WO2007093295A2

WO2007093295A2 - Oil-in-water formulation for arthropod and plathelminth control

Info

Publication number: WO2007093295A2
Application number: PCT/EP2007/000953
Authority: WO
Inventors: Thomas Gernot; Petra Krebs; Friedrich Koch; Nikolaus Müller; Beate Tombeux
Original assignee: Saltigo Gmbh
Priority date: 2006-02-16
Filing date: 2007-02-05
Publication date: 2007-08-23
Also published as: DE102006007549A1; WO2007093295A3

Abstract

The present invention relates to a formulation for arthropod and plathelminth control based on piperidine derivatives in oil-in-water formulations.

Description

Oil-in-water formulation for arthropod and platelet defenses

The present invention relates to a formulation for arthropod and platelet lineage defense based on piperidine derivatives in oil-in-water formulations.

It is known from EP 0 281 908 A1 and EP 0 289 842 A1 that certain piperidine derivatives can be used as agents for repelling arthropods (especially insects) and helminthic parasites. One of the most important structures is compound 1-

Piperidine carboxylic acid 2-hydroxyethyl-l-methylpropyl ester exposed and marketed under the

Wirkstofamen Icaridin and Bayrepel ^® established. This connection is not as

Pure substance, but distributed as a formulated liquid in the form of lotion. The usual concentrations of the active ingredient here are 1 to 40% based on the mass of

Formuherung.

As stable formulations, lotions based on these piperidine compounds as well as water and a volatile alcohol component have become established. As alcohol, physiologically compatible volatile solvents are used here. In addition to phenethyl alcohol and benzyl alcohol, these include monofunctional and polyfunctional aliphatic alcohols (alkanols, alkanediols, alkanetriols). These are, for example, ethanol, propanol, isopropanol, n-butanol, sec-butanol, propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, ethylene or propylene oxide based copolymeric polyether polyols (both block copolymers and random copolymers), 2-ethyl-1,3 Hexanediol, glycerin, trimethylolpropane, etc.

As an example of the state of this art, the following solubility series is given from a ternary system (icaridine, alcohol, water). These mixtures give each stable lotions. In addition to the stability, the viscosity of the formulations was determined in accordance with DIN 53019 of November 1983:

^l) Due to the measuring system it could only be determined for different formulations that their viscosity values are below 10 mPas

These lotions thus have a very low viscosity as a significant technical disadvantage

In some cases, this is so low that the viscosity outside the range of measuring devices for Viskombatsbestemmmung Therefore, a targeted and uniform product order is problematic for the consumer Another technical disadvantage of the lotions lies in the very high ethanol content This leads, on the one hand to deteriorated cosmetic properties

(Skin irritation) On the other hand, he prepares with values by 40% and problems with the

Fire behavior of these formulations These offer a considerable advantage, since the proportion of highly flammable formulation constituents can be significantly reduced

As an alternative to this, oil-in-water emulsions have been established in the pharmaceutical and cosmetic industries. They consist essentially of ternary systems of water, an oil component (for example a hydrocarbon mixture, mineral oil, cyclomethicone, linseed oil, apicose kernel, oleic acid, pinienol, ohvenol , Silicone oils, tallow, tung oil, mink oil, oleic acid, etc.) and a suitable mediating component in the form of a surface-active substance, for example an emulsifier or emulsifier system

Insect repellent formulations as emulsions based on the active ingredient N, N-diethyl-m-toluamide (DEET) are already known. For example, US Pat. No. 5,916,541 A1 describes emulsions containing insect repellent, a sunscreen agent and a film former. US Pat. No. 5,989,529 A1 also describes emulsions which are block polymers US 5,980,871 A1 describes emulsions containing an insect repellent active ingredient, an inorganic sunscreen agent and an anionic emulsifier

If these concepts are applied to oil-in-water formulations with pipendin repellents, it is found that the emulsifier systems found in DEET fail and the formulations that can be obtained are not stable. Simple replacement of the repellent component does not result

The invention therefore has for its object to provide stable oil-in-water formulations which have a low solvent / alcohol content and optionally a high viscosity

This object was achieved by a formulation for the defense of arthropods and Plathelmmthen containing the mixture • 1 to 40% by weight of a repellent

• 0 to 20% by weight of an oil

^β 0 to 3% by weight of a carbomer. Acrylic acid polymer or mixtures thereof and

0.1 to 20% by weight of an aliphatic ester, silicone polyether, glycerol, polydimethylsiloxane, 1'-oxybisoctane or their mixtures thereof and

17 to 98.9% by weight of water.

The formulations are clear and stable.

When using carbomer and / or acrylic acid polymers, it is advantageous to adjust the formulation with the aid of sodium hydroxide in a neutral pH range so that it does not cause skin irritation.

The formulation preferably has a viscosity of> 20 mPas measured according to DIN 53019 from November 1983.

The method for measuring the viscosity is given in the examples.

The formulation preferably additionally contains from 0.1% to 20% by weight of N-methylpyrrolidone, phenethyl alcohol, benzyl alcohol, an aliphatic alcohol, aliphatic ethers, aliphatic polyethers and / or mixtures thereof. This can increase the stability.

The formulation preferably additionally contains 0.1 to 20% by weight of ethanol, propanol, isopropanol, n-butanol, sec-butanol, propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, copolymeric polyether polyols based on ethylene or propylene oxide, 2-ethyl-1, 3-hexanediol, glycerol, trimethylolpropane and / or mixtures thereof.

As a repellent is preferably a piperidine derivative of the general formula:

wherein Ri 'and R ₂ ' are each independently alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl. Hydroxyalkiiryl. Cycloalkyl. Cycloalkenyl, cycloalkynyl, cycloalkoxy, cycloalkenoxy and cycloalkynoxy, and

n is 0 or 1 or mixtures thereof are used.

As a repellent preferably a piperidine derivative of the general formula is used where Ri 'and R ₂ ' independently of one another for Ci-Ci ₂ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, Ci-Ci ₂ hydroxyalkyl, C ₃ -C ₂₀ hydroxyalkenyl, C ₃ -C ₂₀ hydroxyalkynyl C ₃ -C ₀₂ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl, C ₃ -C ₂₀ cycloalkynyl, C ₃ -C ₂₀ cycloalkoxy, C ₃ -C ₂₀ cycloalkenoxy and C ₃ -C _{20 is} cycloalkynoxy, and n is 0 or 1, or mixtures thereof.

The repellent used is preferably 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl ester (icaridine) and 1- (3-cyclohexen-1-ylcarbonyl) -2-methylpiperidine both as a racemic mixture and as a chiral compound, for example (1S, 2'S). - l- (3-cyclohexen-1-ylcarbonyl) -2-methylpiperidine used. Very particular preference is given to 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl ester (icaridine).

As oils are preferably the repellent itself, mineral oils, polycyclic aromatic hydrocarbons, paraffin oils, silicone oils such as polysiloxane, cyclosiloxane, methicone, animal oils such as mink oil, fish oils, natural vegetable oils such as olive oil, sesame oil, linseed oil, palm oil, sunflower oil, peanut oil, rapeseed oil, soybean oil, coconut oil , Paitnkernfett, peach kernel oil, almond oil, castor oil, dehydrated castor oil, pine oil, tall oil and / or mixtures thereof used.

As additional aliphatic esters are preferably synthetic triglycerides such as caprylic / Caprinsäurebiglycerid, Triglyceridgemische with vegetable fatty acids of chain length C ₈ - _I2 or other specially selected natural fatty acids, Partialglyceridgemische saturated or unsaturated possibly hydroxyl-containing fatty acids, mono- and diglycerides of Cs / i ₀ - fatty acids, Fatty acid esters such as ethyl stearate, di-n-butyl adipate, lauric acid hexyl ester, dipropylene glycol pelargonate, cetearyl glucoside, cetearath-15, glyceryl stearate, glyceryl cetearate, isopropyl palmitate, middle chain branched chain fatty acid ester with saturated fatty alcohols of chain length Ci6-i8, Isopropyl myristate, Isopropylpahnitat, caprylic / capric acid esters of saturated fatty alcohols of chain length Cπ-is, isopropyl stearate, Isopropylpahnitat, caprylic / capric acid esters of saturated fatty alcohols of chain length Ci _2-U , oleic acid, esters of oleic acid, E methyl oleate, ethyl lactate, waxy fatty acid esters such as dibutyl phthalate. Adipic diisopropyl ester, the latter related ester mixtures including fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol and / or mixtures used of it. Cetearyl glucosides are very particularly preferred as aliphatic esters. Cetearath-15, glyceryl stearates, glyceryl cetearaths, isopropyl palmitates and / or mixtures thereof.

Particularly preferred is a formulation containing as a mixture of 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl ester, cereraryl glucoside, carbomer and water.

Particularly preferred is a formulation containing as a mixture 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl, silicone polyether, isopropyl palmitate, polydimethylsiloxane, acrylic acid polymer, polycyclic aromatic hydrocarbons and water.

Also particularly preferred is a formulation containing as the mixture 1-piperidinecarboxylic acid 2-hydroxyethyl-1-methylpropyl ester, cetearyl glucoside, acrylic acid polymer and water.

In the formulation, it is preferable to additionally use components for producing a UV filter effect. Oxybenzone, sulisobenzone (2-hydroxy-4-methylbenzophenone-5-sulfonic acid), dioxybenzene (2,2'-dihydroxy-4-methoxybenzophenone), menthylanthranilate, avobenzone, para-aminobenzoic acid are particularly preferred as components for producing a UV filter effect , octyl methoxycinnamate, octocrylene, TEA-sahcylat Drometrizoltrisiloxan, Octylsahcylat, homomenthyl salicylate, octyl dimethyl PABA, titanium dioxide, Butyhnethoxydibenzoylmethan, diendikamfersulfonsäure Methylbenzyhdenkamfer zinc oxide, octyl, terephthalyl, ethyl PABA, hydroxymethylphenyl-benzotriazole, methylene bi- benzotriazoyltetramethylbutylphenol, bis -octyloxyphenol methoxy-phenol-triazine, Novantisol acid and / or mixtures thereof used.

In the formulation, biocides are preferably additionally used. Particularly preferred biocides are benzyl alcohol, trichlorobutanol, o-phenylphenol, para-hydroxybenzoic acid methyl ester, para-hydroxybenzoic acid ethyl ester, para-hydroxybenzoic acid propyl ester, butyl para-hydroxybenzoate, n-butanol, propanol, isopropanol, ethanol and / or mixtures thereof.

In the formulation, it is preferable to additionally use antioxidants. As antioxidants, preference is given to using butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), tocopherol, sulfites, metabisulfites, such as potassium metabisulfite, ascorbic acid, and / or mixtures thereof.

In the formulation, thickeners are preferably used in addition. Particularly preferred thickeners are carboxymethylcellulose, hydroxyethylcellulose, Methyl cellulose and other cellulose and starch derivatives, polyacrylates, polyvinyl acetate, vinyl acetate-crotonic acid copolymer, alginates, gelatin, pectin, casein, agar-agar, gum arabic, aloe vera, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, Polypropylene glycols, block and / or random copolymer of propylene and ethylene glycol units, waxes, colloidal silicic acids, and / or mixtures thereof used.

In the formulation, it is preferable to additionally use dyes or color pigments. As dyes or color pigments, it is particularly preferred to use all dyes approved for human or animal use in dissolved or suspended form and as pigments all pigments approved for human or animal use in dissolved or suspended form, and / or mixtures thereof.

In the formulation, fragrances are preferably used in addition. Fragrances used are particularly preferably perfume oils and other low-boiling substances which are approved for use on humans or animals, and / or mixtures thereof.

The invention also encompasses a process for preparing the formulation, characterized

That 1 to 40 weight percent of a repellant, 0 to 20 weight percent of an oil and 0 to 3 weight percent of a carbomer, acrylic acid polymer or their mixtures thereof are mixed together and then with

0.1 to 20% by weight of an aliphatic ester, silicone polyether, glycerol, polydimethylsiloxane, 1'-oxybisoctane or mixtures thereof and 17 to 98.9% by weight.

% Water

be mixed.

The invention also encompasses the use of the formulations for expelling arthropods and / or platelet mints. The formulation is preferably used to ward off harmful or irritating sucking and biting arthropods, preferably insects, ticks and mites.

The sucking insects mainly include the mosquitoes (for example Aedes aegypti, Aedes vexans, Aedes taeniorhynchus, Aedes albopictus, Culex pipiens fatigans, Culex quinquefasciatus, Culex tarsalis, Anopheles albimanus, Anopheles dirus, Anopheles gambiae, Anopheles sinensis, Anopheles stephensi, Mansonia titillans), insect moths (for example Phlebotomus papatasii, Phlebotomus duboscqi), biting midges (for example Culicoides furens, Culicoides impunctatus), blackflies (for example Simulium damnosum, Simulium venustum), Lynxes (for example Stomoxys calcitrans), tsetse flies (for example Glossina morsitans morsitans), brakes (for example Tabanus nigrovittatus, Haematopota pluvialis, Chrysops caecutiens), true flies (for example Musca domestica, Musca autumnalis, Musca vetustissima, Fannia canicularis) Flesh (for example Sarcophaga carnaria), myiasis-producing flies (for example Lucilia cuprina, Clirysomyia chloropyga, Hypoderma bovis, Hypoderma lineatum, Dermatobia hominis, Oestxus ovis, Gasterophilus intestinalis, Cochliomyia hominivorax), bugs (for example Cimex lectularius, Rhodnius prolixus, Triatoma infestans), lice (for example Pediculus humanis, Haematopinus suis, Damalina ovis), fleas (for example Pulex irritans, Xenopsylla cheopis, Ctenocephalides canis, Ctenocephalides felis) and sand fleas (Dermatophilus penetrans).

The biting insects include, essentially, cockroaches (for example, Blattella germanica, Periplaneta americana, Blatta orientalis, Supella longipalpa), beetles (for example, Sitiophilus granarius, Tenebrio molitor, Dermestes lardarius, Stegobium paniceum, Anobium punctatum, Hylotrupes bajulus), termites (e.g. Example Reticulitermes lucifugus), ants (for example Lasius niger, Monomorium pharaonis), wasps (for example Vespula germanica) and larvae of moths (for example Ephestia elutella, Ephestia cautella, Plodia interpunctella, Hofmannophila pseudospretella, Tineola bisselliella, Tinea pellionella, Trichophaga tapetzella ).

The other arthropods include ticks (eg Ixodes ricinus, Ixodes scapularis, Argas reflexus, Ornithodorus moubata, Ripicephalus sanguineus, Boophilius microplus, Amblyomma hebraeum) and mites (for example Sarcoptes scabiei, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermanyssus gallinae, Acarus siro) ,

Furthermore, the formulations are preferably used against platelet mints, in particular against infectious stages of Plathehnintlien. Preference is given to the formulation for repelling plamelminths such as Schistosomahaematobium, Schistosoma japonicum, Trichobilharzia spp. and Ornithobilharzia spp., but also Echinostoma spp. used.

The formulations are preferably used by applying to the skin of humans or animals by means of dripping, brushing, rubbing, spraying, by dipping / dipping, bathing or washing.

The formulations are preferably for impregnation of a carrier or encapsulation / microencapsulation in a shell of liposomes and / or ureas or

Filling a permeable packaging or container used for later use on the body of a living being. The systems thus obtained can then on the body of a Living being used. The carrier is preferably tissue. Nonwoven, gel and / or polyacrylate used.

The subject of the present invention results not only from the subject matter of the individual claims, but also from the combination of the individual claims with each other. The same applies to all parameters disclosed in the description and their arbitrary combinations.

Based on the following examples, the invention is explained in more detail, without thereby limiting the invention is to be effected.

Examples

I. Description of the measuring methods used

A. Determination of viscosity

The viscosity is determined according to DIN 53019 of November 1983.

B. Determination of the stability of the formulation

The stability of the formulation was determined by the centrifuge microwave assay. The test serves to evaluate the structure of disperse systems. The test method looks like this:

processing

The test sample of the formulation to be tested is acclimated after preparation for about 2 days at room temperature. Approximately 10 g of product are weighed from the test sample into a centrifuge tube (25 ml nominal volume).

Stress test of the formulation

The centrifuge tube is 114 (corresponding to an average power of 75 watts) irradiated 75 seconds with stage 1 of the apparatus AEG Micromat ^® in the microwave. Subsequently, this sample is acclimated for one hour at room temperature and centrifuged for 11 minutes at 4350 revolutions / minute in an Eppendorf centrifuge 5403.

exam

The test of the sample is done visually by the laboratory technician. The sample is examined for homogeneity of the formulation. Differing appearance to the untreated sample, for example occurring phase separation or bubbles in the centrifuge tube are described.

II. Comparative Example

A water-in-oil formulation of the following composition is prepared:

Phase A

70% by weight of water (distilled water) Phase B

20% wt .-% l-piperidinecarboxylic acid-2-hydroxyethyl-l-methylpropyl (Icaridin. Bayrepel ^®)

10% by weight of mineral oil 170 mPas (Merkur 240 PB)

First, phase A is heated to 80 ⁰ C. Then phase B is slowly added at a temperature of about 25 ⁰ C with vigorous stirring. The mixture is then cooled to below 30 ⁰ C with slow further stirring.

III. Example 2

An oil-in-water formulation of the following composition is prepared:

Phase A

73.83% by weight of water (distilled water)

1.0% by weight of cetearyl glucoside (TegoCare CG90)

Phase B

25% wt .-% l-piperidinecarboxylic acid-2-hydroxyethyl-l-methylpropyl (Icaridin, Bayrepel ^®)

0.17% by weight acrylic polymer (Carbopol Ultrez 10)

First, phase A is warmed to 60 ⁰ C and mixed. Subsequently, phase B is mixed with a temperature of about 35 ^° C. and slowly added to phase A with vigorous stirring. The mixture is then cooled to below 30 ° C. with slow further stirring. Subsequently, a pH control is carried out and adjusted if necessary by means of aqueous sodium hydroxide solution in the range pH 5.5 to 7.0.

IV. Example 3

An oil-in-water formulation of the following composition is prepared:

Phase A

71.83% by weight of water (distilled water) 3.0% by weight mixture Glyceryl Stearath, Glyceryl Cetearath (Emulgade SE PF)

Phase B

25% wt .-% l-piperidinecarboxylic acid-2-hydroxyethyl-l-methylpropyl (Icaridin. Bayrepel ^®)

0.17% by weight acrylic polymer (Carbopol Ultrez 10)

First, phase A is warmed to 55 ⁰ C and mixed. Subsequently, phase B is mixed at a temperature of about 35 ^° C. and slowly added with vigorous stirring. The mixture is then cooled to below 30 ⁰ C with slow further stirring. Subsequently, a pH control is carried out and adjusted if necessary by means of aqueous sodium hydroxide solution in the range pH 5.5 to 7.0.

V. Example 4

An oil-in-water formulation of the following composition is prepared:

Phase A

78.70% by weight of water (distilled water)

1% by weight of cereralaryl glucoside (Tego Care CG 90)

Phase B

20% wt .-% l-piperidinecarboxylic acid-2-hydroxyethyl-l-methylpropyl (Icaridin, Bayrepel ^®)

0.30% by weight of carbomer (pioneer NP37G)

First, phase B is mixed at room temperature. Subsequently, phase A at a temperature of about 25 ⁰ C 71.83% wt .-% mixed slowly added with vigorous stirring to phase A. The mixture is then cooled to below 25 ⁰ C with slow further stirring.

Subsequently, a pH control is carried out and adjusted if necessary by means of aqueous sodium hydroxide solution in the range pH 5.5 to 7.0.

VI. Example 5 An oil-in-water formulation of the following composition is prepared:

Phase A

70.70% by weight of water (distilled water)

1.0% by weight of cereralaryl glucoside (Tego Care CG90)

Phase B

0.3% by weight of carbomer (pioneer NP 37G)

3.0% by weight of isopropyl palmitate

First, phase B is mixed at room temperature. Phase A is then mixed at room temperature and slowly added to phase B with vigorous stirring. The mixture is then cooled to below 25 ⁰ C with slow further stirring.

VII. Example 6

An oil-in-water formulation of the following composition is prepared:

Phase A

80, 8% by weight -% water (distilled water)

3.0% by weight of glycerol

3.0% by weight of isopropyl palmitate

3.0% by weight polydimethylsiloxane (Abu 350)

Phase B 10% wt .-% l-piperidinecarboxylic acid-2-hydroxyethyl-l-methylpropyl (Icaridin, Bayrepel ^®)

0.2% by weight acrylic polymer (Carbopol Ultrez 10)

First, phase A is mixed at room temperature. Then phase B is mixed with a temperature of about 25 ⁰ C and slowly added with vigorous stirring. The mixture is then cooled to below 25 ° C. with slow further stirring.

VIII. Example 7

An oil-in-water formulation of the following composition is prepared:

Phase A

74.8% by weight of water (distilled water)

3.0% w / w l, oxybisoctane (Cetiol OE)

3.0% by weight of silicone polyether (Abu Care 85)

4.0% by weight polydimethylsiloxane (Abu 350)

Phase B

10% wt .-% l-piperidinecarboxylic acid-2-hydroxyethyl-l-methylpropyl (Icaridin, Bayrepel ^®)

0.2% by weight acrylic polymer (Carbopol Ultrez 10)

5.0% by weight of polycyclic aromatic hydrocarbons (Merkur 40PB)

First, phase A is mixed at room temperature. Subsequently, phase B is mixed and added slowly at a temperature of about 25 ° C. with vigorous stirring. The mixture is then cooled to below 25 ⁰ C with slow further stirring.

Subsequently, a pH control is carried out and adjusted if necessary by means of aqueous sodium hydroxide solution in the range pH 5.5 to 7.0. IX. Example 8

A water in oil formulation of the following composition is prepared:

Phase A

74.9% by weight of water (distilled water)

3.0% by weight of silicone polyether (Abil Care 85)

3.0% by weight of isopropyl palmitate

4.0% by weight polydimethylsiloxane (Abil 350)

Phase B

10% wt .-% l-piperidinecarboxylic acid-2-hydroxyethyl-l-methylpropyl (Icariditi, Bayrepel ^®)

0.1% by weight of acrylic acid polymer (Carbopol Ultrez 10)

5.0% by weight of polycyclic aromatic hydrocarbons (Merkur 40PB)

First, phase A is mixed at room temperature. Then phase B is mixed and slowly added at a temperature of about 25 ⁰ C with vigorous stirring. The mixture is then cooled to below 25 ⁰ C with slow further stirring.

The formulations thus prepared were stored at room temperature for 3 days and then visually assessed and the viscosity measured:

²⁾ Since the formulation separates rapidly, the viscosity for such an emulsion can not be determined unambiguously

Claims

claims

1. formulation for the defense of arthropods and Plathelminthen containing the mixture:

1 to 40% by weight of a repellent

0 to 20% by weight of an oil

0 to 3 weight percent of a carbomer, acrylic acid polymer or mixtures thereof

0.1 to 20% by weight of an aliphatic ester, silicone polyether, acrylic acid polymer, glycerol, polydimethylsiloxane, 1'-oxybisoctane or mixtures thereof

17 to 98.9 wt .-% water.

2. Formulation according to claim 1, characterized in that the formulation has a viscosity of> 20 mPas.

3. Formulation according to one or more of claims 1 and 2, characterized in that in addition 0.1 to 20% by weight of N-methylpyrrolidone, phenethyl alcohol, benzyl alcohol, an aliphatic alcohol, aliphatic ether, aliphatic polyether and / or

Mixtures thereof are used.

4. A formulation according to claim 3, characterized in that ethanol, propanol, isopropanol, n-butanol, sec-butanol, propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, copolymeric polyether polyols based on ethylene or propylene oxide, 2-ethyl-1,3-hexanediol , Glycerol, trimethylolpropane and / or mixtures thereof.

5. Formulation according to one or more of claims 1 to 4, characterized in that as a repellent preferably a piperidine derivative of the general formula

wherein Ri 'and R ₂ ' independently represent alkyl, alkenyl, alkynyl, hydroxyalkyl, hydroxyalkenyl, hydroxyalkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkoxy, cycloalkenoxy and cycloalkynoxy, and

n is 0 or 1 or mixtures thereof is used.

6. A formulation according to one or more of claims 1 to 5, characterized in that the repellent used as a piperidine derivative of the general formula where Ri 'and R ₂ ' independently of one another for QC ₁₂ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁₂ hydroxyalkyl, C ₃ -C ₂₀ alkenyl, C ₃ -C ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ Cycloalkeyl, C ₃ - C ₂₀ cycloalkynyl, C ₃ -C _{20 is} cycloalkoxy, C ₃ -C ₂₀ cycloalkenoxy and C ₃ -C ₂₀ cycloalkynoxy, and n is 0 or 1, or mixtures thereof.

7. Formulation according to one or more of claims 1 to 6, characterized in that as a repellent l-piperidinecarboxylic acid 2-hydroxyethyl-l-methylpropyl ester and 1- (3-cyclohexen-l-ylcarbonyl) -2-methylpiperidine both as a racemic mixture as well as a chiral compound.

8. Formulation according to one or more of claims 1 to 7, characterized in that as oils of the repellent, mineral oils, polycyclic aromatic hydrocarbons, paraffin oils, silicone oils such Polysüoxan, cyclosiloxane, methicone, animal oils such as mink oil, fish oils, natural vegetable oils such as olive oil, sesame oil , Linseed oil, palm oil, sunflower oil, peanut oil, rapeseed oil, soybean oil, coconut fat, Pahnkernfett, peach kernel oil, almond oil, castor oil, dehydrated castor oil, pine oil, tall oil or mixtures thereof.

9. A formulation according to one or more of claims 1 to 8, characterized in that as aliphatic esters synthetic triglycerides such as caprylic / Caprinsäurebiglycerid, triglyceride mixtures with vegetable fatty acids of chain length C ₈ - _I2 or other specially selected natural fatty acids, Partialglyceridgemische saturated or unsaturated

Fatty acids, mono- and diglycerides of cis _/ io fatty acids, fatty acid esters such as ethyl stearate, di-n-butyl adipate, lauric acid hexester, dipropylene glycol pelargonate, cetearyl glucoside, cetearath-15, glyceryl stearate, glyceryl cetearate, isopropyl palmitate, ester of one branched fatty acid of medium chain length with saturated fatty alcohols of chain length Ci ₆ - _I s, isopropyl myristate, isopropyl palmitate, caprylic / capric acid ester of saturated

Fatty alcohols of chain length QM ₈ , isopropyl stearate, isopropyl palmitate, caprylic / capric acid esters of saturated fatty alcohols of chain length C _12-I g, Oleic acid oleyl ester, oleic acid decyl ester, ethyl oleate, ethyl lactate, waxy fatty acid esters and / or fatty alcohols and / or mixtures thereof may be used.

10. A formulation according to one or more of claims 1 to 9, characterized in that are used as aliphatic esters cetearyl glucoside, cetearath-15, glyceryl stearate, glyceryl cetearaths, Isopropylpalmiats and / or mixtures thereof.

11. A formulation according to one or more of claims 1 to 10, characterized in that the mixture contains 1-piperidinecarboxylic acid 2-hydroxyethyl-l-methylpropyl ester, cereroseric acid, carbomer and water.

12. A formulation according to one or more of claims 1 to 10, characterized in that the mixture l-piperidinecarboxylic acid 2-hydroxyethyl-l-methylpropyl ester, silicone

Polyether, isopropyl palmitate, polydimethylsiloxane, acrylic acid polymer, polycyclic aromatic hydrocarbons and water.

13. A formulation according to one or more of claims 1 to 10, characterized in that the mixture contains 1-piperidinecarboxylic acid 2-hydroxyethyl-l-methylpropyl ester, cetearyl glucoside, acrylic acid polymer and water.

14. A formulation according to one or more of claims 1 to 13, characterized in that in addition components are used to produce a UV filter effect.

15. A formulation according to claim 14, characterized in that components for producing a UV filter effect oxybenzone, SuHsobenzon (2-hydroxy-4-methylbenzophenone-5-sulfonic acid), dioxybenzone (2,2'-dihydroxy-4-methoxybenzophenone),

Menthyl anthranilate, avobenzone, para Aminobenzoesäue, Octylmethoxycinnarnat, octocrylene, Drometrizoltrisiloxan, octyl salicylate, homomenthyl salicylate, octyl dimethyl PABA, TEA salicylate, titanium dioxide, zinc oxide, Butyhnethoxydibenzoylmethan, Metliylbenzylidenkamfer, octyl, Terephthalyldiendikamfersulfonsäure, ethyl PABA, hydroxymethylphenyl-benzotriazole, Metliylen-bi-benzotriazoyltetramethylbutylphenol , Bis-octyloxyphenol-methoxyphenol-triazine, Novantisolsäure and / or mixtures thereof.

16. A formulation according to one or more of claims 1 to 15, characterized in that additionally biocides are used.

17. Formierang according to claim 16, characterized in that as biocides benzyl alcohol, trichlorobutanol, o-phenylphenol, para-hydroxybenzoic acid methyl ester, para Hydroxybenzoic acid ethyl ester, propyl para-hydroxybenzoate, para

Hydroxybenzoate, n-butanol, propanol, iso-propanol, ethanol and / or mixtures thereof.

18. A formulation according to one or more of claims 1 to 17, characterized in that in addition antioxidants are used.

19. A formulation according to claim 18, characterized in that butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), tocopherol, sulfites, metabisulfites such as potassium metabisulfite, ascorbic acid, and / or mixtures thereof are used as antioxidants.

20. A formulation according to one or more of claims 1 to 19, characterized in that additional thickening agents are used.

21. A formulation according to claim 20, characterized in that as thickeners carboxymethylcellulose, hydroxyethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, polyvinyl acetate, vinyl acetate-crotonic acid copolymer, alginates, gelatin, pectin, casein, agar-agar, rubber Arabic, aloe vera,

Polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, polypropylene glycols, block and / or random copolymer of propylene and ethylene glycol units, waxes, colloidal silicas, and / or mixtures thereof.

22. Formulation according to one or more of claims 1 to 21, characterized in that in addition dyes or color pigments are used.

23. A formulation according to claim 22, characterized in that as dyes all approved for use in humans or animals dyes in dissolved or suspended form and as pigments all approved for use on humans or animals pigments in dissolved or suspended form, and / or mixtures thereof be used.

24. A formulation according to one or more of claims 1 to 23, characterized in that in addition fragrances are used.

25. A formulation according to claim 24, characterized in that are used as fragrances perfume oils and other low-boiling substances, which are approved for use in humans or animals, and / or mixtures thereof.

26. A process for the preparation of the formulation according to one or more of claims 1 to 25, characterized in that

• 1 to 40% by weight of a repellents, 0 to 20% by weight of an oil and 0 to 3% by weight of a carbomer, acrylic acid polymer or mixtures thereof are mixed together and then with

<> 0.1 to 20% by weight of an aliphatic ester, silicone polyether, glycerol, polydimethylsiloxane, 1'-oxybisoctane or mixtures thereof and 17 to 98.9% by weight of water

be mixed.

27. Use of formulations according to one or more of claims 1 to 25 for the displacement of arthropods.

28. Use of formulations according to one or more of claims 1 to 25 for the expulsion of Plathelminthen.

29. Use of formulations according to one or more of claims 1 to 25, characterized in that the formulations by application to the skin of humans or animals by means of dripping, brushing, spraying, spraying, by dipping / dipping, bathing or washing.

30. Use of formulations according to one or more of claims 1 to 25 for impregnation of a carrier or encapsulation / microencapsulation in a shell of liposomes and / or ureas or filling a permeable packaging or

Container for later use on the body of a living being.

31. Use of formulations according to claim 3O _3, characterized in that are used as the carrier tissue, nonwoven, gel and / or polyacrylate.