Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
2~6~7~8
BAYER AK1~TGFSELI~C~A~T 51368 Lever~en
Koc~zen~zenhale RP
P~tente Kor~zem Rt/by/977-P
Rodenticidal foams
The present invention relates to rodenticidal foams based on hydrophilic
polymers.
It is known that indanedione derivatives and 4-hydroxycoumarins lower the
prothrombin level of blood. In rodents, they lead to a high mortality owing to
internal
haemorrhages. For this reason, they are employed as rodenticidal agents (in
this context
cf., for example, DE-OS (German Published Specification) 2 506 769, JP-PS
(Japanese
Published Specification) 480 23 942; CH-PS (Swiss Published Specification)
481 580).
In many cases, the rodenticidal active compound is mixed with various agents
which
can be eaten by rodents, such as, for example, cereal, flour, sugar and oil,
and with
inorganic auxiliaries, such as, for example, talc powder, chalk powder and
Ti02
1 ~ powder.
Baits prepared by this method have the disadvantage, however, that their
attractive
power to rodents decreases greatly with time. The decrease in the
attractiveness is to
be attributed to chemical breakdown of the active compound or of the agents
which can
be eaten.
It is known that the attractive power of baits is maintained by coating the
active
compound with polymers, such as, for example, ethylcellulose, ethoxylated
polyarylphenols, polyoxyethylene glycols, hydroxypropylmethylcellulose and the
like
(cf. EP 0 317 260, DE 26 47 722 and CA 107 963). This method has the
disadvantage
Le A 30 764-Foreign Countries
2~.6g'~88
that only the active compound and not the agents which can be eaten by rodents
is
thereby protected from ageing. For this reason, this method is unsuitable for
maintaining the attractive power of baits.
It is furthermore lmown that the attractive power of baits to rodents is
maintained by
employing chemically stable, hydrogenated oils and fats as the carrier
material (in this
context cf. JP-OS (Japanese Published Specification) 620 30 161 ). As a rule,
however,
oils and fats which are completely hydrogenated or have a low double bond
content
have a lower attractive power to rodents.
For this reason, attempts have been made to develop flexible rodenticidal
foams which
are free from agents which are sensitive to oxidation. Such rodenticidal foams
as a rule
comprise aliphatic acids, such as stearic acid; neutral, anionic or cationic
emulsifiers;
and various waxes, water and active compounds (in this context cf., for
example,
GB-PS (British Published Specification) 1 053 088, GB-PS (British Published
Specification) 1 274 442, SU-PS (Soviet Published Specification) 363 474).
However, these rodenticidal foams have the disadvantage that they have a low
storage
stability, and in particular a low stability to low temperatures and moisture.
They
collapse in the course of time to form a compact, highly viscous mass and lose
their
' biological action.
For this reason, attempts have been made to develop storage-stable rigid
rodenticidal
foams based on polystyrenes, polyacrylates and two-component polyisocyanates
(in this
context cf., for example, JP-OS (Japanese Published Specification) 55 085 501,
FR-PS (French Published Specification) 2 676 888 and US-A 4 190 734). These
rigid
rodenticidal foams are distinguished by stability to storage, low temperatures
and
moisture. However, they have the disadvantage that their preparation is
expensive.
Furthermore, their biological action is low in many cases.
The invention is therefore based on the object of developing a new
rodenticidal foam
system which is distinguished by storage stability, resistance to~ moisture
and low
temperatures, easy preparation and application and a good biological action.
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CA 02164788 1996-O1-31
The present in~rent ion x:we~.at,:es to f ~.ex~.ble
rodenticidal foams which comprise the following components:
a) rodentis~idal ac~tiue ~:~.~mpo~and; prei=erably in a
concentration of 0.001 to 5'-~ by weight, based on the weight
of the total far°mulat; tea~u;
b) hydrophi7.ic polymers having an average
molecular weight of ;000 to CO 000 (determined by means of
gel permeat ion chramat~ac~raptzy ( CPC ) t'rwm txue series
consisting of long-chain polyurethanes, polyestersr
polyester-polyol.s, pr~lyst;yrenes, p~~7.ybutadienes and malefic
acid polymers, which are in each case modified in the polymer
chain by carboxylic acid gr~:~ups ~~~r. ar~~~.no groups; preferably
in a content rat ~.on of :? .. 5 tea ~0~ by weight , based on the
weight of the total formulation;
c) long-chain aaipha~:ic:~ c~'~-.Cf~2-fatty acids, such
as palmitic acid, dodetanaic acid and stearic acid, or alkali
metal, alkaline earth metal and ammot~~ium salts thereof;
preferably in a concentratit~n of 2.5 to ~0, particularly
preferable of 2.5 to 12.55 by weight, based on the weight of
the total formul.ation8
d) and, if appropriate, further auxiliaries from
the series consisting rW dyestuffs,, emulaifiec,s, solvents,
preservat Ives , att tact ant s and ba it s ; in a content rat ion of 0
to 15~ by weight , based c>n the weight; c~f the tat~tl
formulation.
The polymers used according to the invention are
described as pa l.nt binders, fCrr example, ira H,. K:i.tt:el,
Lehrbuch der Lacke and Beschichtungen [Textbook of Paints and
._
2:3189-7878
CA 02164788 1996-O1-31
Coatings], Uolurrre IV, pages 76 ttV~ .~O~j '~erlag w.A. Colomb
( 186 ) or in the same ~extbool.:, ~d t ion ( 176 ) , Zlolume l~l,
pages 3~8 to 3~8.
Polymers which care be used aco~arding to the
invention are physically drying bir~rde~r°s, for example tYrose in
which the binders are based orr a oompletel.y reacted linear
polyurethane of ( i ) a pr~l.ye;~ter-~po:iy~:rl, ( 11 ) a chain
lengthening agerdt and ( ~.1~.) a di~.srmyanata and ( iv) a
hydroxycarboxyli.c acid.
Suitable pcrlyester.~-polyols (i) for t.he~ preparation
of such polyuretharres are, ~_or exarrrple, adipic: acid,
alkanediol and polyester°--dira~.s c;~f mol.ecu lan weight range 600
to 3000. The al.kanediols arse, for example, butane-1,4-dial,
hexane-1,6-dial, neopentylglycol or: mixtures of suoh glycols.
Suitable drain l.engthenzng agents ( ~.i ) are, for example,
dials of the type employed for° the prepar~at ion o~f the
polyester-dials, and
3 a ._
X3189-7878
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also diamines, such as hexamethylenediamine or isophoronediamine. Suitable
diisocyanates (iii) are, for example, 4,4-diisocyanatodiphenylmethane,
isophorone
diisocyanate or hexamethylene diisocyanate. The polyurethanes are prepared by
reaction of the starting materials in a manner known per se, a ratio of the
equivalence
of isocyanate groups to groups which are reactive towards isocyanate groups of
about
0.9:1 to 1.1:1 being maintained.
Binders which dry by oxidation can also be used according to the invention.
Such
binders which may be mentioned are those based on polybutadiene, styrene and
malefic
anhydride and having ionic groups, such as are described in the Applications
EP-A 0 170 184 and EP-A 0 270 795.
The hydrophilic polymers which can be used according to the invention have an
average molecular weight of 2000 to 60 000 g/mol, preferably 2500 to 25 000
g/mol.
They are present in the finished formulation in a concentration of 2.5 to 40,
preferably
2.5 to 10% by weight, based on the weight of the total formulation.
All rodenticidal active compounds are in principle suitable for preparation of
the
flexible rodenticidal foam according to the invention. Reference may be made
in
particular in this connection to the anticoagulating substances, such as the 4-
hydroxycoumarin derivatives (1-phenyl-2-acetyl)-3-ethyl-4-hydroxycoumarin
("warfarin"), 3-(a-acetonyl-4-chlorobenzyl~4-hydroxycownarin ("coumachlor"),
[3-(4'-
hydroxy-3'-coumarinyl)-3-phenyl-1-(4'-bromo-4'-biphenyl)-propan-1-of ("broma-
diolone"), 3-(3'-paradiphenylyl-1',2',3',4'-tetrahydro-l'-naphthyl~4-
hydroxycoumarin
("difenacoum") brodifacoum, flocoumafen and 3-(1',2',3',4'-tetrahydro-l'-
naphthyl~4-
hydroxycoumar-in ("coumatetralyl"), the indanedione derivatives, such as 1,1-
diphenyl-
2-acetyl-indane-1,3-dione ("diphacinone") and (1'-p-chlorophenyl-1'-phenyl~2-
acetyl-
indane-1,3-dione ("chlorodiphacinone") and the hydrocy-4-benzothiopyranones,
for
example difethialone.
The following 2-a7acycloallcylmethyl-substituted benzhydryl ketones and
carbinols may
be mentioned as fwther anticoagulants which are suitable for preparation of
the baits
according to the invention:
L,eA30764 _4_
1-phenyl-3-(2-piperidyl~l-(p-tolylr2-propanone, 3,3-Biphenyl-1-(2-pyrolidinyl~-
2-
pentanone, l,l-Biphenyl-3-[2-(hexahydro-1H-azepinyl)]-2-propanone, 1-(4-
fluorophenyl~l-phenyl-3-(2-piperidyl)-2-propanone, 1-(4-methylthiophenyl~l-
phenyl-3-
(5,5-dimethyl-2-pyrrolidinyl~2-propanone, 1-(p-cumenyl}-1-phenyl-3-(4-tert-
butyl-2-
piperidinyl~2-propanone, 3,3-Biphenyl-1-[2-(hexahydro-lH-azepinyl]-2-butanone,
3-
(2,4-dichlorophenyl~3-phenyl-1-(2-piperidyl~2-heptanone,l,1-Biphenyl-3-(5-
methyl-2-
pyrrolidinyl~2-propanones, 3,3-Biphenyl-1-(2-piperidyl)-2-butanone, a-(a-
methyl-a-
phenylbenzyl~2-piperidine-ethanol, a-(a-ethyl-a-phenylbenzyl~2-pyrrolidine-
ethanol,
(2,5-dimethyl-a-phenylbenzyl~2-piperidine-ethanol and a-(diphenylmethyl~2-
(hexa-
hydro-lH azepine~thanol and their salts, which are described in DT-OS 2 417
783,
and 4'-(fluorophenyl~2-(2-pyrrolidinyl}-acetophenone, 4'-phenyl-2-(S,5-
dimethyl-2-
pyrrolidinyl)-acetophenone, 4'-[p-(trifluoromethyl)-phenyl]-2-(2-piperidyl)-
aceto-
phenone, 4'-(p-butoxyphenyl~2-(4-tert-butyl-2-piperidyl~acetophenone, 2'-
phenoxy-2-
(2-piperidyl~acetophenone,4'-(p-fluorophenoxy~2-(5,5-dimethyl-2-
pyrrolidinyl~aceto-
phenone, 4'-(p-chlorophenoxy~2-(2-piperidyl~acetophenone, 4'-[m
(trifluoromethyl~
phenoxy]-2-(2-piperidyl~acetophenone, 4'-(p-butoxyphenoxy~2-(2-
pyrrolidinyl~aceto-
phenone, 2-(2-piperidyl)-4'-(traps-p-tolylvinylene~acetophenone, 2-(2-
hexahydro-lH-
azepinyl)-4'-(traps-styryl~acetophenone, 4'-(m-methoxyphenylvinylene)-2-(2-
pyrroli-
dinyl~acetophenone, 2-(2-piperidyl)-4'-[(p-methylthio~phenylvinylene]-
acetophenone,
4'-(3-phenoxypropoxy~2-(2-piperidyl~acetophenone, 4'-(4-phenylbutyl~2-(2-
piperidyl)-
acetophenone,4'-(a,a-dimethylbenzyl)-2-(piperidyl)-acetophenone,4'-phenethyl-2-
(3,5-
diethyl-2-piperidyl~acetophenone, 4'-phenyl-2-(2-pyrrolidinyl~acetophenone, a-
[2-(2-
phenyl-ethoxy)phenyl]-2-piperidine-ethanol, a-(p-phenoxyphenyl~2-pyrrolidine-
ethanol,
a-[4-(4-bromophenoxy}-phenyl]-6-methyl-2-piperidine-ethanol, a-(p-
phenethyl~phenyl-
2-pyrrolidine-ethanol, a-p-bisphenyl-2-hexanehydro-lH-azepine-ethanol, a-[3-(4-
phenoxybutoxy~phenyl]-2-piperidine-ethanol and a-(4-benzyl)-phenyl-2-
piperidine-
ethanol and their salts, which are described in DT-OS 2 418 480.
Acute poisons can of course also be employed for preparation of the new
flexible
rodenticidal foam.
The following rare earth metal salts can likewise be used as an anticoagulant:
dineodymium dihydroxybenzenedisulphonate (Acta physiol. Acad. Sci. Hungar. 24,
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373), dineaodymium 3-sulphonato-pyridine-4-carboxylate and cerium(III) tris-(4-
aminobenzenesulphonate).
The amount of anticoagulants can be varied widely in the range between 0.001
and 5%
(per cent by weight, based on the total bait composition), amounts of between
0.01 and
1.0% being preferred.
Other active compounds, such as cholecalciferol and calciferol, can of course
be added
to the baits according to the invention in amounts of 0.001 to 1.0%.
The flexible foams according to the invention can of course be provided with
auxiliaries from the group consisting of aatractants, fragrancxs; flavourings,
paraffin
derifatives, hydrogenated fats and oils.
Attractants which may be mentioned are, inter alia, naturally occurring oils,
such as
soya oil, rapeseed oil, coin oil or olive oil, oleic acid esters, such as, for
example,
glycerides, and sorbitan acid esters and mixtures thereof. Sweeteners, such as
sugar,
maltose, sucrose or molasses, may furthermore be mentioned.
The rodenticidal systems prepared in this way are premixes. They may be
diluted with water in amounts of 0-80% before application.
The flexible foams according to the invention can be prepared in a manner
(mown per
se by stirring or shaking. Another possibility is in situ preparation by means
of blowing
agents during application.
Blowing agents which may be mentioned for preparation of the fornlulations
according
to the invention are C02, NZO, lower alkanes, such as propane or n-butane, iso-
butane,
halogen-containing lower alkanes and low-boiling ethers, such as dimethyl
ether, and
mixtures of the said blowing agents.
The foam according to the invention has an outstanding adhesion to the rodent
coat. It
is dimensionally stable for several weeks and has a good rodent activity. It
is suitable
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23189-7878
2~s~~ss
for combating rodents such as rats, mice and the like, including at damp
locations (for
example canals, riverbanks).
The invention will be illustrated in more detail with the aid of the following
embodiment examples, without limiting its scope.
Example 1
1. Coumatetralyl 0.07%
2. Stearic acid 7.50%
3. Triethanolamine 4.16%
4. Polywax 1550 2.50%
5. NP 10, a nonionic emulsifier1.00%
6. Glycerol 8.00%
7. Crystalline sugar 5.00%
8. Bayhydrol VP-LS 2069 10.00%
9. Tap water about 54.27%
10. Isobutane 7.50%
100.00% = 250 g
This formulation was introduced into A1 cans (1 000 ml). Bayhydrol VP-LS 2069
is an
aqueous polyester-polyurethane from Bayer AG, D-51368 Leverkusen. It comprises
soya oil fatty acid, trimethylolpropane, hexanediol, adipic acid, isophthalic
acid,
dimethylolpropionic acid, hexamethyl diisocyanate, isophorone diisocyanate,
neopenthylglycol and dimethylethanolamine.
This formulation leads to flexible foams which are distinguished by their long-
term and
low-temperature stability. The flexible foams thus prepared are stable to low
temperatures at -4°C for several weeks and have an outstanding
biological action
against rodents. They are very suitable for combating mice, rats and the like.
LeA30764 -7-
~~s~7~s
Determination of the biological action
Rattus norvegicus wild strain
The animals originate from traps in the open and are reared in the laboratory.
Weight
of the test animals employed in g: 230/285/234/342/325
Test method:
The test was carried out with brown rats (Rattus norvegicus) vv~'Id form
(number: S) in
a small enclosure in accordance with Guideline 9 - 3.2 of the Federal
Biological
Institute. The enclosure comprised three chambers lying one behind the other.
Each
chamber had a floor area of 1 m2. The individual chambers were connected to
one
another by holes (battery). One chamber, which served the rats as "living
space",
contained a nesting box with hay and cellulose for building nests. The middle
chamber
remained empty. The food and test agent were laid out in the third chamber.
Drinking
water was available ad libitum through the entire test period. After the rats
had been
removed from the rearing pens, they were allowed to acclimatize themselves to
the new
environment for 3 days. After this acclimatization, the rats were prefect with
Altromin O (standard diet) for one day.
A foam carpet (diameter: 40 X 60 cm / height: 1 cm) was then laid out at the
entrance
to the 3rd chamber. Feeding was continued with Altromin O, and the amounts
eaten
were determined daily by reweighing.
Results:
The results are shown in Tables 1 and 2.
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Table 1
Reactions of brown rats to a rodenticide foam carpet between the living and
feeding
area
Start of experimentA semi-circular foam carpet (diameter:
60 X 40 cm /
height: 1 cm) is laid out in the food
basin in front of
the entrance.
1st day The rats have formed 2 circular holes
in the foam,
with the aid of which they can cross
the foam by
jumping in order to reach the food. Some
flakes of
foam lie in the running basin. The rats
have a clean
coat.
2nd day The foam carpet is renewed.
2nd day The rats have formed a passage through
the foam
through which they can reach the food
without
touching the foam. Some flakes of foam
lie in the
nu~ning basin. The test animals have
a clean coat.
3rd day Same result as on the 2nd day.
4th day The 1 st rat is dead; otherwise the result
is the same as
on the preceding day.
5th day The 2nd rat is dead. One animal has coordination
problems. The remaining rats continue
to cross the
foam carpet.
6th day The 3rd rat has died and 1 animal has
poisoning
symptoms.
7th day The 4th rat is dead. The last living
animal shows no
poisoning symptoms.
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21~~7R8
8th-l lth day On the 10th day, the Sth rat also shows poisoning
symptoms. On the l lth day the animal is dead.
T e2
Food intake during the 11 test days (n = 5 brown rats)
Test day 1 st feeding 2nd feeding Dead individuals
point point (total)
g g
S 1 31.6 22.4 0
2 71.1 44.0 0
3 71.7 32.7 0
4 30.9 21.4 1
0.0 2.9 2
6 2..8 0.0 3
7 2.3 2.9 4
8 4.0 0.0 4
9 3.0 0.0 4
10 0.0 3.1 4
11 0.0 0.0 5
The foam carpet between the living and feeding area necessarily had to be run
through
by the animals in order to reach the food. The animals formed a narrow path
through
the foam. Flakes of foam which remained attached to the coat were either
scraped off
in the middle basin or removed from the coat by grooming.
The time before the animals were killed (4-7 days) corresponds to our
experiences with
the "multible dose anticoagulant coumatetralyl".
One animal showed no poisoning symptoms until the 9th day and died only on the
l lth day. It is to be assumed that this animal only crossed the foam carpet
in the first
LeA30764 - 10-
~is~7ss
nights after the other animals of the pack had already formed a lane through
which it
was possible to cross through the foam carpet without contamination.
e2
1. Coumatetrolyl 0.07%
2. Stearic acid 7.50%
3. Triethanolamine 4.16%
4. Polywax 1550 2.50%
5. NP 10 1.00%
6. Glycerol 8.00%
7. Crystalline sugar 5,00%
8. Bayhydrol VP-LS 2845 10.00%
9. Tap water 54.27%
10. Isobutane/propane ( 1:1 ) 7.50%
100.0% = 250 g
This formulation was introduced into 1000 ml cans. Bayhydrol VP-LS 2845 is an
aqueous polyester-polyurethane solution from Bayer AG D-51368 Leverkusen. The
' polyurethane component comprises Soya oil fatty acid, trimethylolpropane,
hexanediol,
adipic acid, isophthalic acid, dimethylolpropionic acid, isophorone
diisocyanate and
dimethylethanolamine. This formulation leads to flexible foams which are
distinguished
by their long-term and low-temperature stability. The flexible foams thus
prepared are
stable to low temperatures at 14°C for several weeks and have an
outstanding
biological activity.
~c a 3
1. Coumatetrolyl 0.07%
2. Stearic acid 7.50%
3. Triethanolamine 4.16%
4. Polywax 1550 2.50%
Le A 30 764 . - 11 -
2~64'~88
5. NP 10 1.00%
6. Glycerol 8.00%
7. Crystalline sugar 5.00%
8. Bayhydrol B 130 10.00%
9. Tap water 54.27%
10. Isobutane 7.50%
Bayhydrol B 130 is an aqueous polymer solution from Bayer AG. The polymer
component comprises malefic anhydride, styrene, polybutadiene and ammonia.
This formulation leads to flexible foams which are distinguished by their long
term and
low temperature stability. The flexible foams thus prepared are stable to low
temperatures at -+-.4°C for several weeks and have an outstanding
biological action
against rodents, such as mice and rats.
Le A 30 764 - 12 -
