des Phenylacetaldehydsj "Pentranol-diethyl-acetal" (DRAGOCO) or Resedylacetal (DRAGOCO) or mixtures of such compounds. 49. Preparation according to one or more of the claims 35 to 48, characterized in that it contains methyl hexyl ketone, methyl nonyl ketone, methyl heptenone, "Musk ketone" as component (E) (NITINE INC.) Or benzophenone or mixtures of such compounds contains. 50. Preparation according to one or more of the claims 35 to 49, characterized in that they are used as component (E) esters of alkanols, alkenols, cyclohexyl alcohols or phenylalkyl alcohols and lower fatty acids or esters from lower fatty alcohols and pelargonic acid ^ capric acid, lauric acid., benzoic acid, £ 09838 / 10.28 Cumic acid, phenylacetic acid, cinnamic acid, salicylic acid, anisic acid or methoxycinnamic acid or mixtures of such esters. 51. Preparation according to claim 50, characterized in that it contains as component (E) acetate of 6 ~ methyl-5-hepten-2-ol, Methyl laurate, methyl caprate, dimethyl fumarate, diethyl fumarate, Diallyl fumarate n-hexyl acetate, 2-henenyl acetate, dimethyl succinate, Dimethyl maleate, diethyl succinate or diethyl maleate or mixtures the same contains. 52. Preparation according to one or more of claims 1 to 51, characterized in that it is used as component (A) Contains dimethyl 2,2-dichlorovinyl phosphate. 53. Preparation according to one or more of claims 1 to 52, characterized in that it is used as component (E) contains a volatile substance whose vapor pressure at 30 ° C is in the range from 0.013 to 0.666 mbar. 54. Preparation according to one or more of claims 1 to 53, characterized in that it contains 0.5 to 30% by weight, based on the total weight of the composition, of an additive consisting of a volatile insecticidal agent which is different from (A) ' , an insect repellent, a dye, pigment, bactericidal agent, fungicidal agent, additional diluent, dispersant, inert inorganic or organic filler or a mixture of such additives. \ ^: .. =, .. Λ 0 9 8 3 8/1 0 2 8 55. Preparation according to claim 54, characterized in that it contains an additional insecticide consisting of 1,2,3,4,5,6-7-hexaehlorcyclohexane, 1,4-dichlorobenzene, naphthalene, bromonaphthalene, Contains dichloronaphthalene and / or aldrin. 56. Preparation according to one of claims 54 or 55, characterized in that it is used as an insect repellent, Commercial acid alkyl esters, in particular mandelic acid hexyl ester or Mandelic acid isobutyl ester, morpholine acetate of isoborneol, Dimethyl carbamate, dimethyl phthalate, lower alkyl tartrates, Diisopropyl tartrate, 2-ethyl-1,3-hexanediol, 2i-cyclohexylcyclohexanol, 2-phenylcyclohexanol, dimethylhexahydrophthalate, Diethyl hexahydrophthalate, pentane l, 5-diyl dipropionate, jB-tetralol, 1,2,3,6 "tetrahydrophthalimide, amylbutoxyacetamide, with lower Alky! Radicals Ν, Ν-disubstituted formamides or acetamides, in particular dimethylformamide, diethylformamide, dimethyl acetamide, Contains diethylacetamide, dipropylacetamide or dibutylformamide or mixtures of such agents. 57. Preparation according to one or more of claims 54 to 56, characterized in that it is used as an additional Diluent an amide, a nitrile, a non-pesticidal Phosphoric acid esters, in particular their methyl, ethyl, propyl, butyl, octyl, decyl, dodecyl, phenyl, cresyl or diphenyl triesters contains. 40983 S / 10? 8 58. Preparation according to one or more of the claims 54 to 57, characterized in that it is an inorganic filler consisting of coagulated Siliciutridioxyd with preferably spherical particles, the mean diameter of which is in the range from 5 to 50 ηιμ, natural fossil or non-fossil Silica, artificial precipitated silica, inert metal oxides, anhydrous calcium sulfate, brick, pumice stone, vermiculite, kaolin, dried clay, calcium carbonate, Contains pyrophyllite, dolomite, glass fibers, gypsum or talc or a mixture of such fillers. 59. Preparation according to one or more of the claims. 54 to 58, characterized in that it is an organic Contains filler consisting of wood flour, cellulose fibers or starch. 60. Preparation according to one or more of the claims 1 to 59, characterized in that they. the shape of a plate, a rod, a prism, a roller of a hollow cylinder or a granulate " 61. Preparation according to one or more of the claims 1 to 60, characterized in that it is a molded decorative Article or a coating forms. 409838 / 1Ό28. 62. Preparation according to one or more of the claims 1 to 61, characterized in that they are impermeable to the volatile substances present in the preparation Case is included. 63. Preparation according to one or more of the claims 1 to 62, characterized in that they contain 25% by weight of DDVP, 40% by weight of stearon, 20% by weight of diphenyl ether, 4% by weight of aluminum distearate, 10 Wt% isooctyl epoxystearate and 1 wt%: one Stabilizer for DDVP. 64. Preparation according to claim 63, characterized in that the stabilizer is the disodium monocalcium salt Ethylenediamine tetraacetic acid is. i09833 / 1-028