SK280990B6 - Rodenticidal soft foams - Google Patents

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 2,000 to 60,000 (determined by means of gel permeation chromatography (GPC) from the series consisting of ling-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

Technical field

The invention relates to rodenticidal foams based on hydrophilic polymers.

BACKGROUND OF THE INVENTION

Indandione derivatives and 4-hydroxycoumarins are known to reduce the level of prothrombin in the blood. They cause high mortality in rodents due to internal bleeding. Therefore, they are used as rodenticidal agents (see, for example, DE-OS2506769, JP-PS48023942 and CH-PS481580).

In many cases, the rodenticidal active ingredient is mixed with various rodent-consuming agents such as cereal, flour, sugar and oil, optionally with inorganic excipients such as talc, chalk and titanium dioxide powder.

However, according to this method, the baits produced have the disadvantage that their attraction to rodents decreases strongly over time. The loss of attractiveness is caused by chemical degradation of the active substance or ingestible substances.

It is known that the attraction of the bait is achieved by coating the active ingredient with polymers such as ethylcellulose, ethoxylated polyarylphenols, polyoxyethylene glycols, hydroxypropylmethylcellulose and the like (see, for example, EP0317260, DE2647722 and CA107963). This method has the disadvantage that only the active substance is protected from aging, but not the substances consumed by rodents. Therefore, this method is unsuitable for gaining the attraction of the bait.

It is further known that the attraction of rodent bait is achieved by using chemically stable, hydrogenated oils and fats as carrier material (see, for example, JP-OS62030161). As a rule, however, they are completely hydrogenated or poorly bonded with poor oils and fats for rodents of low attraction.

For these reasons, attempts have been made to find rodenticidal foams which do not contain oxidizing sensitive compositions. Such rodenticidal foams generally contain aliphatic acids such as stearic acid, neutral anionic or cationic emulsifiers, waxes of all kinds, water and active ingredients (see, for example, GB-PS1053088, GB-PS1274442 and SU-PS363474).

However, these rodenticidal foams have the disadvantage that they have poor storage stability and, in particular, poor stability against cold or moisture. Over time, it becomes a compact, highly viscous mass and loses its biological effect.

Therefore, stable rodenticide rigid foams based on polystyrene, polyacrylates and two-component polyisocyanates have been sought for storage (see, for example, JP-OS55085501, FR-PS2676888 and US-PS4190734).

These rodenticide hard foams are characterized by storage stability, moisture stability and cold stability. However, they have the disadvantage that their production is expensive. In many cases, their biological effect is negligible.

SUMMARY OF THE INVENTION

The invention therefore solves the object of finding a novel rodenticide foam system which is characterized by storage stability, wet and cold stability, easy manufacture and application as well as good biological effect.

Accordingly, the present invention provides a rodenticidal soft foam comprising the following components:

(a) a rodenticidal active substance,

(b) a hydrophilic polymer with an average molecular weight of 2000 to 60000 (determined by gel permeation chromatography (GPC)) from the group of polyurethanes, polyesters, polyester polyols, polystyrenes, polybutadienes and long-chain maleic acid polymers which are modified in the polymer chain by carboxylic acid groups; amino groups,

(c) a long-chain aliphatic fatty acid having 6 to 22 carbon atoms, such as palmitic acid, dodecanoic acid and stearic acid, or their alkali metal, alkaline earth metal and ammonium salts, and

(d) where appropriate, other adjuvants from the group of dyes, emulsifiers, solvents, preservatives, attractants and baits.

The polymers used according to the invention are described, for example, in H. Kittel, Lehrbuch der Lacke und Beschichtungen, Vol. IV, p. 76 to 306, publ. W. A. Colomb (1986) or the same publication, 1976, Volume IV, p. 328 to 358 as binders for varnishes.

The polymers used according to the present invention are physically dried by binder means, for example those whose binders are based on reacted linear polyurethanes of (i) polyester polyol, (ii) chain extender, (iii) diisocyanate and (iv) hydroxycarboxylic acid.

Suitable polyester polyols (i) for the preparation of such polyurethanes are, for example, adipic acid, alkanediols and polyester diols in the molecular weight range of 600 to 3000. The alkanedioles are, for example, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol or mixtures of such glycols. Suitable chain extenders (ii) are, for example, diols of the type used for the production of polyester diols, as well as diamines such as hexamethylenediamine or isophorone diamine. Suitable diisocyanates (iii) are, for example, 4,4-diisocyanatodiphenylmethane, isophorone diisocyanate or hexamethylene diisocyanate. Polyurethanes are prepared in a known manner by reaction of the starting materials, maintaining a ratio of isocyanate group equivalents to isocyanate group reactive groups of about 0.9: 1 to 1.1: L

Oxidative drying binders are also useful in the present invention. As such, binders based on polybutadiene, styrene and maleic anhydride are described in EP-OS0170184 and EP-OS0270705.

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 preparations in a concentration of 2.5 to 40% by weight, preferably 2.5 to 10% by weight, based on the total weight of the preparation.

In principle, all rodenticidal active substances are suitable for the production of the rodenticidal foam according to the invention. In particular, anticoagulants such as 4-hydroxycoumarin (1-phenyl-2-acetyl) -3-ethyl-4-hydroxycoumarin ("warfarin"), 3- (α-acetonyl-4-chlorobenzyl) derivatives may be mentioned in this context. -4-hydroxycoumarin ("Coumachlor"), [3- (T-hydroxy-S'-coumarinyl) -5-phenyl-N'-bromo-1'-biphenyl)] - propan-1-ol ("Bromadiolone"), 3- (3'-p-diphenyl-1 ', 2', 3 ', 4'-tetrahydro-1'-naphthyl) -4-hydroxycoumarin ("Difenacoum"), Brodifacoum, Flocoumafen and 3- (1', 2 ', 3' 4'-tetrahydro-1'-naphthyl) -4-hydroxycoumarin ("Coumatetralyl"); indanone dione derivatives such as 1,1-diphenyl-2-acetylindan-1,3-dione ("Diphacinone"); and (1 ' p-chlorophenyl-phenyl-T) 2

SK 280990-6

-2-acetyl-indan-1,3-dione - ("Chlorodiphacinone") and hydroxy-4-benzothiopyranones such as Difethialone.

Other anticoagulants suitable for making the baits of the present invention include the following 2-azacycloalkylmethyl substituted benzhydryl ketones and -carbinols: 1-phenyl-3- (2-piperidyl) -1- (p-tolyl) -2-propanone 1,3,3-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; - (p-cumenes) -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, 3,3-diphenyl-1- (2-piperidyl) -2-butanone, α- (α-methyl-α-phenylbenzyl) -2-piperidinethanol, α- (α-ethyl-α-phenylbenzyl) -2 -pyrrolidinethanol, (2,5-dimethyl-α-phenylbenzyl) -2-piperidinethanol and α- (diphenylmethyl) -2- (hexahydro-1H-azepine) -ethanol and salts thereof, as described in DT-OS2417783 as well as i 4 '- (f fluorophenyl) -2- (2-pyrrolidinyl) acetophenone, 4'-phenyl-2- (5,5-dimethyl-2-pyrrolidinyl) acetophenone, 4 '- [p- (trifluoromethyl) phenyl] -2- (2 -piperidyl) acetophenone, 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) 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-azepinyl) -4 '- (transstyryl) acetophenone, 4' - (m-methoxyphenylvinylene) -2- (2-pyrrolidinyl) acetophenone, 2- (2-piperidyl) -4 '- [(p-Methylthiophenylvinylene) acetophenone, 4' - (3-phenoxypropoxy) -2- (2-piperidyl) acetophenone, 4 '- (4-phenylbutyl) -2- (2-piperidyl) - acetophenone, 4 '- (α, α-dimethylbenzyl) -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- (pf) enoxyphenyl) -2-pyrrolidinethanol, α- [4- (4-bromophenoxy) -phenyl] -6-methyl-2-piperidinethanol, α- (p-phenethyl) -phenyl-2-pyrrolidinethanol, α-bisphenyl-2-hexahydro -1H-azepinethanol, α- [3- (4-phenoxybutoxy) phenyl] -2-piperidinoethanol and α- (4-benzyl) phenyl-2-piperidinoethanol and salts thereof, which are described in DT-OS2418480.

Of course, current poisons can also be used to produce new rodenticidal soft foams.

The following noble metal salts can also be used as anticoagulants: dineodymium dihydroxybenzene disulfonate (Acta Physiol. Acad. Sci. Hungar., 24, 373), dineodymium-3-sulfonato-pyridine-4-carboxylate and tris (4-aminobenzenesulfonate) cerium.

The amount of anticoagulant may be in the range of 0.01 to 5% (% by weight, based on the total weight of the bait), with a preferred amount being in the range of 0.01 to 1.0%.

The baits of the present invention may, of course, be mixed with other active ingredients such as cholecalciferol and calciferol in an amount of 0.001 to 1.0%.

Of course, the soft foams of the present invention may be provided with adjuvants from the group of lures, fragrances, flavorings, paraffin derivatives and hydrogenated fats and oils.

Attractants include, but are not limited to, natural oils such as soybean oil, rapeseed oil, corn oil or olive oil, oleic acid esters such as glycerides and sorbic esters, and mixtures thereof. Sweetening agents such as sugar, maltose, sucrose or molasses may also be mentioned.

Rodenticide systems so produced are masterbatches. As a rule, they must be diluted with water in an amount of 0 to 80% before application.

The production of the soft foam according to the present invention can be carried out by known methods by stirring or shaking. Another possibility is to produce in situ using blowing agents during application.

Blowing agents for making the compositions of the present invention include carbon dioxide, nitrous oxide, lower alkanes such as propane, n-butane or isobutane, halogens containing lower alkanes, as well as low boiling ethers such as dimethyl ether, as well as mixtures of said blowing agents.

The foam of the present invention has excellent adhesion to rodent fur. It is dimensionally stable for several weeks and has good activity on rodents. It is suitable for combating rodents such as rats, mice and the like, also on wet habitats (e.g. canals, river banks and the like).

Without limiting the scope of the invention, the following Examples illustrate the invention in more detail.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

1. Coumatetrolyl 0,07%

2. Stearic acid 7,50%

3. triethanolamine 4,16%

4. Polywachs 1550 2.50%

5. NP10 (non-ionic emulsifier) 1.00%

6. glycerol

7. crystal sugar

8. Bayhydrol VP-LS 2069

9. Tap water approx. 54,27%

10. Isobutane _____________________ 7.50% ________

100.00% = 250 g _c

This preparation was filled into aluminum containers (1000 mL). Bayhydrol VP-LS 2069 is an aqueous polyester polyurethane from Bayer AG, Leverkusen. It consists of fatty acids soybean oil, trimethylolpropane, hexanediol, adipic acid, isophthalic acid, dimethylolpropionic acid, hexamethyldiisocyanate, isophorone diisocyanate, neopentyl glycol and dimethylethanolamine.

This preparation results in soft foams which are characterized by long-term shelf life and stability in the cold. The soft foams thus produced are stable for several weeks at -4 ° C and have excellent biological activity against rodents. They are well suited for combating mice, rats and the like.

Determination of biological effect

Wild tribe Rattus norvegieus

Animals are taken from the wild and are kept in a laboratory. The weight of test animals used in grams is: 230/285/234/342/325.

Experimental method:

The experiment is conducted with rats (Rattus norvegieus) wild-type (number: 5) in a corresponding establishment according to Guideline 9-32BBA. This device consists of three consecutive chambers. Each chamber has a base surface

SK 280990 Β6 m ² . The individual chambers are connected to each other by hiding holes (batteries). One chamber, which serves rats as a "living", contains a nest with hay and pulp to build a stash. The center chamber remains empty. Food and test composition are placed in the third chamber. Drinking water is available as desired throughout the experiment. After taking the rats from the grower they can get used to the new environment for 3 days. After this treatment, rats are pre-fed for one day with Altromine O (standard diet).

A foam coating (diameter: 40 x 60 cm, height 1 cm) is then applied in the third inlet chamber. Feeding is further carried out with Altromine O and the fed amounts are determined daily by back weighing.

The results are shown in Tables 1 and 2 below.

Table 1

Reaction of rats to rodenticidal foam coating between living and feed area

Beginning of the experiment

A semicircular foam carpet (diameter 60 x 40 cm, height 1 cm) is applied in the feed chamber prior to entry.

1 day

The rats created two circular openings in the foam through which they can overcome the foam by jumping to reach feed. Some foam flakes lie in a continuous chamber. Rats have clean fur.

Day 2

The foam carpet is restored.

Day 2

The rats created a passage through the foam through which they could reach the feed without touching the foam. Some foam flakes lie in a continuous chamber. Rats have clean fur.

Day 3

Same result as Day 2.

Day 4

The first rat is dead, otherwise the same result as the previous day.

Day 5

The second rat is dead. Animals have coordination problems. The foam carpet is further overcome by the remaining rats.

Day 6

The third rat is dead and one animal has symptoms of poisoning.

Day 7

The fourth rat is dead. The last living animal has no poisoning symptoms.

8. -11.day

On day 10, symptoms of poisoning show in the last rat and day 11 is dead.

Table 2

Food intake during 11 days of experiment (n = 5 rats)

Experiment Day i. kŕnne aleato 2 Dead individuals (búmJ 1 31.6 22.4 0 2 71.1 44.0 0 3 71.7 32.7 0 4 30.9 21.4 1 5 0.0 2.9 2 6 2S 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 animals had to run through the foam carpet between the living area and the feed area in order to obtain feed. The animals formed a narrow path through the foam. The flakes of foam that remained hanging on the hair were either dropped in the middle zone or removed by cleaning the hair.

The time to sacrifice of animals (4 to 7 days) corresponds to the experience of multiple dose Anticoagulanz Coumatetralyl.

One animal showed symptoms of poisoning on day 9 and died on day 11. It is to be assumed that this animal in the first nights then overcame the foam carpet, when the other animals of the group had already established a path through which the foam carpet was overcome without contamination.

Example 2

0,07%

7.50%

4.16%

2.50%

1. Coumatetrolyl

2. stearic acid

3. trictanolamine

Polywachs 1550

5. NP10 (non-ionic emulsifier) 1.00%

6. glycerol

7. crystal sugar

8. Bayhydrol VP-LS 2845

9. tap water

10. Isobutane / Propane (1: 1)

8,00%

5,00%

10.00% approx. 54,27%

7,50%

100.00% = 250 g

This preparation was filled into aluminum containers (1000 mL). Bayhydrol VP-LS2845 is an aqueous polyesterpolyurethane solution from Bayer AG, Leverkusen. The polyurethane component consists of soybean oil fatty acids, trimethylolpropane, hexanediol, adipic acid, isophthalic acid, dimethylolpropionic acid, isophorone diisocyanate and dimethylethanolamine. This preparation results in soft foams which are characterized by long-term shelf life and stability in the cold. The soft foams thus produced are stable for several weeks at 14 ° C and have an excellent biological effect.

Example 3

1. Coumatetrolyl

2. stearic acid

3. triethanolamine

Polywachs 1550

5. NP10 (non-ionic emulsifier) 1.00%

6. glycerol

7. crystal sugar

8. Bayhydrol B-130

9. tap water

10. isobutane

0,07%

7,50%

4.16%

2,50%

8,00%

5,00%

10.00% approx. 54,27%

7,50%

SK 280990-6

Bayhydrol B130 is an aqueous polymer solution from Bayer AG, Leverkusen. The polymer components consist of maleic anhydride, styrene, polybutadiene and ammonia.

This preparation results in soft foams which are characterized by long-term shelf life and stability in the cold. The soft foams thus produced are stable for several weeks at 4 ° C and have excellent biological activity against rodents such as mice and rats.

Claims (2)

PATENT CLAIMS 1. Rodenticidal soft foam consisting of a rodenticidal active substance, a hydrophilic polymer having an average molecular weight of 2000 to 60,000, as determined by gel permeation chromatography, of the group of polyurethanes, polyesters, polyester polyols, polystyrenes, polybutadienes and long-chain maleic polymers, they are modified in the polymer chain by carboxylic acid or amino groups and an aliphatic fatty acid having 6 to 22 carbon atoms. Rodenticidal soft foam according to claim 1, characterized in that it contains further auxiliaries from the group of dyes, emulsifiers, solvents, preservatives, attractants and bait substances.