FI110052B - Rotanmyrkkyvaahtoja - Google Patents

Description

110052

The present invention relates to a rat poison foam based on hydrophilic polymers.

It is known that indanedione derivatives and 4-hydroxy coumarins reduce blood prothrombin levels. In rodents, they lead to an increase in mortality due to internal bleeding. For this reason, they are used as rat poisons (cf. e.g. references DE-A-2,506,769, JP-A-48 023 942 and CH-A-A-481 580).

In many cases, the rat-killing agent may be mixed with foods ingested by rodents, such as cereals, flour, sugar and oil, or inorganic adjuvants such as talc, chalk, and TiO2 powders.

However, the drawback of baits made in this way is that their ability to attract rodents is greatly diminished over time. The decrease in attractiveness is due to the chemical degradation of the active ingredient or edible foodstuff.

It is known that the attractiveness of baits can be maintained by coating the active ingredient with poly- /. with ethers such as ethyl cellulose, ethoxylated polyaryl phenols, polyoxyethylene glycols, hydroxypropylmethyl cellulose, etc. (cf. EP-0 317 260, DE-2 647 722 and CA-107 963). The disadvantage of these methods, however, is that in this way only the active ingredient is protected from aging, and no food is eaten by rodents. These methods are, therefore, unsuitable for maintaining the attractiveness of the baits.

It is further known that the ability of baits to attract rodents can be maintained by using chemically stable, hydrogenated oils and fats as carrier materials (cf., in this respect, JP-A-35 62 030 161). However, fully hydrogenated or low double bond oils and fats tend to attract little rodents.

For this reason, attempts have been made to develop rat foam soft foams which do not contain substances which are susceptible to oxidation. Such rat poisonous foams generally contain aliphatic acids such as stearic acid, neutral, anionic or cationic emulsifiers, various waxes, water and active ingredients (cf., for example, British Patent Specification 1,053,088, British Patent Specification 101274442, U.S. Pat. ).

But such rat-foaming foams have the drawback of low storage stability and especially low frost or moisture resistance. Over time, they collapse into a compact, highly viscous mass and lose their biological effect.

For this reason, attempts have been made to develop rat poison hard foams based on polystyrenes, polyacrylates, and bicomponent polyisocyanates (cf., for example, JP Application 55,085,501, FR 20,667,888 and US 4,473). These rat venom foams are resistant to storage, frost and humidity. But their drawback is laborious manufacturing. In addition, the biological effect is in many cases negligible.

The object of the invention has thus been to develop a novel rat foam foam system which is characterized by storage, moisture and frost resistance, ease of manufacture and use, and good biological effect.

The present invention relates to rat venom soft foams, which comprise the following components: a) a rat killer, preferably in an amount of 0.001 to 5% by weight, based on the total weight of the formulation; b) hydrophilic polymers having an average molecular weight of from 2000 to 60,000 (as determined by gel permeation chromatography (GPC)) selected from the group consisting of long chain polyurethanes, polyesters, polyester polyols, polystyrenes, polybutyrenes and males, in each case modified by carboxylic acid or amino groups, the amount of polymers being preferably from 2.5 to 40% by weight based on the weight of the total formulation; c) long chain, aliphatic C6-C22 fatty acids, for example palmitic acid, dodecanoic acid and stearic acid or their alkali, alkaline earth and ammonium salts, preferably in the amount of 2.5 to 20 and particularly preferably 2.5 to 12, 5% by weight based on the total formulation weight; and d) optionally, other excipients selected from the group consisting of dyes, emulsifiers, solvents, preservatives, attractants and baits in an amount of 0-15% by weight of the total formulation.

The polymers used in accordance with the invention are described, for example, in H. Kittel, Lehrbuch der Lacke und 20 Beschichtungen, Vol. IV, p. 76 306, Verlag W.A. Colomb (1986) or in the same textbook, edition (1976), Volume IV, pp. 328-358, as binders for varnishes.

The polymers used in accordance with the invention are physically drying binders, e.g., those in which the binder is based on a fully reacted linear polyurethane consisting of (i) polyester polyol, (ii) a chain extender and (iii) diisocyanate and (iv) hydroxycarboxylic acid.

Suitable polyester polyols (i) for the preparation of such polyurethanes include, for example, adipic acid, alkane diol, polyester diols having a molecular weight range of 600 to 3000. The alkane diol is e.g. butanediol-1,4, hexanediol-1,6, neopentyl glycol or the like. alloys. Suitable chain extending agents (ii) include, for example, diols used to prepare polyester diols, and also diamines, such as hexaraethylene di-110052 4 amine or isophorone diamine. Suitable diisocyanates (iii) are, for example, 4,4-diisocyanatodiphenylmethane, isophorone diisocyanate or hexamethylene diisocyanate. Polyurethanes are prepared in a manner known per se to react the anta-5 club starting materials so that the equivalent ratio of isocyanate groups to isocyanate reactive groups is maintained in the range of about 0.9: 1 to 1.1: 1.

Also useful according to the invention are binders which are desiccant drying. As such, ionic group-based binders based on polybutadiene, styrene and maleic anhydride, such as those described in European Patent Application Publication No. O 170 184 and European Patent Application 0 270 795, are mentioned.

The hydrophilic polymers useful according to the invention have a molecular weight of 2,000 to 60,000 g / mol, preferably 2,500 to 25,000 g / mol. Their concentration in the finished formulation is from 2.5 to 40, preferably from 2.5 to 10% by weight, based on the weight of the total formulation.

In principle, all rat lethal agents are useful in the preparation of the rat venom soft foam according to the invention. In this context, particular reference is made to anticoagulants, examples of which are 4-hydroxycoumarin derivatives (1-phenyl-2-acetyl) -25 3-ethyl-4-hydroxycoumarin ("warfarin"), 3- (a-acetonyl-4-chlorobenzyl). -4-hydroxycoumarin ("coumachlor"), 3- (4'-hydroxy-3'-coumarinyl) -3-phenyl-1- (4'-bromo-4'-biphenyl) propan-1-ol ("bromadiolone"), 3- (3'-para-diphenylyl-1,2,4,3,4,4-tetrahydro-1'-naphthyl) -4-hydroxy-30-sicumarin ("difenacum"), brodifacum, flocoumafen, and 3- (1, 2, 3, 3, 4'4-Tetrahydro-1'-naphthyl) -4-hydroxycoumarin ("coumatetralyl"), indanedione derivatives such as 1,1-diphenyl-2-acetylindan-1,3-dione ("dipakinone") (1'-p-Chlorophenyl-1'-phenyl) -2-acetylindan-1,3-35 dione ("chlorodipakinone") and hydroxy-4-benzothiopyranones such as difethialone.

110052 5

Other anticoagulants useful in the preparation of the baits of the invention include the following 2-azacycloalkylmethyl-substituted benzhydryl ketones and carbinols: 5-phenyl-3- (2-piperidyl) -1- (p-tolyl) -2-propanone, 3,3-diphenyl -1- (2-pyrrolidinyl) -2-pentanone, 1,1-diphenyl-3- [2- (hexahydro-1H-azepinyl)] -2-propanone, 1- (4-fluorophenyl) -1-phenyl- 3- (2-piperidyl) -2-propanone, 1- (4-methylthiophenyl) -1-phenyl-3- (5,5-dimethyl-2-pyrrolidinyl) -2-propanone, 1- (p-cumenyl) -1-phenyl-3- (4-tert-butyl-2-piperidinyl) -2-propanone, 3,3-diphenyl-1- [2- (hexahydro-1H-azepinyl] -2-butanone, 3- (2,4-Dichlorophenyl) -3-phenyl-1- (2-piperidyl) -2-heptanone, 1,1-diphenyl-3- (5-methyl-2-pyrrolidinyl) -2-propanone, , 3-diphenyl-1- (2-piperidyl) -2-butanone, α- (α-methylphenylbenzyl) -2-piperidinethanol, α- (α-ethyl-α-phenylbenzyl) -2-pyrrolidine ethanol, (2) , 5-dimethyl-α-phenyl-benzyl) -2-piperidinethanol and α- (d) ifenylmethyl) -2- (hexahydro-1-azepine) ethanol and salts thereof, as disclosed in DT application 2,417,783, and 4 '- (fluorophenyl) -2- (2-pyrrolidinyl) acetophenone, 4' -phenyl-2- (5,5-dimethyl-2-pyrrolidinyl) acetophenone, 4- [p- (trifluoromethyl) phenyl] -2- (2-piperidinyl) acetophenone, 4 '- (p-butoxyphenyl) ) -2- (4-tert-butyl-2-piperidyl) acetophenone, 2'-phenoxy-2- (2-piperyl) acetophenone, 4 '- (p-fluorophenoxy) -2- (5.5 -dimethyl-2-pyrrolidinyl) acetophenone, 4 '- (p-chlorophenoxy) -2- (2-piperidyl) acetophenone, 4' - [m- (trifluoromethyl) phenoxy] -2- (2-piperidyl) acetophenone , 4 '- (p-butoxyphenoxy) -2- (2-pyrrolidinyl) acetophenone, 2- (2-piperidyl) -4' - (trans-p-tolylvinylene) acetophenone, 2- (2-hexahydro-1H-azep -nyl) -4 '- (transstyryl) acetophenone, 4' - (m-methoxyphenylivinylene) -2- (2-pyrrolidinyl) acetophenone, 2- (2-piperidyl) -4 '[(p-methylthio) ) phenylvinylene] acetophenone, 4'-35 (3-phenoxypropoxy) -2- (2-piperidyl) acetophenone, 4 '- ( 4-phenylbutyl) -2- (2-piperidyl) acetophenone, 4 '- (α, α-di 110052 6-methylbenzyl) -2- (piperidyl) acetophenone, 4'-phenethyl-2 ( 3,5-diethyl-2-piperidyl) acetophenone, 4'-phenyl-2- (2-pyrrolidinyl) acetophenone, α- [2- (2-phenylethoxy) phenyl] -2-piperidinethanol, α- (p- phenoxyphenyl) -2-pyrrol-5-lidinethanol, α- [4- (4-bromophenoxy) phenyl] -6-methyl-2-piperidinethanol, α- (p-phenethyl) phenyl-2-pyrrolidine ethanol, ap-bisphenyl- 2-Hexanehydro-1H-azepine ethanol, α- [3- (4-phenoxybutoxy) phenyl] -2-piperidine ethanol and α- (4-benzyl) phenyl-2-piperidine ethanol and salts thereof as described in the DT application 2,418,480.

It is clear that acute poisons can also be used in the preparation of the new rat foam soft foam.

Likewise, the following rare earth salts may be used as anticoagulants: dineodymium hydroxybenzene disulfonate (Acta Physiol. Acad. Sci. Hungar. 24, 373), dineodymium 3-sulfonatopyridine carboxylate (4) and cerium (III) trisis (4-amine).

The amount of anticoagulants can vary widely within the range of 0.001 to 5% (based on weight percent of the total weight of the bait), with amounts of 0.01 to 1.0% being preferred.

Of course, other active ingredients such as cholecalciferol and calciferol may be added to the feeds of the invention in an amount of 0.001 to 1.0%.

Of course, the soft foams of the invention may be supplemented with excipients from the group consisting of attractants, perfumes, flavorings, paraffin derivatives, hydrogenated fats and oils.

30 Examples of attractants include: natural oils such as soybean oil, rapeseed oil, corn oil or olive oil, oleic acid esters such as glycerides and sorbitan esters and mixtures thereof. In addition, sweeteners such as sugar, maltose, sucrose or molasses may be mentioned.

The rat poison systems so prepared are premixes. Before use, they should usually be diluted with 0-80% water.

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The foams of the invention may be prepared by mixing or shaking in a manner known per se. In addition, propellants may be manufactured during use.

Suitable propellants useful in the preparation of the formulations of the invention include CO 2, N 2 O, lower alkanes such as propane or n-butane isobutane, lower alkanes halogenated, and low boiling ethers such as dimethyl ether and mixtures of said propellants.

The foam according to the invention adheres very well to the rodent's Turkey. It is persistent for several weeks and is very effective against rodents. It is suitable for the control of rodents such as rat, mouse, etc. even in humid places 15 (eg canals, river channels).

The following Examples illustrate the invention without limiting its scope.

Example 1 1. Coumatetralyl 0.07% ··· 2. Stearic acid 7.50% I.. 3. Triethanolamine 4.16% 4. Polywachs 1550 2.50% 5. NP 10, Nonionic Emulsifier 1.00% 6. Glycerol 8.00% 25 7. Granulated Sugar 5.00% 0 8. Bayhydrol VP-LS 2069 10.00% 9. Tap Water About 54.27% 10. Isobutane _7.50% 100.00% =. 30 250 g ·· This formulation was packed in aluminum boxes (1000 µl). Bayhydrol VP-LS 2069 is an aqueous polyester polyurethane made by Bayer AG, D-51 368 Leverkusen. It consists of soybean oil fatty acid, trimethylolpropane, hexane, 35 diidiol, adipic acid, isophthalic acid, dimethylolpropionic acid, hexamethyldiisocyanate, isophorone diisocyanate and neopentyl glycolate.

This formulation provides soft foams that are resistant to prolonged storage and frost. The soft foams thus produced are frost-resistant for several weeks at -4 ° C and have excellent biological activity in rodents. They are very well suited for the control of mice, rats, etc.

Determination of biological effect 10 Wild strain of Rattus norvegicus

The animals were caught in the field and bred in the laboratory. Weight of test animals used in grams: 230/285/234/342/325.

Experimental Procedure 15 The experiment was performed on a rat (Rattus norvegicus) wild-type (number 5) in mini-fencing according to BBA Guidelines 9 - 3.2. The enclosure consisted of three successive chambers. Each chamber had a floor area of 1 m2. The individual chambers were connected to each other by creep openings. One of the chambers, considered by the rats as a "living room," contained a nest box and hay and pulp nesting * | for. The middle chamber remained empty. Food and test substance were placed in the third chamber. Drinking water was freely available i.i throughout the trial. Rats were taken from the breeding enclosures: · 25 and were accustomed to the new environment for 3 days.

:: After this habituation time, the rats were fed Altromin O (standard diet) for one day.

A foam mat (diameter 40 x 60 cm, pack 30 cm 1 cm) was then placed at the entrance of the third chamber. Feeding with Altromin 0 was continued and the quantities eaten were determined by daily weighing.

'! . Results v The results are shown in Tables 1 and 2.

t * · 9 11005?

table 1

Rats Reactions to the Rat Toxic Foam Mat Between the Living and Dining Area 5 An initial semicircular foam mat (through 60 x 40 cm, 1 cm thick) was placed in front of the entrance to the food pool.

On day 1, the rats had made two round holes in the foam, through which they could reach the food with a hyp-10 head.

There were a few pieces of foam plastic in the running pool. The rats' coat was clean.

Day 2 The foam mat was replaced.

On day 2, the rats had made a foam passage, 15 where they reached for food without touching the foam. There were a few pieces of foam in the running pool. The coat of the experimental animals was clean.

Day 3 The results were the same as on Day 2.

.. 20 Day 4 First rat was dead, results. were otherwise the same as the first • _ · day.

• · Day 5 Another rat was dead. One animal had coordination problems. Remaining:, · 25 rats continued to puncture the foam mat.

:: Day 6 The third rat was dead and one animal showed signs of intoxication.

Day 7 The fourth rat was dead. The last surviving animal showed no signs of intoxication.

8-11. On the tenth day in the fifth rat; day showed signs of intoxication. The animal died on the 11th.

v day.

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Table 2

Food intake for 11 experimental days (n = 5 rats)

Experiment Day 1 Feeding 2 Feeding Deaths 5 g g g individuals (sum) 1 31.6 22.4 0 2 71.1 44.0 0 10 3 71.7 32.7 0 4 30.9 21, 4 1 5 0.0 2.9 2 6 2.8 0.0 3 7 2.3 2.9 4 15 8 4.0 0.0 4 9 3.0 0.0 4 10 0.0 3.1 4 11 0,0 0,0 5 20 Animals were forced to break out of living and dining. an area foam mat for food access. Animals *; cleared a narrow path through the foam. The pieces of foam adhering to Turkey were either rubbed in the middle basin or removed during cleaning.

* t · 25 The time to death of the animals (4-7 days) corresponds to our experiments: "multiple doses of anticoagulant coummetal allyl".

One animal did not show signs of intoxication until the ninth day and died only on the 1st to 30th day. It can be assumed that this animal did not pass through the foam mat in the first nights until after the crowd; , other animals had already carved an alley that allowed them to pass through the foam mat without being contaminated.

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Example 2 1. Coumetrolyl 0.07% 2. Stearic acid 7.50% 3. Triethanolamine 4.16% 5 4. Polywachs 1550 2.50% 5. NP 10 1.00% 6. Glycerol 8.00 % 7. Granulated Sugar 5.00% 8. Bayhydrol VP-LS 2845 10.00% 10 9. Tap Water 54.27% 10. Isobutane / Propane (1: 1) 7.50% 100.0% = 250 g This formulation was packaged in 1000 ml cartons.

Bayhydrol VP-LS 2845 is a polyester polyurethane aqueous solution, manufactured by Bayer AG, D-51 368 Leverkusen. The polyurethane component consists of soybean oil fatty acid, trimethylolpropane, hexanediol, adipic acid, isophthalic acid, dimethylolpropanoic acid, isophorone diisocyanate and dimethylethanolamine. With this formulation is obtained

Il · ^> ». soft foams for long-term storage * »· V and frost. The foams thus prepared are cold; lasting several weeks at 14 ° C and having an excellent biological effect;

»1 1. ' Example 3 i 1. Coumetrolyl 0.07% 2. Stearic acid 7.50% 3. Triethanolamine 4.16%, 30 4. Polywachs 1550 2.50% (5. NP 10 1.00% '· J 6. Glycerol 8.00% 7. Granulated Sugar 5.00% 8. Bayhydrol B 130 10.00%, 35 9. Tap Water 54.27% It · 10. Isobutane 7.50% * i »110052 12

Bayhydrol B 130 is a polymeric aqueous solution manufactured by Bayer AG. The polymer component consists of maleic anhydride, styrene, polybutadiene and ammonia.

This formulation provides soft foams that withstand cold for several weeks at + 4 ° C and exhibit excellent biological activity in rodents such as mice and rats.

Claims (9)

1. Steering wheel foam, characterized in that they consist of the following components: a) a rectifying killer, b) hydrophilic polymers with an average mole mass of 2,000 - 60,000 (determined by gel permeation chromatography (GPC)); selected from the group of long-chain polyurethanes, polyesters, polyester polyols, polystyrenes, polybutadienes, maleic acid polymers, whose polymer chain was modified at each occasion with carboxylic acid or amino groups, c) long chain aliphatic C6-C22 fatty acids, and d) dyes, emulsifiers, solvents, preservatives, lids and pastures. 2. A curing foam according to claim 1, characterized in that the amount of the correcting agent is 0.001 - 5% by weight calculated by the weight of the total formulation. 3. A foamed foam according to claim 1 or 2, characterized in that the amount of the hydrophilic polymers is 2.5 - 40% by weight calculated by the total weight of the formulation. • «• '.2' 25 4. An aqueous foam according to any one of claims 1 - 3, characterized in that the long-chain aliphatic C6-C22 fatty acids are selected from the group of palmitic acid, dodecanoic acid and stearic acid and their alkali, alkaline earth and ammonium salts thereof and the amount of compounds is 2.5 - 20% by weight calculated by the weight of the total formulation. 5. Ancillary foam according to claim 4, characterized in that the long-chain aliphatic C6-C22 - fatty acid content is 2.5 - 12.5% by weight calculated by the weight of the total formulation. 16 110052 6. A bale foam according to any one of claims 1 to 5, characterized in that the amount of the other auxiliaries is 0 to 15% by weight calculated by the weight of the total formulation. 5 7. Premixtures for the production of rectifying foams, characterized in that they consist of the following: a) a rectifying killer, b) hydrophilic polymers having an average molar mass of 2,000 - 60,000, selected from the group long chain polyurethanes, polyesters, polyester polyols, polystyrenes, polybutadienes, maleic acid polymers, whose polymer chain was modified at each time with carboxylic acid or amino groups; c) long chain, C6-C22 aliphatic fatty acids, e.g. d) selectable other adjuvants selected from the group of dyes, emulsifiers, solvents, preservatives, lids and pastes. Preparation of premixes according to claim 7, characterized in that the correcting agent is dissolved, dispersed, emulsified or suspended in a premix solution consisting of polymer, grease; · 25 acid and selectable by other aids. T 9. A process for the preparation of rectifying foam ··· from premix according to claim 7, characterized in that 0 - 80% water is added to the premixes and then prepared by stirring, shaking or in situ by means of propellant under use. »