CA2164788C - Rodenticidal foams - Google Patents
Rodenticidal foams Download PDFInfo
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- CA2164788C CA2164788C CA002164788A CA2164788A CA2164788C CA 2164788 C CA2164788 C CA 2164788C CA 002164788 A CA002164788 A CA 002164788A CA 2164788 A CA2164788 A CA 2164788A CA 2164788 C CA2164788 C CA 2164788C
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/16—Foams
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to rodenticidal foams based on hydrophilic polymers, of the following composition:
a) rodenticidal active compound, b) hydrophilic polymers having an average molecular weight of 2000 to 60 000 (determined by means of gel permeation chromatography (GPC)) from the series consisting of long-chain polyurethanes, polyesters, polyester-polyols, polystyrenes, polybutadienes and maleic acid polymers, which are in each case modified in the polymer chain by carboxylic acid groups or amino groups, c) long-chain aliphatic C6-C22-fatty acids, such as palmitic acid, dodecanoic acid and stearic acid, or alkali metal, alkaline earth metal and ammonium salts thereof, d) and if appropriate further auxiliaries from the series consisting of dyestuffs, emulsifiers, solvents, preservatives, attractants and baits.
a) rodenticidal active compound, b) hydrophilic polymers having an average molecular weight of 2000 to 60 000 (determined by means of gel permeation chromatography (GPC)) from the series consisting of long-chain polyurethanes, polyesters, polyester-polyols, polystyrenes, polybutadienes and maleic acid polymers, which are in each case modified in the polymer chain by carboxylic acid groups or amino groups, c) long-chain aliphatic C6-C22-fatty acids, such as palmitic acid, dodecanoic acid and stearic acid, or alkali metal, alkaline earth metal and ammonium salts thereof, d) and if appropriate further auxiliaries from the series consisting of dyestuffs, emulsifiers, solvents, preservatives, attractants and baits.
Description
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.
LeA30764 _2_ 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 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 ._ 2164'~R8 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~-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, (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, LeA30764 . -5-~t 6'i9 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 LeA30764 _6_ 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%
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.
LeA30764 _2_ 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 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 ._ 2164'~R8 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~-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, (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, LeA30764 . -5-~t 6'i9 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 LeA30764 _6_ 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.
LeA30764 -g_ ~~~4"~R8 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.
LeA30764 -9-21~~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 -
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.
LeA30764 -g_ ~~~4"~R8 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.
LeA30764 -9-21~~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 -
Claims (11)
1. A flexible rodenticidal foam which comprises the following components:
a) a rodenticide, b) a hydrophilic polymer having an average molecular weight of 2000 to 60 000 selected from long-chain polyurethanes, polyesters, polyester-polyols, polystyrenes, polybutadienes and maleic acid polymers, each of which is modified in the polymer chain by carboxylic acid groups or amino groups, c) and a long-chain aliphatic C6-C22-fatty acid.
a) a rodenticide, b) a hydrophilic polymer having an average molecular weight of 2000 to 60 000 selected from long-chain polyurethanes, polyesters, polyester-polyols, polystyrenes, polybutadienes and maleic acid polymers, each of which is modified in the polymer chain by carboxylic acid groups or amino groups, c) and a long-chain aliphatic C6-C22-fatty acid.
2. A foam according to claim 1 further comprising d) a dyestuff, emulsifier, solvent, preservative, attractant or bait.
3. A premix for the preparation of a flexible rodenticidal foam comprising:
a) a rodenticide, b) a hydrophilic polymer having an average molecular weight of 2000 to 60 000 selected from long-chain polyurethanes, polyesters, polyester-polyols, polystyrenes, polybutadienes and maleic acid polymers, each of which is modified in the polymer chain by carboxylic acid groups or amino groups, c) and a long-chain aliphatic C6-C22-fatty acid.
a) a rodenticide, b) a hydrophilic polymer having an average molecular weight of 2000 to 60 000 selected from long-chain polyurethanes, polyesters, polyester-polyols, polystyrenes, polybutadienes and maleic acid polymers, each of which is modified in the polymer chain by carboxylic acid groups or amino groups, c) and a long-chain aliphatic C6-C22-fatty acid.
4. A premix according to claim 3 further comprising d) a dyestuff, emulsifier, solvent, preservative, attractant or bait.
5. A premix according to claim 3 wherein the long-chain aliphatic fatty acid is palmitic, dodecanoic or stearic acid or an alkali metal, alkaline earth metal or ammonium salt thereof .
6. A premix according to claim 4 wherein the long-chain aliphatic fatty acid is palmitic, dodecanoic or stearic acid or an alkali metal, alkaline earth metal or ammonium salt thereof .
7. A process for preparing a premix according to claim 3 comprising dissolving, dispersing, emulsifying or suspending the rodenticide in a premix solution of the polymer and fatty acid.
8. A process according to claim 7 wherein the premix further comprises d) a dyestuff, emulsifier, solvent, preservative, attractant or bait.
9. A process according to claim 7 wherein the long-chain aliphatic fatty acid is palmitic, dodecanoic or stearic acid or an alkali metal, alkaline earth metal or ammonium salt thereof .
10. A process according to any one of claims 7 to 9 further comprising adding up to 80% water to the premix and forming a foam by means of a blowing agent.
11. A process according to claim 10 further comprising stirring or shaking the premix during formation of the foam.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4444261.0 | 1994-12-13 | ||
| DE4444261A DE4444261A1 (en) | 1994-12-13 | 1994-12-13 | Rodenticides foams |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2164788A1 CA2164788A1 (en) | 1996-06-14 |
| CA2164788C true CA2164788C (en) | 2007-02-13 |
Family
ID=6535623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002164788A Expired - Fee Related CA2164788C (en) | 1994-12-13 | 1995-12-08 | Rodenticidal foams |
Country Status (22)
| Country | Link |
|---|---|
| EP (1) | EP0719498B1 (en) |
| JP (1) | JP3498159B2 (en) |
| AR (1) | AR000174A1 (en) |
| AT (1) | ATE180384T1 (en) |
| AU (1) | AU696810B2 (en) |
| BR (1) | BR9505761A (en) |
| CA (1) | CA2164788C (en) |
| CZ (1) | CZ290972B6 (en) |
| DE (2) | DE4444261A1 (en) |
| DK (1) | DK0719498T3 (en) |
| ES (1) | ES2132499T3 (en) |
| FI (1) | FI110052B (en) |
| GR (1) | GR3030435T3 (en) |
| HU (1) | HU222007B1 (en) |
| NO (1) | NO305461B1 (en) |
| PL (1) | PL185220B1 (en) |
| RU (1) | RU2143803C1 (en) |
| SK (1) | SK280990B6 (en) |
| TR (1) | TR199501266A2 (en) |
| TW (1) | TW290429B (en) |
| UA (1) | UA40620C2 (en) |
| ZA (1) | ZA9510543B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4549027B2 (en) * | 2002-02-04 | 2010-09-22 | アース製薬株式会社 | Poisonous bait for mice and method for stabilizing the same |
| MY143382A (en) * | 2005-11-18 | 2011-05-13 | Basf Se | Aqueous rodenticide formulations |
| AU2008309681A1 (en) * | 2007-10-01 | 2009-04-16 | Basf Se | Rodenticide mixture |
| WO2013003946A1 (en) * | 2011-07-04 | 2013-01-10 | Contech Enterprises Inc. | Compositions and methods for attracting and stimulating feeding by mice and rats |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES312702A1 (en) * | 1964-06-02 | 1966-02-16 | Mcneil Laboratories Incorporated | A procedure to prepare a raticite bait. (Machine-translation by Google Translate, not legally binding) |
| US3816610A (en) * | 1969-04-25 | 1974-06-11 | Westinghouse Electric Corp | Palatable foamed rodent control material |
| CH592189B5 (en) * | 1972-06-21 | 1977-10-14 | Ciba Geigy Ag | |
| US4207335A (en) * | 1975-09-23 | 1980-06-10 | Beecham Group Limited | Indan-1,3-diones |
| US4836939A (en) * | 1986-07-25 | 1989-06-06 | Rockwood Systems Corporation | Stable expandable foam & concentrate & method |
-
1994
- 1994-12-13 DE DE4444261A patent/DE4444261A1/en not_active Withdrawn
-
1995
- 1995-10-13 TR TR95/01266A patent/TR199501266A2/en unknown
- 1995-10-20 TW TW084111065A patent/TW290429B/zh not_active IP Right Cessation
- 1995-11-21 AR AR33431795A patent/AR000174A1/en unknown
- 1995-11-30 EP EP95118834A patent/EP0719498B1/en not_active Expired - Lifetime
- 1995-11-30 DE DE59506027T patent/DE59506027D1/en not_active Expired - Lifetime
- 1995-11-30 ES ES95118834T patent/ES2132499T3/en not_active Expired - Lifetime
- 1995-11-30 AT AT95118834T patent/ATE180384T1/en not_active IP Right Cessation
- 1995-11-30 DK DK95118834T patent/DK0719498T3/en active
- 1995-12-06 AU AU40268/95A patent/AU696810B2/en not_active Ceased
- 1995-12-08 CA CA002164788A patent/CA2164788C/en not_active Expired - Fee Related
- 1995-12-11 PL PL95311777A patent/PL185220B1/en unknown
- 1995-12-11 FI FI955937A patent/FI110052B/en active
- 1995-12-11 JP JP34542395A patent/JP3498159B2/en not_active Expired - Fee Related
- 1995-12-12 BR BR9505761A patent/BR9505761A/en not_active IP Right Cessation
- 1995-12-12 UA UA95125272A patent/UA40620C2/en unknown
- 1995-12-12 NO NO955021A patent/NO305461B1/en unknown
- 1995-12-12 CZ CZ19953279A patent/CZ290972B6/en not_active IP Right Cessation
- 1995-12-12 ZA ZA9510543A patent/ZA9510543B/en unknown
- 1995-12-12 SK SK1554-95A patent/SK280990B6/en unknown
- 1995-12-13 HU HU9503559A patent/HU222007B1/en not_active IP Right Cessation
- 1995-12-13 RU RU95120581/13A patent/RU2143803C1/en not_active IP Right Cessation
-
1999
- 1999-06-09 GR GR990401522T patent/GR3030435T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HU9503559D0 (en) | 1996-02-28 |
| DE4444261A1 (en) | 1996-06-20 |
| HU222007B1 (en) | 2003-03-28 |
| ES2132499T3 (en) | 1999-08-16 |
| NO955021L (en) | 1996-06-14 |
| FI955937A (en) | 1997-08-13 |
| JPH08225403A (en) | 1996-09-03 |
| NO955021D0 (en) | 1995-12-12 |
| TR199501266A2 (en) | 1996-07-21 |
| EP0719498A1 (en) | 1996-07-03 |
| DK0719498T3 (en) | 1999-11-15 |
| PL311777A1 (en) | 1996-06-24 |
| TW290429B (en) | 1996-11-11 |
| AU696810B2 (en) | 1998-09-17 |
| EP0719498B1 (en) | 1999-05-26 |
| GR3030435T3 (en) | 1999-09-30 |
| CZ327995A3 (en) | 1996-07-17 |
| FI955937A0 (en) | 1995-12-11 |
| NO305461B1 (en) | 1999-06-07 |
| UA40620C2 (en) | 2001-08-15 |
| BR9505761A (en) | 1998-01-06 |
| HUT74436A (en) | 1996-12-30 |
| PL185220B1 (en) | 2003-04-30 |
| SK155495A3 (en) | 1997-01-08 |
| ATE180384T1 (en) | 1999-06-15 |
| CZ290972B6 (en) | 2002-11-13 |
| CA2164788A1 (en) | 1996-06-14 |
| RU2143803C1 (en) | 2000-01-10 |
| ZA9510543B (en) | 1996-06-13 |
| SK280990B6 (en) | 2000-10-09 |
| DE59506027D1 (en) | 1999-07-01 |
| AU4026895A (en) | 1996-06-20 |
| AR000174A1 (en) | 1997-05-21 |
| JP3498159B2 (en) | 2004-02-16 |
| FI110052B (en) | 2002-11-29 |
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