WO1994006298A1

WO1994006298A1 - Repellant material

Info

Publication number: WO1994006298A1
Application number: PCT/GB1993/001939
Authority: WO
Inventors: Anthony Pisacane
Original assignee: Anthony Pisacane
Priority date: 1992-09-12
Filing date: 1993-09-13
Publication date: 1994-03-31
Also published as: CA2144517A1; GB9219384D0; AU4979693A; EP0660669A1

Abstract

There is disclosed a composition comprising a terpene or terpene derivative and a polymer substituted by amine or amide groups. Optionally binders, thickeners and other conventional additives may also be included. The composition has insect repelling, aquatic organism repelling and fungi repelling properties.

Description

REPELLANT MATERIAL

The present invention is concerned with a repellant material, and especially with a material which is repellant to fungi, aquatic organisms and insects.

Flying insects are often considered to be a nuisance and are a source of distraction or irritation to many people. Insects which bite or sting can cause physical discomfort, with local irritation and pain being experienced at the bite or sting site. Where the number of bites or stings are large, or where the victim is particularly vulnerable to such bites or stings, the pain caused can be considerable and there have been instances where the shock induced is large enough to cause coma.

More importantly, many insects transmit disease and therefore pose a serious health hazard. Thus, for example nagana (tsetse fly disease) or "sleeping sickness" is transmitted by tsetse flies and may affect both man and cattle in Africa and South America. Likewise malaria, which is transmitted by mosquitos, remains a health problem in many tropical areas.

Insects, including flying insects, also have important ramifications in animal husbandry and the economic value of animal herds may be adversely affected by insect presence or action. However, treating animals with an insecticide can be labour intensive, expensive and cause environmental side-effects.

Similarly, aquatic organisms can cause fouling of boats, ships or oil-rigs and the like causing damage if the surface affected is not cleaned on a regular basis which can be a difficult and expensive process. Fungal growth, for example in buildings, on plants or even medical fungal infections can also be a serious problem. Established fungal growth in buildings (eg, dry rot) may cause structural and ultimately safety difficulties. However, complete eradication or treatment of any fungal infections is time-consuming and difficult.

Conventional insect repellants include DDT, rotenone, lead arsenic, Gammexane, hydrogen cyanide, ethylene oxide and formaldehyde. However, due to their toxic nature, such insecticides are not suitable for general human use as a means of avoiding insect contact. Moreover, these insecticides tend to be highly non- selective and can therefore have wide-ranging effects on the environment.

Insect repellants generally contain diethyltoluamide (deet) as the active ingredient. However, diethyltoluamide is also toxic and is absorbed through the skin causing side effects ranging from skin irritation to the death of children who are over- exposed to it.

The present invention provides a composition comprising a terpene or terpene derivative and a polymer substituted by amine and/or amide groups.

The term "terpene" includes all compounds of formula (C_jH_jj),, whether of acyclic or cyclic structure. Cyclic terpenes may be either onocyclic or bicyclic. Monoterpenes (of formula C,₍,H_I6, ie, n is 2) are preferred, but the invention also encompasses sesquiterpenes (C₁₅H₂₄) , diterpenes (C₂₀H₃₂) , triterpenes (C₃₀H₄₈) and tetraterpenes (C₄₀H_M) .

The term "terpene derivative" includes substituted terpene compounds, terpene compounds having one or more double and/or triple carbon-carbon bonds, and the nor- terpenes (wherein a methyl group is replaced by hydrogen) . Substituents of the terpene derivatives mentioned above include alkyl groups, especially lower alkyl groups such as C,_.6 alkyl, hydroxy groups, amino groups, thiol groups and halogen atoms, for example chlorine, bromine, fluorine or iodine.

As examples of terpene compounds, the following may be mentioned:

p-menthane

thujane

carane

pmane

bornane

1,1,2,3-tetramethylcyclohexane

As examples of terpene derivatives, the following may be mentioned:

4 (lθ)-thujene

5-iεopropyl-bicyclo[3.1.0]-hex-2-ene

camphene

Preferred terpene derivatives are terpene alcohols such as terpineol (C₁₀H₁₇OH) .

A mixture of terpenes and terpene derivatives may also be used in the composition of the present invention. One naturally occurring source of a terpene mixture is pine oil, which may conveniently be used in the composition.

The polymer substituted by amine or amide groups used in the composition are preferably water-dispersible and may be a polyamine, a polya ide or a polyamidoamine. Conveniently the polymer is water soluble. Mixtures of two or more polya ines, polyamides or polyamidoamines are acceptable. Preferably the polymer is an aliphatic or cycloaliphatic polyamine such as isophoronedia ine, polyoxypropylenediamine, 3-[ (6-aminotrimethylhexyl) - amino]proprionitrile, a polyethylene amine, or mixtures thereof.

Preferably, the composition of the present invention comprises of from 1% to 99% by weight of terpene, terpene derivative or mixtures thereof and from 99% to 1% by weight of polymer. More usually, however, the composition will comprise of from 2% to 75% by weight of terpene, terpene derivative or mixtures thereof and from 75% to 2% by weight of polymer.

Advantageously, the terpene, terpene derivative or mixtures thereof (hereinafter referred to as the "terpene component") may be present in a ratio of from 1:3 to 3:1 (by weight) relative to the polymer.

The composition may be formulated in any convenient form, for example, as a spray, liquid, dispersion, paste, gel or cream.

The amount of terpene component and polymer will vary depending on the exact formulation required. Thus, for example, a spray formulation may contain up to 20%, for example 2-15%, preferably 4-10% by weight of terpene component and up to 10%, for example up to 5%, such as 1 to 2% by weight of polymer.

In a cream, gel or paste composition there may be a higher proportion of terpene component, for example, 10 to 99%, preferably 50 to 95% and more preferably 75 to 95% by weight of terpene component. The composition may also contain 2 to 20%, preferably 5 to 15% by weight of polymer. The composition according to the invention is of use in repelling insects, aquatic organisms or fungi. Insect repulsion may be desirable, in particular, for people wishing to avoid irritation or medical problems caused by insects, and also in applications in animal husbandry where insect presence or action could cause damage to the animals.

In another aspect, the present invention provides a method of producing the composition described above, said method comprising admixing a terpene or terpene derivative with a polymer substituted by amine and/or amide groups.

It is possible to impregnate or coat a surface which the composition according to the present invention. Where repulsion of insects is desired then the composition may be applied to articles of clothing such as socks, hats, gloves, jackets, plimsolls etc. Accessories such as hairbands, wristbands, ankle bands and shoe insoles may also be treated with the composition.

Where repulsion of the aquatic organisms or fungi is required, the object to be protected may be simply coated with the composition.

The treated objects referred to above also form a further aspect of the invention.

Conventional additives may also be included in the composition, for example, binders (eg, resins) , viscosity increasing agents, buffers, osmotic regulators, gelling agents, surfactants, dispersants, pigments, colourants, dyes etc. Optionally one or more conventional insect repellants or insecticides may also be included, although generally only at low concentrations to reduce toxicity. Suitable additives will be well-known to those skilled in the art.

One particularly useful embodiment is the blending of the composition with pigments, resins and other materials to make paints or coatings which retain the repellant properties of the composition.

Mention may be made of acrylic resins such as epoxy resins, butyl acrylate resin and acrylonitrile resins which are suitable as binders. Other suitable binders include collagen, starches (eg, flour) and alginate . Bentonite may be used as a thickener. Preferably the binder has a pH of approximately 7 to 9 to be compatible with the amine or amide groups of the polymer. Any surfactant used is preferably a non-ionic surfactant.

In another useful embodiment the composition, preferably in the form of a paste, cream or gel is inserted into a pre-formed container which is then sealed or placed onto a membrane which is used in forming a sealed container (the word "container" here refers to any package, packet, sachet, box, carton or bag) . The volatile components of the composition diffuse through a permeable layer of the sealed container whilst the binders and other additives are substantially retained within the container. This embodiment allows a composition having a high concentration of the terpene and polymer components to be formulated without risk of any side-effects. Moreover the requirement for diffusion through the permeable layer slows down the rate at which the volatile compounds are released into the surroundings, leading to a long effective life. Polyethene and cellulose may form barrier layers having the required permeability. The exact permeability of the layer may be varied, depending upon the rate of diffusion required.

Thus, the present invention also provides a repellant apparatus comprising an admixture of a terpene or terpene derivative and a polymer substituted by amino or amide groups sealed within a container comprising a permeable layer.

The present invention further provides a method of repelling insects from a surface, said method comprising applying a composition as defined above to said surface. Likewise, the present invention also provides a method of repelling aquatic organisms or of repelling fungi since a surface so treated with the composition will also have this effect.

In another aspect, the invention provides the use of the composition described above in repelling insects, aquatic organisms and/or fungi.

In yet another aspect, the invention provides the use of terpenes, terpene derivatives or mixtures thereof in the manufacture of a composition to repel insects, aquatic organisms and/or fungi. The following examples can illustrate applications of the process (all quantities are given by weight, except where otherwise specified) :

1. INSECT REPELLANT

Pine Oil 8.80 Surfactant 0.88 Polyamidoamine 1.76 Butyl Acrylate/ Acrylonitrile Resin44.56 Water 44.00

100.00

When supplied to surfaces in buildings such as door frames, window frames, skirting boards etc, the surfaces become repellant to some crawling insects. When applied to articles of clothing such as hats, gloves, jackets etc, the surfaces become repellant to some flying insects of the mosquito type.

2. FUNGI REPELLANT

Terpineol Surfactant Polyamidoamine

The above mixture can be added to normal emulsion and gloss paints in the ratio of approximately 20ml to one litre of paint, and mixed thoroughly. When applied to interior surfaces of buildings the surfaces become repellant to some fungi, moulds and crawling insects.

3. AQUATIC ORGANISM REPELLANT

Pine Oil 5.71 Polyamidoamine 9.52 Epoxide resin 9.40 Bentonite 0.45 Titanium dioxide 11.31 Copper thiocyanate 35.70 Water 27.91

100.00

When applied to surfaces such as wood, glass fibre laminate etc and allowed to dry and then immersed in sea water, the surface becomes repellant to many animal and plant organisms to a degree efficiency greater than can be expected by similar compositions based on copper thiocyanate with resin in organic solvent.

4. INSECT REPELLANT

Terpineol 85.00 Wheat flour 10.00 Polyamidoamine 5.00

100.00 The components are admixed together into a paste.

5. INSECT REPELLANT SACHET

The paste from Example 4 is inserted into a polyethene film tube which is then sealed at both ends.

6. AQUATIC ORGANISM REPELLANT

Example 3 was repeated with 57.12 units (by weight) Cuprous oxide replacing the Copper thiocyanate.

7. INSECT REPELLANT

8. INSECT REPELLANT

9.

Terpineol 85.00 Wheat flour 10.00 Polyethyleneamine 5.00

100.00

Claims

1. A composition comprising a terpene component selected from a terpene, a terpene derivative or a mixture thereof, and a polymer substituted by amine and/or amide groups.

2. A composition as claimed in Claim 1 wherein said terpene component is present in an amount of from 1% to 99% by weight and said polymer is present in an amount of from 99% to 1% by weight.

3. A composition as claimed in either of Claims 1 and 2 wherein said terpene component is present in an amount of from 2 to 75% by weight and said polymer is present in an amount of from 75% to 2% by weight.

4. A composition as claimed in any one of Claims 1 to 3 wherein said terpene component is present in a ratio of from 1:3 to 3:1 by weight relative to said polymer.

5. A composition as claimed in any one of Claims 1 to 4 wherein said terpene component comprises a terpene alcohol.

6. A composition as claimed in any one of Claims 1 to 5 wherein said terpene component comprises pine oil.

7. A composition as claimed in any one of Claims 1 to 6 wherein said terpene component comprises terpineol.

8. A composition as claimed in any one of Claims 1 to 7 wherein said polymer is a polyamine.

9. A composition as claimed in claim 8 wherein said polyamine is isophoronediamine, polyoxypropylene- diamine, 3-[ (6-aminotrimethylhexyl)amino]- propionitrile, a polyethyleneamine, or mixtures thereof.

10. An apparatus comprising a composition as claimed in any one of claims 1 to 9 sealed within a container which comprises a permeable layer.

11. A method of repelling insects from a surface, said method comprising applying a composition as claimed in any one of Claims 1 to 9 to said surface.

12. An insect repelling object, characterised in that at least one surface thereof has been treated with a composition as defined in any one of Claims 1 to 9.

13. A method of repelling aquatic organisms from a surface, said method comprising applying a composition as claimed in any one of Claims 1 to 9 to said surface.

14. An aquatic organism repelling object, characterised in that at least one surface thereof has been treated with a composition as defined in any one of Claims 1 to 9.

15. A method of repelling fungi from a surface, said method comprising applying a composition as claimed in any one of Claims 1 to 9 to said surface.

16. A fungus repelling object, characterised in that at least one surface thereof has been treated with a composition as defined in one of Claims 1 to 9.

17. Use of a composition as claimed in any one of Claims 1 to 9 for repelling insects, aquatic organisms and/or fungi.

18. An insect repellant comprising a terpene, a terpene derivative or a mixture thereof.

19. An aquatic organism repellant comprising a terpene, a terpene derivative or a mixture thereof.

20. A fungal repellant comprising a terpene, a terpene derivative or a mixture thereof.