Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~094/06298 2 14 ~ ~ 17 PCT/GB93/01939
1 REPELLANT MATERIAL
4 The present invention is concerned with a repellant
material, and especially with a material which is
6 repellant to fungi, aquatic organisms and insects.
8 Flying insects are often considered to be a nuisance
9 and are a source of distraction or irritation to many
people. Insects which bite or sting can cause physical
11 discomfort, with local irritation and pain being
12 experienced at the bite or sting site. Where the
13 number of bites or stings are large, or where the
14 victim is particularly vulnerable to such bites or
stings, the pain caused can be considerable and there
16 have been instances where the shock induced is large
17 enough to cause coma.
18
19 More importantly, many insects transmit disease and
therefore pose a serious health hazard. Thus, for
21 example nagana (tsetse fly disease) or "sleeping
22 sickness" is transmitted by tsetse flies and may affect
23 both man and cattle in Africa and South America.
24 Likewise malaria, which is transmitted by mosquitos,
remains a health problem in many tropical areas.
26
27 Insects, including flying insects, also have important
28 ramifications in animal husbandry and the economic
29 value of animal herds may be adversely affected by
W094/06298 2 1~ ~ ~ 17 PCT/GB93/019
1 insect presence or action. However, treating animals
2 with an insecticide can be labour intensive, expensive
3 and cause environmental side-effects.
Similarly, aquatic organisms can cause fouling of
6 boats, ships or oil-rigs and the like causing damage if
7 the surface affected is not cleaned on a regular basis
8 which can be a difficult and expensive process. Fungal
9 growth, for example in buildings, on plants or even
medical fungal infections can also be a serious
11 problem. Established fungal growth in buildings (eg,
12 dry rot) may cause structural and ultimately safety
13 difficulties. However, complete eradication or
14 treatment of any fungal infections is time-consuming
and difficult.
16
17 Conventional insect repellants include DDT, rotenone,
18 lead arsenic, Gammexane, hydrogen cyanide, ethylene
19 oxide and formaldehyde. However, due to their toxic
20 nature, such insecticides are not suitable for general
21 human use as a means of avoiding insect contact.
22 Moreover, these insecticides tend to be highly non-
23 selective and can therefore have wide-ranging effects
2 4 on the environment.
26 Insect repellants generally contain diethyltoluamide
27 (deet) as the active ingredient. However,
28 diethyltoluamide is also toxic and is absorbed through
29 the skin causing side effects ranging from skin
30 irritation to the death of children who are over-
31 exposed to it.
32
3 3 The present invention provides a composition comprising
34 a terpene or terpene derivative and a polymer
21~517
1 substituted by amine and/or amide groups.
3 The term '~terpene" includes all compounds classified as
4 monoterpenes of formula CloHl6 whether of acyclic or
cyclic structure. Cyclic terpenes may be either
6 monocyclic or bicyclic.
8 The term "terpene derivative" includes substituted
9 terpene compounds, terpene compounds having one or more
double and/or triple carbon-carbon bonds, and the nor-
11 terpenes (wherein a methyl group is replaced by
12 hydrogen). Substituents of the terpene derivatives
13 mentioned above include alkyl groups, especially lower
14 alkyl groups such as Cl6 alkyl, hydroxy groups, amino
groups, thiol groups and halogen atoms, for example
16 chlorine, bromine, fluorine or iodine.
17
18 As examples of terpene compounds, the following may be
19 mentioned:
22 p-menthane
24
26 thujane
28
29
carane
32
33
A',Y'.ET~DE~ SHEET
W094/06298 21 4 ~ 51 7 PcT/GB93/ol939
1 pinane
6 bornane ~ ~
8 ~ /
9 1,1,2,3-tetramethylcyclohexane
11
12
13 As examples of terpene derivatives, the following may
14 be mentioned:
l7 1-p-menthane
19
21 1,4 (8)-p-menthadiene ~
23 1 /
24 1,2,3,3-tetramethyl-1-cyclohexene
26
27
29 4(10)-thujene
31
S-isopropyl-blcyclo[3.l.0]-hex-2-ene
2lA ~ ~1 ~ PCT/GB93/01939
W094/06298
~D
1 camphene
2-carene~ ~
7 ~ \ ~ C
9 2(10),3-pinadiene
1 \
13 ~-terpinene
14
lG
17 pinene
18
21 Preferred terpene derivatives are terpene alcohols such
22 as terpineol (C,(,H~70H).
23
24 A mixture of terpenes and terpene derivatives may also
be used in the composition of the present invention.
26 One naturally occurring source of a terpene mixture is
27 pine oil, which may conveniently be used in the
28 composition.
29
The polymer substituted by amine or amide groups used
31 in the composition are preferably water-dispersible and
32 may be a polyamine, a polyamide or a polyamidoamine.
33 Conveniently the polymer is water soluble. Mixtures of
34 two or more polyamines, polyamides or polyamidoamines
are acceptable. Preferably the polymer is an aliphatic
W094/06298 PCT/GB93/019.
2144~17 6
1 or cycloaliphatic polyamine such as isophoronediamine,
2 polyoxypropylenediamine, 3-[(6-aminotrimethylhexyl)-
3 amino]proprionitrile, a polyethylene amine, or mixtures
4 thereof.
6 Preferably, the composition of the present invention
7 comprises of from 1% to 99% by weight of terpene,
8 terpene derivative or mixtures thereof and from 99% to
9 1% by weight of polymer. More usually, however, the
composition will comprise of from 2% to 75% by weight
11 of terpene, terpene derivative or mixtures thereof and
12 from 75% to 2% by weight of polymer.
13
14 Advantageously, the terpene, terpene derivative or
mixtures thereof (hereinafter referred to as the
16 "terpene component") may be present in a ratio of from
17 1:3 to 3:1 (by weight) relative to the polymer.
18
19 The composition may be formulated in any convenient
form, for example, as a spray, liquid, dispersion,
21 paste, gel or cream.
22
23 The amount of terpene component and polymer will vary
24 depending on the exact formulation required. Thus, for
example, a spray formulation may contain up to 20%, for
26 example 2-15%, preferably 4-10% by weight of terpene
27 component and up to 10%, for example up to 5%, such as
28 1 to 2% by weight of polymer.
29
In a cream, gel or paste composition there may be a
31 higher proportion of terpene component, for example, 10
32 to 99%, preferably 50 to 95% and more preferably 75 to
33 95% by weight of terpene component. The composition
34 may also contain 2 to 20~, preferably 5 to 15% by
weight of polymer.
W O 94/06298 21~ ~ Sl 7 PC~r/GB93/01939
1 The composition according to the invention is of use in
2 repelling insects, aquatic organisms or fungi. Insect
3 repulsion may be desirable, in particular, for people
4 wishing to avoid ir~itation or medical problems caused
by insects, and also in applications in animal
6 husbandry where insect presence or action could cause
7 damage to the animals.
9 In another aspect, the present invention provides a
method of producing the composition described above,
11 said method comprising admixing a terpene or terpene
12 derivative with a polymer substituted by amine and/or
13 amide groups.
14
It is possible to impregnate or coat a surface which
16 the composition according to the present invention.
17 Where repulsion of insects is desired then the
18 composition may be applied to articles of clothing such
19 as socks, hats, gloves, jackets, plimsolls etc.
Accessories such as hairbands, wristbands, ankle bands
21 and shoe insoles may also be treated with the
22 composition.
23
24 Where repulsion of the aquatic organisms or fungi is
required, the object to be protected may be simply
26 coated with the composition.
27
28 The treated objects referred to above also form a
29 further aspect of the invention.
31 Conventional additives may also be included in the
32 composition, for example, binders (eg, resins),
33 viscosity increasing agents, buffers, osmotic
34 regulators, gelling agents, surfactants, dispersants,
pigments, colourants, dyes etc. Optionally one or more
W094/06298 214 ~ 517 PCT/GB93/019
~ .
1 conventional insect repellants or insecticides may also
2 be included, although generally only at low
3 concentrations to reduce toxicity. Suitable additives
4 will be well-known to those skilled in the art.
6 one particularly useful embodiment is the blending of
7 the composition with pigments, resins and other
8 materials to make paints or coatings which retain the
9 repellant properties of the composition.
11 Mention may be made of acrylic resins such as epoxy
12 resins, butyl acrylate resin and acrylonitrile resins
13 which are suitable as binders. Other suitable binders
14 include collagen, starches (eg, flour) and alginate .
Bentonite may be used as a thickener. Preferably the
16 binder has a pH of approximately 7 to 9 to be
17 compatible with the amine or amide groups of the
18 polymer. Any surfactant used is preferably a non-ionic
19 surfactant.
21 In another useful embodiment the composition,
22 preferably in the form of a paste, cream or gel is
23 inserted into a pre-formed container which is then
24 sealed or placed onto a membrane which is used in
forming a sealed container (the word "container" here
26 refers to any package, packet, sachet, box, carton or
27 bag). The volatile components of the composition
28 diffuse through a permeable layer of the sealed
29 container whilst the binders and other additives are
substantially retained within the container. This
31 embodiment allows a composition having a high
32 concentration of the terpene and polymer components to
33 be formulated without risk of any side-effects.
34 Moreover the requirement for diffusion through the
permeable layer slows down the rate at which the
W094/06298 ~ PCT/GB93/01939
2tq~l 7
1 volatile compounds are released into the surroundings,
2 leading to a long effective life. Polyethene and
- 3 cellulose may form barrier layers having the required4 permeability. The exact permeability of the layer may
~ 5 be varied, depending upon the rate of diffusion
6 required.
8 Thus, the present invention also provides a repellant
9 apparatus comprising an admixture of a terpene or
terpene derivative and a polymer substituted by amino
11 or amide groups sealed within a container comprising a
12 permeable layer.
13
14 The present invention further provides a method of
repelling insects from a surface, said method
16 comprising applying a composition as defined above to
17 said surface. Likewise, the present invention also
18 provides a method of repelling aquatic organisms or of
19 repelling fungi since a surface so treated with the
composition will also have this effect.
21
22 In another aspect, the invention provides the use of
23 the composition described above in repelling insects,
24 aquatic organisms and/or fungi.
26 In yet another aspect, the invention provides the use
27 of terpenes, terpene derivatives or mixtures thereof in
28 the manufacture of a composition to repel insects,
29 aquatic organisms and/or fungi.
W094/06298 1 PCT/GB93/01g~
`- ?.,~44~ lo
2 The following examples can illustrate applications of
3 the process (all quantities are given by weight, except
4 where otherwise specified):
s
6 1. INSECT REPELLANT
8 Pine Oil 8.80
9 Surfactant 0.88
Polyamidoamine1.76
11 Butyl Acrylate/
12 Acrylonitrile Resin44.56
13 Water 44.00
14 ______
100. 00
16
17
18 When supplied to surfaces in buildings such as
19 door frames, window frames, skirting boards etc,
the surfaces become repellant to some crawling
21 insects. When applied to articles of clothing
22 such as hats, gloves, jackets etc, the surfaces
23 become repellant to some flying insects of the
24 mosquito type.
26 2. FUNGI REPELLANT
27
28 Terpineol 85.00
29 Surfactant 10.00
Polyamidoamine5.00
31 _______
32 100.00
33 _______
34
35 The above mixture can be added to normal emulsion and
W094/06298 PCT/GB93/01939
- 21~q~l7
1 gloss paints in the ratio of approximately 20ml to one
2 litre of paint, and mixed thoroughly. When applied to
3 interior surfaces of buildings the surfaces become
4 repellant to some flngi, moulds and crawling insects.
6 3. AOUATIC ORGANISM REPELLANT
8 Pine Oil 5.71
9 Polyamidoamine 9.52
Epoxide resin 9.40
11 Bentonite 0.45
12 Titanium dioxide 11.31
13 Copper thiocyanate 35.70
14 Water 27.91
_______
16 100.00
17 _______
18
19
20 When applied to surfaces such as wood, glass fibre
21 laminate etc and allowed to dry and then immersed in
22 sea water, the surface becomes repellant to many animal
23 and plant organisms to a degree efficiency greater than
24 can be expected by similar compositions based on copper
25 thiocyanate with resin in organic solvent.
26
27 4. INSECT REPELLANT
28
29 Terpineol 85.00
Wheat flour 10.00
31 Polyamidoamine 5.00
32
33 _______
34 100.00
_______
WO 94/06298 ~ S 17 12 PCI`/GB93/019-
2 The components are admixed together into a paste.
4 5. INSECT REPELLANT SACHET
6 The paste from Example 4 is inserted into a
7 polyethene film tube which is then sealed at both
8 ends.
6. AOUATIC ORGANISM REPELLANT
11
12 Example 3 was repeated with 57.12 units (by
13 weight) Cuprous oxide replacing the Copper
14 thiocyanate.
16 7. INSECT REPELLANT
17
18 Pine Oil 8.80
19 Surfactant 0.88
Polyamine 1.76
21 Butyl Acrylate/
22 Acrylonitrile Resin44.56
23 Water 44.00
24 ______
100.00
26 ______
27
W094/06298 2 1 4 ~ 5 17 13 PCT/GB93/01 ! ~
2 8. INSECT REPELLANT
4 Pine Oil 8.80
Surfactant 0.88
6 Polyamide 1.76
7 Butyl Acrylate/
8 Acrylonitrile Resin44.56
g Water 44.00
______
11 100. 00
12
13
14 9. INSECT REPELLANT
16 Terpineol 85.00
17 Wheat flour 10.00
18 Polyethyleneamine 5.00
19
_______
21 100.00
22
23
